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1.1 Chemistry & Measurements
Scientists throughout the world use the International System of Units, abbreviated SI, for their
measurements. There are seven base units in the SI system.
Measurements can involve very large or very small units that do not correspond with the base SI
units. SI units are conveniently modified by a series of prefixes that represent multiples of the
base units. Thus 1/1000th of a meter (or 0.001m) becomes 1 millimeter or simply 1 mm.
Because the numbers chemists use are often very small or very large, it is convenient to express
these numbers in scientific notation. Notice also that all measurements contain both a number
and the unit of measure.
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meanings. Mass is the amount of matter in an object, while weight is a measure of the pull of
gravity on an object.
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An understanding of the three temperature scales will help you make temperature conversions
without blindly applying a formula. Look at the number of degrees that separate the freezing
point of water and the boiling point of water on the Fahrenheit scale: There are 180 degrees.
This same temperature interval is separated by 100C and 100 K. Thus, one F is 100/180 or
5/9 the size of a kelvin or C. That is, there are fewer Celsius degrees than Fahrenheit degrees in
the same range because Celsius degrees are "fatter". The Fahrenheit scale is offset from the
Celsius scale by 32F. These facts lead to the following conversion equations:
The Kelvin scale is offset from the Celsius scale by 273.15. Thus,
Volume, the amount of space occupied by an object, is measured in SI units by the cubic
meter, abbreviated m3. Smaller, more convenient measures of volume are frequently used.
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1 dm3 = 1 liter (1 L)
1 cm3 = 1 milliliter (1 mL)
Measuring liquid volume is a common laboratory task. Some of the specialized glassware used in
chemistry labs is shown below. Which one is the buret?
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1.6 Derived Units: Measuring Density
Density is an intensive physical property that relates the mass of an object to its volume.
Notice the wide range of densities of common substances listed in the table below.
The volume of many substances changes with temperature, so densities, too, are temperature
dependent.
Density provides a useful link in the laboratory between the mass of a substance and its volume.
It is sometimes simpler to use volumetric glassware to measure a particular volume of a
substance, and then to convert that volume to mass.
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ELEMENTS and COMPOUNDS
MIXTURES and their separation
CHEMICAL REACTIONS and EQUATIONS
KEYWORDS ... atom ... chemical change ... chromatography ... compound ... covalency ...
distillation (simple/fractional) ... element ... equations - (word, picture, symbol, quizzes) ...
formula ... impure/pure ... ionic equations ... ionic valency ... magnet ... mixture ...
molecule ... physical change ... products ... reactants ... separating mixtures ... chemical
symbols - (elements, formula, in equations) ... state symbols ... valency ... working out
formulae ...
ELEMENT
and symbols
H I Na Al Fe C
Ag U?
COMPOUND
and FORMULA
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CH4
MIXTURE
PURE
PURE means that only one substance present in the material and can
be an element or compound.
A simple physical test for purity and helping identify a compound is to
measure the boiling point of a liquid. Every pure substance melts and
boils at a fixed temperature.
o If a liquid is pure it may boil at a constant temperature (boiling
point).
o An impure liquid could boil higher or lower than the expected
boiling point and over a range of temperature.
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o
o
IMPURE
PURIFICATION
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METHODS of SEPARATING MIXTURES
Simple Distillation
Fractional Distillation
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points in a huge fractionating column. At the top are the very low boiling fuel gases like
butane and at the bottom are the high boiling big molecules of waxes and tar.
Paper Chromatography
This method of separation is used to see what coloured materials
make up eg a food dye analysis.
It is possible to analyse colourless mixture if the components can be made coloured eg protein can be
broken down into amino acids and coloured purple by a chemical reagent called ninhydrin and
many colourless organic molecules fluoresce when ultra-violet light is shone on them.
FILTRATION
EVAPORATION
CRYSTALLISATION
This can be used to separate iron from a mixture with sulphur (see below). It is
used in recycling to recover iron and steel from domestic waster ie the 'rubbish'
is on a conveyer belt that passes a powerful magnet which pluck's out magnetic
materials.
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PHYSICAL CHANGES
These are changes which do not lead to new substances being
formed. Only the physical state of the material changes. The
substance retains exactly the same chemical composition. Examples
...
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THE CONSTRUCTION OF CHEMICAL EQUATIONS
"How to write and understand chemical equations"
For any reaction, what you start with are called the reactants, and what you form are called the products.
o So any chemical equation shows in some way the overall chemical change of ...
o REACTANTS ==> PRODUCTS, which can be written in words or symbols/formulae.
It is most important you read about formula in an earlier section of this page.
empirical formula and molecular formula are dealt with on another page.
In the equations outlined below several things have been deliberately simplified. This is to allow the 'starter' chemistry
student to concentrate on understanding formulae and balancing chemical equations. Some teachers may disagree with
this approach BUT my simplifications are:
o the word 'molecule' is sometimes loosely used to mean a 'formula',
o the real 3D shape of the 'molecule' and the 'relative size' of the different element atoms is ignored
o if the compound is ionic, the ion structure and charge is ignored, its just treated as a formula
A molecular formula gives the types and the count of atoms for each element in a compound. An example
of a molecular formula is ethane, C2H6. Here the formula indicates carbon and hydrogen are combined in
ethane. The subscripts tell us that there are 2 carbon atoms and 6 hydrogen atoms in a formula unit.
The structural formula shows the atoms in a formula unit and the bonds between atoms as lines. Single
bonds are one line, Double bonds are two lines. Triple bonds are three lines. The Lewis dot structure shows
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the number of valence electrons and types of bonds in the molecule.
Lewis dot structure
Electron pairs that are shared are physically between the symbols for the
atoms. Electron pairs that are unshared are called lone pairs. Lone pairs are
not between atom symbols.
1a
or the formula FeS means one atom of iron is chemically combined with 1 atom of sulphur to form the
compound called iron sulphide
or the formula NaOH means 1 atom of sodium is combined with 1 atom of oxygen and 1 atom of
hydrogen to form the compound called sodium hydroxide
or the formula HCl means 1 atom of hydrogen is combined with 1 atom of chlorine to form 1 molecule of
the compound called hydrochloric acid
or the formula NaCl means 1 atom of sodium are combined with 1 atom chlorine to form the
compound called sodium chloride
or the formula H2O means 2 atoms of hydrogen are chemically combined with 1 atom of oxygen to
form the compound called water.
or S 1
2a
3a
(see example 2)
or 2HCl means two separate molecules of the compound called hydrochloric acid
or the formula MgCl2 means 1 formula of the compound called magnesium chloride, made of
one atom of magnesium and two atoms of chlorine.
atoms
or the formula H2 means 1 molecule of the element called hydrogen made up of two joined hydrogen
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4a
or the formula CuCO3 means one formula of the compound called copper carbonate, made up
of one atom of copper is combined with one atom of carbon and three atoms of oxygen to form the compound
copper carbonate
or the formula H2SO4 means one formula of the compound called sulphuric acid, which is
made up of two atoms of hydrogen, one atom of sulphur and four atoms of oxygen
or the formula CuSO4 means one formula of the compound called copper sulphate which is
made up of one atom of copper, one atom of sulphur and four atoms of oxygen
H2O (example 2)
or the formula CO2 means one molecule of the compound called carbon dioxide which is a
chemical combination of one atom of carbon and two atoms of oxygen.
or the formula CH4 means one molecule of the compound called methane which is made of one
atom of carbon combined with four atoms of hydrogen
or 2O2 means two separate molecules of the element called oxygen, and each oxygen
molecule consists of two atoms of oxygen
CO2 (see also example 4)
5a
also example 2)
or 2H2O means two separate molecules of the compound called water (see
6a
or the formula Mg(OH)2 is the compound magnesium hydroxide made up of one magnesium, two
oxygen and two hydrogen atoms BUT the OH is a particular combination called hydroxide within a compound, so it
is best to think of this compound as a combination of an Mg and two OH's, hence the use of the ( ).
or 2HNO3 means two separate molecules of the compound nitric acid, each
molecule is made up of one hydrogen atom, one nitrogen atom and three oxygen atoms.
10
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nitrate is a particular combination of atoms within a compound and hence the use of ( ) again.
7a
2 and 5)
or 2H2O meaning two molecules of the compound water (see also examples
or the formula Al2O3 means one formula of the compound called aluminium oxide, made up
of two atoms of aluminium Al and three atoms of oxygen O
1b
2b
3b
4b
copper
+ sulphuric ==> copper + water + carbon
carbonate
acid
sulphate
dioxide
5b
6b
7b
11
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Chemical picture equations
There are three main points to writing and balancing equations
1c
on average one atom of iron chemically combines with one atom of iron forming one molecule of iron
sulphide
atom balancing, sum left = sum right: 1 Fe + 1 S = (1 Fe + 1S)
two elements chemically combining to form a new compound
the reactants are one molecule of sodium hydroxide and one molecule of hydrochloric acid
the products are one molecule of sodium chloride and one molecule of water
all chemicals involved are compounds
atom balancing, sum left = right: ( 1 Na + 1 O + 1 H) + (1 H +1 Cl) = (1 Na + 1 Cl) + (2 H's + 1 O)
the reactants are one formula of copper carbonate and one molecule of sulphuric acid
the products are one formula of copper sulphate, one molecule of water and one molecule of carbon
dioxide
all molecules are compounds in this reaction
2c
3c
4c
12
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one formula of magnesium hydroxide reacts with two molecules of nitric acid to form one formula of
magnesium nitrate and two molecules of water (all compounds)
atom balancing, sum left = sum right: (1 Mg + 2O's + 2 H's) + (1 H + 1 N + 3O's) + (1 H + 1 N +
3O's) = (1 Mg + 2 N's + 6 O's) + (2 H's + 1 O) + (2 H's + 1 O)
5c
6c
7c
one formula of aluminium oxide reacts with three molecules of sulphuric acid
to form one formula of aluminium sulphate and three molecules of water
note the first use of numbers (3) for the sulphuric acid and water!
so picture three of them in your head, otherwise the picture gets a bit big!
atom balancing, sum left = sum right: (2 Al's + 3 O's) + 3 x (2 H's + 1 S + 4 O's) = (2 Al's + 3 S's + 12
O's) + 3 x (2 H's + 1 O)
2d
3d
13
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4d
5d
6d
7d
atom balancing, sum left = sum right: (1 C + 4 H's) + 2 x (2 O's) = (1 C + 2 O's) + 2 x (2 H's + 1 O)
atom balancing, sum left = sum right: (1 Mg + 2O's + 2 H's) + 2 x (1 H + 1 N + 3 O's) = (1 Mg + 2 N's
+ 6 O's) + 2 x (2 H's + 1 O)
atom balancing, sum left = sum right: (2 Al's + 3 O's) + 3 x (2 H's + 1 S + 4 O's) = (2 Al's + 3 S's + 12
O's) + 3 x (2 H's + 1 O)
NOTE 1:
means a reversible reaction, it can be made to go the 'other way' if the conditions are
changed. Example:
o nitrogen + hydrogen
ammonia
o N2(g) + 3H2(g)
2NH3(g)
o balancing: 2 nitrogen's and 6 hydrogen's on both sides of equation
Note 2 on the state symbols X(?) of reactants or products in equations
(2nd draft) The valency of an atom or group of atoms is its numerical combining power with other atoms or groups
of atoms.
The theory behind this, is all about stable electron structures!
o The combining power or valency is related to the number of outer electrons.
o You need to consult the page on "Bonding" to get the electronic background.
A group of atoms, which is part of a formula, with a definite composition, is sometimes referred to as a radical.
In the case of ions, the charge on the ion is its valency or combining power (list below).
To work out a formula by combining 'A' with 'B' the rule is:
o number of 'A' x valency of 'A' = number of 'B' x valency of 'B',
However it is easier perhaps? to grasp with ionic compound formulae.
o In the electrically balanced stable formula, the total positive ionic charge must equal the total negative ionic
charge. Example:
o Aluminium oxide consists of aluminium ions Al3+ and oxide ions O2o number of Al3+ x charge on Al3+ = number of O2- x charge on O2o the simplest numbers are 2 of Al3+ x 3 = 3 of O2- x 2 (total 6+ balances total 6-)
o so the simplest whole number formula for aluminum oxide is Al 2O3
14
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Examples of ionic combining power of ions (left, valency = numerical
charge value)
Examples of covalent combining power of atoms (valencies below)
Hydrogen H (1)
Chlorine Cl and other halogens (1)
Oxygen O and sulphur S (2)
Boron B and aluminium Al (3)
Nitrogen (3, 4, 5)
Carbon C and silicon Si (4)
Phosphorus (P 3,5)
'B' (valency)
deduced formula
1 of carbon C (4)
1 x 4 = 4 x 1 = CH4
1 of nitrogen (3)
1 x 3 = 3 x 1 = NCl3
1 of carbon C (4)
1 x 4 = 2 x 2 = CO2
2 of Na (1)
1 of Mg
2+
1 of Fe
3+
2 of Fe
3+
(2)
(3)
(3)
'B' (charge=valency)
2 x 1 = 1 x 2 = Na2O
1 x 2 = 2 x 1 = MgCl2
1 x 3 = 3 x 1 = FeF3
balances 1 of O (2)
balances 2 of Cl (1)
balances 3 of F (1)
balances 3 of
deduced formula
2-
SO42-
(2)
2 x 3 = 3 x 2 = Fe2(SO4)3
15
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The Structure of Atoms
Atoms are the smallest particles of matter whose properties we study in Chemistry. However from experiments
done in the late 19th and early 20th century it was deduced that atoms were made up of three fundamental
sub-atomic particles (listed below)
A Portrait of an Atom
The diagram below gives some idea on the structure of an atom, it also includes some important
definitions and notation used to describe atomic structure.
The atomic number (Z) is also known as the proton number of the nucleus of a particular element.
It is the proton number that determines the specific identity of a particular element and its electron
structure.
The mass number (A) is also known as the nucleon number (N), that is the number of particles in
the nucleus of a particular isotope.
Protons and neutrons are the nucleons present in the positive nucleus and the negative
electrons are held by the positive nucleus in 'orbits' called energy levels or shells.
In a neutral atom the number of protons equals the number of electrons.
ISOTOPES
Isotopes are atoms of the same element with different numbers of neutrons. This gives each
isotope of the element a different mass or nucleon number but being the same element they have
the same atomic or proton number.
There are small physical differences between the isotopes eg the heavier isotope has a greater
density or boiling point.
However, because they have the same number of protons they have the same electronic structure and
identical chemically. Examples are illustrated below.
Do NOT assume the word isotope means it is radioactive, this depends on the stability of the nucleus
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i.e. unstable atoms (radioactive) might be referred to as radioisotopes. Many isotopes are
stable and NOT radioactive i.e. most of the atoms that make up you and the world around you!
,
and
are the three isotopes of hydrogen with mass numbers of 1, 2 and 3, with 0,
1 and 2 neutrons respectively, but all have 1 proton. Hydrogen-1 is the most common, there is a trace
of hydrogen-2 naturally but hydrogen-3 is very unstable and is used in atomic fusion weapons.
and
are the two isotopes of helium with mass numbers of 3 and 4, with 1 and 2
neutrons respectively but both have 2 protons. Helium-3 is formed in the Sun by the initial nuclear
fusion process. Helium-4 is also formed in the Sun and as a product of radioactive alpha decay of an
unstable nucleus. An alpha particle is a helium nucleus, it picks up two electrons and becomes the
atoms of the gas helium.
and
are the two isotopes of sodium with mass numbers of 23 and 24, with 12
and 13 neutrons respectively but both have 11 protons. Sodium-23 is quite stable e.g. in common salt
(NaCl, sodium chloride) but sodium-24 is a radio-isotope and is a gamma emitter used in medicine as a
radioactive tracer e.g. to examine organs and the blood system.
The relative atomic mass of an element is the average mass of all the isotopes present compared to
1/12th of the mass of carbon-12 atom (12C = 12.00000 ie the standard).
The electrons are arranged in energy levels or shells around the nucleus and with
increasing distance from the nucleus.
Each electron in an atom is in a particular energy level (or shell) and the electrons
must occupy the lowest available energy level (or shell) available nearest the nucleus.
When the level is full, the next electron(s) go into the next highest level (shell) available.
There are rules about the maximum number of electrons allowed in each shell and you
have to be able to work out the arrangements for the first 20 elements (see the Periodic
Table diagrams further down).
st
o The 1 shell has a maximum of 2 electrons
o The 2nd shell has a maximum of 8 electrons
o The 3rd shell has a maximum of 8 electrons
th
th
th
o The 19 and 20 electrons go into the 4 shell (limit of GCSE knowledge)
If you know the atomic (proton) number, you know it equals the number of
electrons in a neutral atom, you then apply the rules to work out the electron
arrangement (configuration).
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On Period 1
On Period 2
On Period 3
On Period 4
(2 elements only)
....
....
....
(3 of the 8 elements)
(3 of the 8 elements)
===> Kr [2.8.18.8],
Below are the electron arrangements for elements 1 to 20 set out in Periodic Table format
(Hydrogen and The Transition metals etc. have been omitted). When you move down to the next
period you start to fill in the next shell according to the maximum electrons in a shell rule (see
previous section)
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o
o
o
The first element in a period has one outer electron (eg sodium Na 2.8.1), and the last
element has a full outer shell (eg argon Ar 2.8.8)
Apart from hydrogen (H, 1) and helium (He, 2) the last electron number is the group
number.
and the number of shells used is equal to the Period Number.
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Structure, Bonding and properties
1. Why do atoms bond together?
Some atoms are very reluctant to combine with other atoms and exist in the air around us as single
atoms. These are the Noble Gases and have very stable electron arrangements eg 2, 2.8 and
2.8.8 because their outer shells are full. The first three are shown in the diagrams below and explains why Noble
Gases are so reluctant to form compounds with other elements.
All other atoms therefore, bond together to become electronically more stable, that is to
become like Noble Gases in electron arrangement. Bonding produces new substances and usually involves
only the 'outer shell' or 'valency' electrons
The phrase CHEMICAL BOND refers to the strong electrical force of attraction between the atoms or ions in the
structure. The combining power of an atom is sometimes referred to as its valency and its value is linked to the number
of outer electrons of the original uncombined atom
COVALENT BONDING - sharing electrons to form molecules with covalent bonds, the bond is usually formed
between two non-metallic elements in a molecule.
METALLIC BONDING The crystal lattice of metals consists of ions NOT atoms surrounded by a 'sea of
electrons' forming giant lattice. These free or 'delocalised' electrons are the 'electronic glue' holding the particles
together. There is a strong electrical force of attraction between these mobile electrons (-) and the 'immobile'
positive metal ions (+) and this is the metallic bond.
The atom losing electrons forms a positive ion (cation) and is usually a metal.
The atom gaining electrons forms a negative ion (anion) and is usually a non-metallic element.
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NOBLE GASES are very reluctant to share, gain or lose electrons to form a chemical bond. For most other elements
the types of bonding and the resulting properties of the elements or compounds are described in detail below. In all the
electronic diagrams ONLY the outer electrons are shown.
2. Covalent Bonding
Covalent bonds are formed by atoms sharing electrons to form molecules. This type of bond usually formed
between two non-metallic elements. The molecules might be that of an element ie one type of atom only OR from
different elements chemically combined to form a compound.
The covalent bonding is caused by the mutual electrical attraction between the two positive nuclei of the two atoms of the
bond, and the electrons between them.
One single covalent bond is a sharing of 1 pair of electrons, two pairs of shared electrons between the same two
atoms gives a double bond and it is possible for two atoms to share 3 pairs of electrons and give a triple bond.
Example 1: 2 hydrogen atoms (1) form the molecule of the element hydrogen H2
and
combine to form
where both atoms have a pseudo helium structure of 2 outer
electrons around each atom's nucleus. Any covalent bond is formed from the mutual attraction of two positive
nuclei and negative electrons between them.
Example 2: 2 chlorine atoms (2.8.7) form the molecule of the element chlorine Cl2
and
combine to form
where both atoms have a pseudo argon structure of 8
outer electrons around each atom. All the other halogens would be similar eg F2, Br2 and I2 etc. Valency of halogens is 1
here.
Example 3: 1 atom of hydrogen (1) combines with 1 atom of chlorine (2.8.7) to form the molecule of the compound
hydrogen chloride HCl
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and
combine to form
where hydrogen is electronically like helium and chlorine like
argon. All the other hydrogen halides will be similar eg HF, HBr and HI etc.
Example 4: 2 atoms of hydrogen (1) combine with 1 atom of oxygen (2.6) to form the molecule of the compound we
call water H2O
and
and
combine to form
helium and the oxygen atom becomes like neon. The molecule can be shown as
with two hydrogen - oxygen
single covalent bonds. Hydrogen sulphide will be similar, since sulphur (2.8.6) is in the same Group 6 as oxygen. Valency
of oxygen and sulphur is 2 here.
Example 5: 3 atoms of hydrogen (1) combine with 1 atom of nitrogen (2.5) to form the molecule of the compound
we call ammonia NH3
three of
and one
combine to form
like helium and the nitrogen atom becomes like neon. The molecule can be shown as
hydrogen single covalent bonds (
Example 6: 4 atoms of hydrogen (1) combine with 1 atom of carbon (2.4) to form the molecule of the compound we
call methane CH4
four of
and one of
combine to form
like helium and the nitrogen atom becomes like neon. The molecule can be shown as
with four carbon hydrogen single covalent bonds. SiH4 will be similar because silicon (2.8.4) is in the same group as carbon.
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All the bonds in the above examples are single covalent bonds. Below are three examples 7-9, where there is a
double bond in the molecule, in order that the atoms have stable Noble Gas outer electron arrangements around each
atom. Carbon has a valency of 4.
Example 7:
Two atoms of oxygen (2.6) combine to form the molecules of the element oxygen O2.
Example 8:
. Oxygen valency 2.
One atom of carbon (2.4) combines with two atoms of oxygen (2.6) to
Example 9:
Two atoms of carbon (2.4) combine with four atoms of hydrogen (1) to
Examples 10-13: The scribbles below illustrate some more complex examples. Ex. 10 nitrogen; Ex. 11
ethane; Ex. 12 chloromethane and Ex. 13 methanol. The valencies or combining power in theses examples are N 3, H 1, C
4, Cl 1 and O 2.
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MULTIPLE BONDS
Why multiple bonds form: Nonmetal atoms bond to reach a stable or low energy condition. This
happens when a main-group atom shares enough electrons to achieve a rare gas valence shell.
Sometimes the number of electrons needed cannot be provided by sharing electrons simply in single
bonds(pairs).
Nitrogen molecules are an example of this situation. Nitrogen atoms have five valence electrons. We
know that molecules of N2 exist based on a great deal of measurements. If two nitrogen atoms
simply formed a single bond the dot structure would look like the illustraton below. Each nitrogen
atom would have only six electrons not an octet. The single bond doesn't provide the two nitrogen
atoms with an octet. If the octet rule is to be followed, the nitrogen atoms must share more than two
electrons.
The trial and error method is used to decide how many shared electrons are needed to create a
structure where the octet rule is met. Since one bond didn't work the next thing to try is a double
bond where the atoms share four electrons. Unfortunately the double bond structure only provides 7
valence shell electrons not eight.
Because the single and double bonds didn't do the trick the next thing to try is a triple bond where the nitrogen
atoms share six electrons. The count for both atoms when a triple bond is used in the structure shows that the
octet rule is met.
Multiple bonds are very common in carbon compounds. The carbon atom can form four bonds. These
four bonds can be all single,CH3CH3, two single and one double, CH2CH2, two double, one single and
one triple, CHCH.
Ethane has a single bond carboncarbon bond
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The carbon-carbon double bond has a The carbon-carbon triple bond has a
bond length of 133 picometers.
bond length of 120 picometers.
The carbon-carbon bond lengths decrease as the number of shared electrons and bonds increase. This is reasonable
because there are more electrons attracted to each nucleus. The repulsions between positive nuclei decrease as more
electrons are shared. The relative lengths for the three types of bonds are summarized here. REMEMBER these
compare bonds between pairs of atoms like ;
C:::C, C::C, C:C or C:::N, C::N, C:N or N:::N, N::N N:N or N::O , N:O
The electrical forces of attraction, that is the chemical bond*, between atoms in any molecule are
strong and most molecules do not change chemically on moderate heating.(* sometimes referred to as the
intramolecular bond)
However, the electrical forces** between molecules are weak and easily weakened further on
heating.
These weak attractions are known as **intermolecular forces and consequently the bulk material is not
usually very strong.
Consequently small covalent molecules tend to be volatile liquids, easily vapourised, or low melting
point solids.
On heating the inter-molecular forces are easily overcome with the increased kinetic energy gain of the particles
and so have low melting and boiling points.
They are also poor conductors of electricity because there are no free electrons or ions in any state to
carry electric charge.
Most small molecules will dissolve in a solvent to form a solution.
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(macromolecules - giant covalent networks and polymers)
Carbon also occurs in the form of graphite. The carbon atoms form
joined hexagonal rings forming layers 1 atom thick.
There are three strong covalent bonds per carbon, BUT, the fourth
bond carbon can form from its four outer electrons, is shared between the
three bonds shown (this requires advanced level concepts to fully explain,
and this bonding situation also occurs in fullerenes described below).
The layers are only held together by weak intermolecular forces
shown by the dotted lines NOT by strong covalent bonds.
Like diamond and silica (above) the large molecules of the layer ensure
graphite has typically very high melting point because of the strong
2D bonding network (note: NOT 3D network)..
Graphite will not dissolve in solvents because of the strong bonding
BUT there are two crucial differences compared to diamond ...
o Electrons, from the 'shared bond', can move freely through
each layer, so graphite is a conductor like a metal (diamond is
an electrical insulator and a poor heat conductor). Graphite is used in
electrical contacts eg electrodes in electrolysis.
o The weak forces enable the layers to slip over each other so
where as diamond is hard material graphite is a 'soft' crystal, it
feels slippery. Graphite is used as a lubricant.
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The bonding in polymers or plastics is no different in principle to the examples described above, but there is quite
a range of properties and the difference between simple covalent and giant covalent molecules can get a bit
'blurred'.
o Bonds between atoms in molecules, eg C-C, are called intra-molecular bonds.
o The much weaker electrical attractions between individual molecules are called inter-molecular forces.
In thermosoftening plastics like poly(ethene) the bonding is like ethane except there are lots of carbon
atoms linked together to form long chains. They are moderately strong materials but tend to soften on heating
and are not usually very soluble in solvents. The structure is basically a linear 1 dimensional strong
bonding networks.
Graphite structure is a layered 2 dimensional strong bond network made of layers of joined
hexagonal rings of carbon atoms with weak inter-molecular forces between the layers.
Thermosetting plastic structures like melamine have a 3 dimensional cross-linked giant covalent
structure network similar to diamond or silica in principle, but rather more complex and chaotic! Because of the
strong 3D covalent bond network they do not dissolve in any solvents and do not soften on heating and are much
stronger than thermoplastics.
More on polymers in Oil Notes and Extra Organic Chemistry Notes.
3. Ionic Bonding
Ionic bonds are formed by one atom transferring electrons to another atom to form ions. Ions are atoms, or groups
of atoms, which have lost or gained electrons.
The atom losing electrons forms a positive ion (a cation) and is usually a metal. The overall charge on the ion is
positive due to excess positive nuclear charge (protons do NOT change in chemical reactions).
The atom gaining electrons forms a negative ion (an anion) and is usually a non-metallic element. The overall
charge on the ion is negative because of the gain, and therefore excess, of negative electrons.
The examples below combining a metal from Groups 1 (Alkali Metals), 2 or 3, with a non-metal from Group 6 or Group 7
(The Halogens)
Example 1: A Group 1 metal + a Group 7 non-metal eg sodium + chlorine sodium chloride NaCl or ionic formula
Na+Cl- In terms of electron arrangement, the sodium donates its outer electron to a chlorine atom forming a single
positive sodium ion and a single negative chloride ion. The atoms have become stable ions, because electronically, sodium
becomes like neon and chlorine like argon.
Na (2.8.1) + Cl (2.8.7) Na+ (2.8) Cl- (2.8.8)
can be summarised electronically as [2,8,1] + [2,8,7] [2,8]+ [2,8,8]-
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ONE
to form
ONE
to form
see *
* NOTE you can draw two separate chloride ions, but in these examples a number subscript has been used, as in
ordinary chemical formula.
Example 3: A Group 3 metal + a Group 7 non-metal eg aluminium + fluorine aluminium fluoride AlF3 or ionic
formula Al3+(F-)3 In terms of electron arrangement, the aluminium donates its three outer electrons to three fluorine
atoms forming a triple positive aluminium ion and three single negative fluoride ions. The atoms have become stable ions,
because electronically, aluminium and fluorine becomes electronically like neon. Valency of Al is, F is 1.
Al (2.8.3) + 3F (2.7) Al3+ (2.8) 3F- (2.8)
can be summarised electronically as [2,8,3] + 3[2,7] [2,8]3+ [2,8]-3
ONE
to form
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Example 4: A Group 1 metal + a Group 6 non-metal eg potassium + oxygen potassium oxide K2O or ionic
formula (K+)2O2- In terms of electron arrangement, the two potassium atoms donates their outer electrons to one
oxygen atom. This results in two single positive potassium ions to one double negative oxide ion. All the ions have the
stable electronic structures 2.8.8 (argon like) or 2.8 (neon like). Valencies, K 1, oxygen 2. Na 2O, Na2S, K2S etc. will be
similar.
2K (2.8.8.1) + O (2.6) 2K+ (2.8.8) O2- (2.8)
can be summarised electronically as 2[2,8,8,1] + [2,6] [2,8,8]+2 [2,8]2-
TWO
to form
Example 5: A Group 2 metal + a Group 6 non-metal eg calcium + oxygen calcium oxide CaO or ionic formula
Ca2+O2- In terms of electron arrangement, one calcium atom donates its two outer electrons to one oxygen atom. This
results in a double positive calcium ion to one double negative oxide ion. All the ions have the stable electronic structures
2.8.8 (argon like) or 2.8 (neon like). the valency of both calcium and oxygen is 2. MgO, MgS, or CaS will be similar
electronically (S and O both in Group 6)
Ca (2.8.8.2) + O (2.6) Ca2+ (2.8.8) O2- (2.8)
can be summarised electronically as [2,8,8,2] + [2,6] [2,8,8]2+ [2,8]2-
ONE
to form
Example 6: A Group 3 metal + a Group 6 non-metal eg aluminium + oxygen aluminium oxide Al2O3 or ionic
formula (Al3+)2(O2-)3 In terms of electron arrangement, two aluminium atoms donate their three outer electrons to
three oxygen atoms. This results in two triple positive aluminium ions to three double negative oxide ions. All the ions
have the stable electronic structure of neon 2.8. Valencies, Al 3 and O 2.
2Al (2.8.3) + 3O (2.6) 2Al3+ (2.8) 3O2- (2.8)
can be summarised electronically as 2[2,8,3] + 3[2,6] [2,8]3+2 [2,8]2-3
TWO
to form
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4. BONDING IN METALS
Electron-Sea Model of Metals
In the electron-sea model, a metal crystal is considered to be a
three-dimensional array of metal cations immersed in a sea of
valence electrons. The delocalized valence electrons are free to
move throughout the crystal and are not associated with any
one particular metal cation. The mobility of the electrons
accounts for the high electrical conductivity of metals.
Thermal conductivity can also be ascribed to the mobile
electrons that conduct heat by carrying kinetic energy from
one part of the crystal to another. Three-dimensional
delocalized bonding allows the metal to be both malleable and
ductile.
The crystal lattice of metals consists of ions NOT atoms surrounded by a 'sea of electrons' forming another
type of giant lattice.
11
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between these mobile electrons (-) and the 'immobile' positive metal ions (+) and this is the
metallic bond.
1. Shows the regular arrangement of the atoms in a metal crystal and the white spaces show where the free
electrons are (yellow circles actually positive metal ions).
2. Shows what happens when the metal is stressed by a strong force. The layers of atoms can slide over each other
3.
and the bonding is maintained as the mobile electrons keep in contact with atoms, so the metal remains intact
BUT a different shape.
Shows an alloy mixture. It is NOT a compound but a physical mixing of a metal plus at least one other material
(shown by red circle, it can be another metal eg Ni, a non-metal eg C or a compound of carbon or manganese,
and it can be bigger or smaller than iron atoms). Many alloys are produced to give a stronger metal. The
presence of the other atoms (smaller or bigger) disrupts the symmetry of the layers and reduces the 'slip ability'
of one layer next to another. The result is a stronger harder less malleable metal.
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A coordinate covalent bond is special because it involves a shared pair of electrons that came from a single atom. Ammonia had
a nitrogen atom with an unshared pair of electrons. These can be shared with an electron defficient atom like H +.
ammonia
ammonia
proton
ammonium ion
Water molecules have two unshared pairs of electrons. These form coordinate covalent bonds with cations that are dissolved in
water. This is one reason why water dissolves many ionic solids. The energy released when the water molecules bond to the
cations is often enough to break up the ionic solid.
water
cation
6. INTERMOLECULAR FORCES
Intermolecular forces are those forces that occur between particles (molecules, atoms, or ions).
The strength of these forces at a given temperature dictates whether a substance will have the
properties of a solid, a liquid, or a gas. The term van der Waals forces encompasses all types of
intermolecular forces. All intermolecular forces arise from electrostatic interactions governed by
the basic rule that like charges repel and unlike charges attract.
Hydrogen Bonds
13
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A hydrogen bond is an attractive interaction between a hydrogen that is bonded to a very electronegative atom (O, N,
or F) and an unshared electron pair on another electronegative atom.
Hydrogen bonds can be quite strong. Substances that form hydrogen bonds have unusually high boiling
points due to the extra energy that must be used to separate the molecules.
DONE
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CHEMICAL TESTS
INORGANIC TESTS
TEST FOR
hydrogen
gas H2
carbon dioxide gas
CO2
oxygen gas O2
Hydrogen
chloride gas
HCl, in water
hydrochloric acid
HI
TEST
METHOD
bubble into
turns cloudy fine Ca(OH)2(aq) + CO2(g) ==> CaCO3(s) + H2O(l)
limewater
milky white precipitate
(aqueous calcium of calcium carbonate
hydroxide solution)
glowing splint or
spill
re-ignites it flame
Hydrogen
As above. In water as above but cream
bromide HBr and they are
HBr or yellow HI
Hydrogen iodide hydrobromic acid precipitate
and hydriodic acid.
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Sulphur
dioxide
gas SO2
freshly made
potassium
dichromate(VI)
paper
Chlorine (i) blue litmus, (ii) pungent green gas, (i) (i) non-metal, is acid in aqueous solution and a
gas Cl2 drop silver nitrate litmus turns red and powerful oxidising agent, (ii) forms chloride ion in
Iodine solid
then is bleached
white, (ii) white
precipitate
water
NO2
(i) white
anhydrous
copper(II)
sulphate, (ii) dry
blue cobalt
chloride paper
(i) turns from white to (i) blue hydrated copper(II) crystals or solution
blue, (ii) turns from
formed, (ii) hydrated cobalt ion formed
blue to pink
[Co(H2O)6]2+
fizzing - colourless
gas - turns
limewater milky
cloudy (see above
CO2)
(or hydrogencarbonate
HCO3-)
Sulphate
ion [sulphate(VI)]
SO42-
Sulphite ion
2[sulphate(IV)] SO3
(i) acrid
choking
sulphur
dioxide gas formed,
(ii) the dichromate
paper turns from
orange to green
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dichromate(VI)
paper
dangerous hydrogen
sulphide formed
Chloride ion
(i) white
precipitate
of silver
chloride soluble in
dilute ammonia, (ii)
get fumes of
hydrogen chloride
which turn blue litmus
red and give a white
precipitate with silver
nitrate solution
(i) cream
precipitate
of silver
bromide, only soluble
in concentrated
ammonia, (ii) orange
vapour, test for
sulphur dioxide.
(i) yellow
precipitate
of silver
iodide insoluble in
concentrated
ammonia, (ii) purple
vapour and rotten egg
smell!, (iii) a yellow
precipitate forms
Cl-
Bromide ion
Br-
Iodide ion I-
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meet a brown ring
forms
(ii) Add iron(ii)
sulphate solution
and then conc.
sulphuric acid (the
'brown ring' test)
Nitrite ion [or No simple test, (i) in acid solution it decomposes to give nasty brown fumes of NO2, (ii) it
nitrate(III)]
NO2
smelly
ammonia
evolved!
and red
litmus
Hydroxide ion
ie an alkali
OH- (note: to
completely identify
alkalis you need to test
for the cation eg sodium
for NaOH etc.)
Positive metal
cations via
flame tests
(see below for
NaOH and NH3
for metal ion
tests too)
Positive metal
cations via sodium
hydroxide (NaOH)
Dilute sodium
hydroxide
solution is added
to a solution
copper(II) Cu2+
blue/green
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containing the
or ammonia (NH3)
solutions (both alkalis, suspected ion.
giving hydroxide ions,
OH-, in their solutions)
Both the
precipitate
formed and the
effect of excess
alkali are
important
observations.
All precipitates
white, unless
otherwise stated
and all tend to be
gelatinous in
nature.
MISCELLANEOUS
CATION TESTS:
(i) add potassium (i) Pb2+(aq) +2I-(aq) ==>PbI2(s) lead(II) iodide ppt.
iodide solution =>
yellow precipitate
Metal Carbonates
Sometimes heating
a metal carbonate
strongly to
decompose it
provides some
clues to its
identity. Adding
acid => CO2 and
the colour of the
resulting solution
(eg blue Cu2+(aq),
may also provide
clues. The metal
ion solution might
also give a flame
colour or a
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hydroxide
precipitate with
sodium hydroxide
eg copper.
ORGANIC TESTS
TEST FOR
TEST
METHOD
ALKENE or
bubble gas
through, or add
liquid to, a solution
of bromine in
hexane or water
OBSERVATIONS
TEST CHEMISTRY
the orange/brown
R2C=CR2 + Br2 ==> BrR2C-CR2Br
bromine, decolourises,
as a saturated
RC CR + 2Br2 ==> Br2RC-CRBr2
colourless organic
bromo-compound is
R = H, alkyl or aryl
formed (saturated
alkanes give no fast
reaction with bromine)
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Almost no forces of attraction between the particles so they are completely free of each other.
Particles widely spaced and scattered at random throughout the container so there is no order in the
system.
Particles move rapidly in all directions, frequently colliding with each other and the side of the
container.
With increase in temperature, the particles move faster as they gain kinetic energy.
Gases have a very low density (light) because the particles are so spaced out in the container.
o Density order: solid > liquid >>> gases
Gases flow freely because there are no effective forces of attraction between the particles.
o Ease of flow order: gases > liquids >>> solids (no real flow in solid unless you powder it!)
Gases have no surface, and no fixed shape or volume, and because of lack of particle attraction,
they always spread out and fill any container (so gas volume = container volume).
Gases are readily compressed because of the empty space between the particles.
o Ease of compression order: gases >>> liquids > solids (almost impossible to compress a
solid)
If the container volume can change, gases readily expand* on heating because of the lack of
particle attraction, and readily contract on cooling.
o On heating, gas particles gain kinetic energy, move faster and hit the sides of the
container more frequently, and significantly, they hit with a greater force.
o Depending on the container situation, either or both of the pressure or volume will increase
(reverse on cooling).
o Note: * It is the gas volume that expands NOT the molecules, they stay the same size!
The natural rapid and random movement of the particles means that gases readily spread or
diffuse. Diffusion is fastest in gases where there is more space for them to move.
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o
o
The rate of diffusion increases with increase in temperature as the particles gain
kinetic energy and move faster.
Other evidence for random particle movement:
When smoke particles are viewed under a microscope they appear to 'dance around'
when illuminated with a light beam at 90o to the viewing direction. This is because the
smoke particles show up by reflected light and 'dance' due to the millions of random hits
from the fast moving air molecules. This is called 'Brownian motion'. At any given
instant of time, the hits will not be even, so the smoke particle get a greater bashing in a
random direction.
If a long glass tube is filled at one with a plug of cotton wool soaked in conc.
hydrochloric acid, and a similar plug of conc. ammonia solution at the other end. If left
undisturbed and horizontal, despite the lack of tube movement (eg shake to mix), a
white cloud forms about 1/3rd along from the conc. acid tube end.
What happens is the colourless gases ammonia and hydrogen chloride diffuse
down the tube and react to form fine white crystals of the salt ammonium
chloride.
NH3(g) + HCl(g) ==> NH4Cl(s)
Note the rule: The smaller the molecular mass, the faster the molecules
move.
Therefore the smaller the molecular mass, the faster the gas diffuses.
eg Mr(NH3) = 14 + 1x3 = 17, moves faster than Mr(HCl) = 1 + 35.5 =
36.5
AND that's why they meet nearer the HCl end of the tube!
So the experiment is not only evidence for molecule movement, its
also evidence that different molecular masses move on at
different speeds.
A coloured gas, that is heavier than air, is
put into a gas jar and a second gas jar is
placed over it separated with a cover.
If the cover is removed than coloured gas
diffuses into the colourless air above. It
can't be due to convection because the
more dense gas starts at the bottom!
No 'shaking' or other means of mixing is
required. The random movement of both
lots of particles is enough to ensure that
both gases are completely mixed
eventually.
This is clear evidence for the process of
diffusion due to particle movement.
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Much greater forces of attraction between the particles in a liquid compared to gases, but not
quite as much as in solids.
Particles quite close together but still arranged at random throughout the container, there is a little
close range order as you can get clumps of particles clinging together temporarily.
Particles moving rapidly in all directions but more frequently collisions with each other than in
gases due to shorter distances between particles.
With increase in temperature, the particles move faster as they gain kinetic energy, so increased
collision rates, increased collision energy and increased rate of diffusion.
Liquids have a much greater density than gases (heavier) because the particles are much closer
together because of the attractive forces.
Liquids usually flow freely despite the forces of attraction between the particles but liquids are not as
fluid as gases.
o Note 'sticky' or viscous liquids have much stronger attractive forces between the
molecules BUT not strong enough to form a solid.
Liquids have a surface, and a fixed volume (at a particular temperature) because of the increased
particle attraction, but the shape is not fixed and is merely that of the container itself.
Liquids are not readily compressed because of the lack of empty space between the particles.
Liquids will expand on heating but nothing like as much as gases because of the greater particle
attraction restricting the expansion (will contract on cooling).
o Note: When heated, the liquid particles gain kinetic energy and hit the sides of the container
more frequently, and more significantly, they hit with a greater force, so in a sealed container
the pressure produced can be considerable!
The natural rapid and random movement of the particles means that liquids spread or
diffuse. Diffusion is much slower in liquids compared to gases because there is less space for the
particles to move in and more blocking collisions happen.
Evidence for random particle movement in liquids:
o If coloured crystals of eg the highly coloured salt crystals of potassium manganate(VII) are
dropped into a beaker of water and covered at room temperature. Despite the lack of mixing,
convection etc. the bright purple colour of the dissolving salt slowly spreads throughout all of the
liquid but it is much slower than the gas experiment described above.
o When pollen grains are viewed under a microscope they appear to 'dance around' when
illuminated with a light beam at 90o to the viewing direction. This is because the pollen grains
show up by reflected light and 'dance' due to the millions of random hits from the fast moving
water molecules. This is called 'Brownian motion' after a botanist called Brown first described
the effect. At any given instant of time, the hits will not be even all round the pollen grain, so
they get a greater number of hits in a random direction.
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The greatest forces of attraction are between the particles in a solid and they pack together as tightly as possible
in a neat and ordered arrangement.
The particles are too strongly held together to allow movement from place to place but the particles vibrate about
there position in the structure.
With increase in temperature, the particles vibrate faster and more strongly as they gain kinetic energy.
Solids have the greatest density (heaviest) because the particles are closest together.
Solids cannot flow freely like gases or liquids because the particles are strongly held in fixed
positions.
Solids have a fixed surface and volume (at a particular temperature) because of the strong particle
attraction.
Solids are extremely difficult to compress because there is no real empty space between the
particles.
Solids will expand a little on heating but nothing like as much as liquids because of the greater
particle attraction restricting the expansion (contract on cooling).
o The expansion is caused by the increased energy of particle vibration, forcing them further apart.
Diffusion is almost impossible in solids because the particles are too strongly held and there are no
empty spaces for particles to move into.
Changes of State
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Condensing (gas to liquid)
On cooling, gas particles lose kinetic energy and eventually become attracted together to form a
liquid.
There is an increase in order as the particles are much closer together and can form clumps of
molecules.
The process requires heat to be lost to the surroundings ie heat given out, so condensation is
exothermic.
o This is why steam has such a scalding effect, its not just hot, but you get extra heat transfer to
your skin due to the exothermic condensation on your surface!
When a solid is heated the particles vibrate more strongly as they gain kinetic energy and the
particle attractive forces are weakened.
Eventually, at the melting point, the attractive forces are too weak to hold the particles in the structure
together in an ordered way and so the solid melts.
The particles become free to move around and lose their ordered arrangement.
Energy is needed to overcome the attractive forces and give the particles increased kinetic energy
of vibration.
So heat is taken in from the surroundings and melting is an endothermic process.
On cooling, liquid particles lose kinetic energy and so can become more strongly attracted to each
other.
Eventually at the freezing point the forces of attraction are sufficient to remove any remaining freedom
and the particles come together to form the ordered solid arrangement.
Since heat must be removed to the surroundings freezing is an exothermic process!!!
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Cooling and Heating Curves
Note the temperature stays constant during
the state changes of condensing Tc and
freezing Tf. This is because all the energy
removed on cooling at these temperatures
weakens the inter-particle forces without
temperature fall.
A cooling curve summarises the changes:
gas liquid solid
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Sublimation
Sublimation:
o This is when a solid, on heating, directly changes into a gas, AND the gas on cooling
re-forms a solid directly. They usually involve just a physical change BUT its not always
that simple!
Theory in terms of particles:
o When the solid is heated the particles vibrate with increasing force from the added thermal
energy.
If the particles have enough kinetic energy of vibration to partially overcome the particleparticle attractive forces you would expect the solid to melt.
HOWEVER, if the particles at this point have enough energy at this point that would have
led to boiling, the liquid will NOT form and the solid turns directly into a gas.
Overall endothermic change, energy absorbed and 'taken in' to the system.
o On cooling, the particles move slower and have less kinetic energy.
Eventually, when the particle kinetic energy is low enough, it will allow the particleparticle attractive forces to produce a liquid.
BUT the energy may be low enough to permit direct formation of the solid, ie the
particles do NOT have enough kinetic energy to maintain a liquid state!
Overall exothermic change, energy released and 'given out' to the
surroundings.
Examples:
1. Even at room temperature bottles of solid iodine show crystals forming at the top of the bottle
above the solid. The warmer the laboratory, the more crystals form when it cools down at night!
2.
I2 (s)
I2 (g) (physical change only)
The formation of a particular form of frost involves the direct freezing of water vapour (gas).
Frost can also evaporate directly back to water vapour (gas) and this happens in the 'dry'
extremely cold winters of the Gobi Desert.
3.
H2O (s)
H2O (g) (physical change only)
Solid carbon dioxide (dry ice) is formed on cooling the gas down to less than -78oC. On
warming it changes directly to a very cold gas!, condensing any water vapour in the air to a
'mist', hence its use in stage effects.
4.
CO2 (s)
CO2 (g) (physical change only)
On heating strongly in a test tube, the white solid ammonium chloride, decomposes into a
mixture of two colourless gases ammonia and hydrogen chloride. On cooling the reaction is
reversed and solid ammonium chloride reforms at the cooler top of the test tube.
NH4Cl(s)
NH3(g) + HCl(g)
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SOLUTIONS & SOLUBILITIES
Solutions
A solution is a homogeneous mixture consisting of particles 0.12.0 nm in diameter.
Homogeneous mixtures having larger particles (2500 nm) are classified as colloids.
Suspensions are mixtures with even larger particles, but they are not considered true
solutions because they separate upon standing.
We usually think of solutions as solids dissolved in liquids, or perhaps a mixture of two
liquids, but there are many other kinds of solutions as well. Some examples are provided in
Table 11.1.
For solutions in which a gas or solid is dissolved in a liquid, the dissolved substance is
called the solute and the liquid is called the solvent. When one liquid is dissolved in
another, the minor component is usually considered the solute.
Solution: a homogeneous mixture containing particles the size of a typical ion or covalent
molecule
Colloid: a homogeneous mixture containing particles with diameters in the range 2500 nm
Solute: the dissolved substance in a solution
Solvent: the major component in a solution
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A supersaturated solution can form when more than the equilibrium amount of solute is
dissolved at an elevated temperature, and then the supersaturated solution is slowly cooled.
The amount of solute per unit solvent required to form a saturated solution is called the
solute's solubility. A substance's solubility is a characteristic of that substance. Figure 11.5
illustrates the solubilities of some solids, and their temperature dependence.
When two liquids are completely soluble in each other they are said to be miscible.
The effect of temperature on gas solubility is more predictable than solid solubility. Most
gases become less soluble in water as the temperature increases.
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Pressure has little effect on the solubility of liquids and solids. The solubility of gases is
strongly influenced by pressure
Saturated solution: a solution containing the maximum possible amount of dissolved solute at
equilibrium
Supersaturated solution: a solution containing a greater-than-equilibrium amount of solute
Solubility: the amount of a substance that dissolves in a given volume of solvent
Miscible: mutually soluble in all proportions
Henry's law: The solubility of a gas in a liquid at a given temperature is directly proportional to the
partial pressure of the gas over the solution
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METALS
IMPORTANCE OF METALS
More then three quarters of elements in the periodic table are metals.
We cook food, heat the food on metals stoves.
We travel in metallic vehicals like car, airplanes, ships.
The concreate wall and roofs of houses are reinforced with metal rods.
Coins, taps, cutlary, pins, needles paper pins etc. are all made up of metals.
PROPERTY
REASON
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Magnesium reacts very slowly with cold water but vigrously with steam to form salt and hydrogen gas.
Magnesium + steam --------- Magnesium oxide + hydrogen gas
Mg(s) + H2O (g) ------------- MgO(s) + H2(g)
Zinc do not react with cold water but reacts slowly with steam to form zinc oxide and hydrogen gas.
Zink + steam --------------- Zink oxide + hydrogen gas
Zn(s) + H2O (g) ------------- ZnO(s) + H2(g)
Iron do not react with cold water but rusting occur very slowly in the presence of oxygen. Red hot iron
reacts very slowly with steam to produce salt and hydrogen gas.
Iron + steam --------------- Iron oxide + hydrogen
3Fe(s) + 4H2O (g) ------------- Fe3O4(s) + 4H2(g)
Copper do not react with water under any condition
Silver do not react with water in any condition.
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Magnesium reacts very fastly to form magnesium chloride and hydrogen gas.
Magnesium + hydrochloric acid -------- Magnesium chloride + hydrogen gas
Mg(s) + 2HCl (aq) ------------- MgCl2(aq) + H2(g)
Zinc reacts moderately to form zinc chloride and hydrogen gas.
Zink + hydrochloric acid ------ Zink chloride + hydrogen gas
Zn(s) + 2HCl (aq) ------------- ZnCl2(aq) + H2(g)
Iron reacts slowly to produce iron chloride and hydrogen gas.
Iron + hydrochloric acid -------- Ironchloride + hydrogen gas
Fe(s) + 2HCl (aq) ------------- FeCl2(aq) + H2(g)
+ O2(g)
-------------------
2K2O(s)
2Cu(s)
+ O2(g) -------------------
2CuO(s)
Iron powder or wire burns with a bright yellow flame to form iron oxide Fe3O4
Iron
Fe(s)
+ Oxygen ----------------
+ O2(g) -------------------
Iron oxide
2Fe3O4(s)
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Magnesium burns with a bright white flame to produce white solid magnesium oxide. MgO
Magnesium + oxygen ----------- Magnesium oxide
2Mg(s)
+ O2(g) -------------------
2MgO(s)
REACTIVITY SERIES
Metals can be arranged in order of their chemical reactivity. The reactivity series is based on the reaction
of metals with water or dilute hydrochloric acid. When metal recats with acid or water, the metal atom
lose electron to become ion.
Metal(s) + H2O (l)
H2 (g)
Metal (s) + HCl (aq) ----------------
Metal + ion
+
+
OH- ion +
Cl- ion
H2(g)
The more readily a metal gives up electrons to form ions, the more reactive it is.
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Hydrogen is sometimes placed in the reactivity series. Metals below hydrogen in the series do not react
with acids to produce hydrogen gas.
+ CuSO4 (aq)
--------------------------
Cu(s)
ZnSO4 (aq)
Zinc displace copper from the copper sulphate solution because it is more reactive than copper and readily
give up electrons to form positive ions. The electrons are transferred from zinc atom to copper (II) ions.
Cu2+ (aq) + Zn(s)
blue solution
---------------- Cu (s)
redish-brown solid
Zn2+ (aq)
colourless
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Other examples:
Ag+ (aq) +
Cu (s)
Zn2+ (aq)
Mg (s)
------------------
----------------
+ CuO(s)
------heat-------------
+ hydrogen
CuO (s)
-------heat------------
+ H2
+ water.
H2O (l)
----heat--------- copper
water.
The less reactive the metal, the easier it is for hydrogen to take oxygen from its oxide. The oxides of vary
recative metals such as aluminium oxide and sodium oxide cannot be reduced to the metal by hydrogen.
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Copper (II) oxide
2CuO (s)
+ C(s)
+ carbon dioxide.
+ CO2 (g)
The more reactive the metal the more harder it for carbon to take oxygen from its oxide. Iron is more
reactive than copper, iron oxide and carbon must be heated very strongly for the reaction to take place.
Iron (II) oxide
2FeO (s)
2Fe
Iron
+
+ carbon dioxide.
CO2
Carbon is unable to take oxygen from the oxides of very reactive such as calcium and sodium.
Chemical Name
Formula
Metal extracted
Bauxite
Aluminium oxide
Al2O3
Aluminium
Galena
Lead sulphide
PbS
Lead
Haematite
Sphalerite
Fe2O3
ZnS
Iron
Zinc
Copper pyrite
Copper iron
sulphide
CuFeS2
Copper
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Introduction
The Earth's crust contains many different rocks. Rocks are a mixture of minerals and from some we
can make useful substances.
A mineral can be a solid metallic or non-metallic element or a compound found naturally in the
Earth's crust.
A metal ore is a mineral or mixture of minerals from which economically viable amounts of
metal can be extracted, i.e. its got to have enough of the metal, or one of its compounds, in it to be
worth digging out! Ores are often oxides, carbonates or sulphides. They are all finite resources so
we should use them wisely!
In order to extract a metal, the ore or compound of the metal must undergo a process called
reduction to free the metal (i.e. the positive metal ion gains negative electrons to form the
neutral metal atom, or the oxide loses oxygen, to form the free metallic atoms).
Generally speaking the method of extraction depends on the metals position in the reactivity
series.
The reactivity series of metals can be presented to include two non-metals, carbon and
hydrogen, to help predict which method could be used to extract the metal.
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The ore or compound must be molten or dissolved in a solution in an electrolysis cell to
allow free movement of ions (electrical current).
Metals below carbon can be extracted by heating the oxide with carbon or carbon monoxide.
The non-metallic elements carbon will displace the less reactive metals in a smelter or blast
furnace e.g. iron or zinc and metals lower in the series.
o Metals below hydrogen will not displace hydrogen from acids. Their oxides are easily
reduced to the metal by heating in a stream of hydrogen, though this is an extraction method
rarely used in industry. In fact most metal oxides below carbon can be reduced when heated in
hydrogen, even if the metal reacts with acid.
Some metals are so unreactive that they do not readily combine with oxygen in the air or any other
element present in the Earth's crust, and so can be found as the metal itself. For example gold (and
sometimes copper and silver) and no chemical separation or extraction is needed. In fact all the metals
below hydrogen can be found as the 'free' or 'native' element.
Other methods are used in special cases using the displacement rule. A more reactive metal can be
used to displace and extract a less reactive metal but these are costly processes since the more
reactive metal also has to be produced in the first place! See Titanium or see at the end of the section
on copper extraction
Sometimes electrolysis is used to purify less reactive metals which have previously been extracted
using carbon or hydrogen (eg copper and zinc). Electrolysis is also used to plate one metal with
another.
The demand for raw materials does have social, economic and environmental implications eg
conservation of mineral resources by recycling metals, minimising pollution etc.
Historically as technology and science have developed the methods of extraction have improved to
the point were all metals can be produced. The reactivity is a measure of the ease of compound
formation and stability (ie more reactive, more readily formed stable compound, more difficult to reduce
to the metal).
o The least reactive metals such as gold, silver and copper have been used for the past 10000
years because the pure metal was found naturally.
o Moderately reactive metals like iron and tin have been extracted using carbon based
smelting for the past 2000-3000 years.
o BUT it is only in the last 200 years that very reactive metals like sodium or aluminium have
been extracted by electrolysis.
o
21.2 Metallurgy
Metallurgy is the combination of science and technology used to extract metals from their ores. Ores
are complex mixtures of metal-containing material and useless impurities called gangue. The steps
involved in extracting a metal include the following:
The metal may be mixed with other elements to modify its properties or to form an alloy, a metallic
solution of two or more elements
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Concentration and Chemical Treatment of Ores
The different physical properties of the mineral and the gangue, such as density and magnetic charge,
can be used to concentrate the mineral and remove the gangue. Metal sulfide ores are concentrated by
flotation, a process that exploits differences in the ability of water and oil to wet the surfaces of the
mineral and the gangue. Mineral particles float to the top of the tank along with soapy air bubbles, while
the gangue sinks to the bottom.
Ores can also be concentrated by chemical means. In the Bayer process, the Al 2O3 in bauxite is
separated from Fe2O3 impurities by treating the ore with NaOH.
Roasting, or heating in air, is another chemical treatment used to convert minerals to compounds that
are more easily reduced to the metal.
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Reduction
The more active metals are obtained by reducing their ores with a chemical reducing agent. Zinc is
obtained by reducing ZnO with coke, a form of carbon.
Carbon cannot be used to reduce metals that form stable carbides, such as tungsten. Tungsten(VI) oxide
is reduced with hydrogen gas.
The most active metals cannot be reduced with chemical reducing agents, so these metals are produced
by electrolytic reduction,.
Refining
The metals obtained from reducing ores generally require purification. Some metals, including zinc, can
be purified by distillation. Nickel is purified using the Mond process, a chemical method in which
Ni(CO)4 is formed and then decomposed at a higher temperature. The equilibrium shift at the higher
temperature favors pure nickel.
Extraction
of Metal
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Raw Materials:
Iron Ore eg
haematite ore
[iron(III) oxide,
Fe2O3]
coke (carbon, C)
hot air (for the O2
in it)
limestone (calcium
carbonate, CaCO3)
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The cast iron or pig iron produced in a blast furnace must be purified. In the basic oxygen process,
molten iron from the blast furnace is mixed with pure oxygen gas in a furnace lined with basic
oxides. The impurities in the iron are oxidized and the acidic oxides react with CaO to yield a
molten slag. Phosphorus impurities react in this process to form a calcium phosphate slag.
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adding it to the resulting copper(II) sulphate solution.
iron + copper(II) sulphate ==> iron(II) sulphate + copper
Fe(s) + CuSO4(aq) => FeSO4(aq) + Cu(s)
Titanium ore is mainly the oxide TiO 2, which is converted into titanium tetrachloride TiCl4
The chloride is then reacted with sodium or magnesium to form titanium metal and sodium
chloride or magnesium Chloride.
This reaction is carried out in an atmosphere of inert argon gas so non of the metals
involved becomes oxidised by atmospheric oxygen.
TiCl4 + 2Mg ==> Ti + 2MgCl2 or TiCl4 + 4Na ==> Ti + 4NaCl
These are examples of metal displacement reactions eg the less reactive titanium is
displaced by the more reactive sodium or magnesium.
Overall the titanium oxide ore is reduced to titanium metal (overall O loss, oxide => metal)
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o
o
Aluminium is a reactive metal but it is resistant to corrosion. This is because aluminium reacts
in air to form a layer of aluminium oxide which then protects the aluminium from further
attack.
o This is why it appears to be less reactive than its position in the reactivity series of
metals would predict.
For some uses of aluminium it is desirable to increase artificially the thickness of the
protective oxide layer in a process is called anodising.
o This involves removing the oxide layer by treating the aluminium sheet with sodium
hydroxide solution.
o The aluminium is then placed in dilute sulphuric acid and is made the positive electrode
(anode) used in the electrolysis of the acid.
o Oxygen forms on the surface of the aluminium and reacts with the aluminium metal to
form a thicker protective oxide layer.
Aluminium can be alloyed to make 'Duralumin' by adding copper (and smaller amounts
of magnesium, silicon and iron), to make a stronger alloy used in aircraft components (low
density = 'lighter'!), greenhouse and window frames (good anti-corrosion properties), overhead
power lines (quite a good conductor and 'light'), but steel strands are included to make the
'line' stronger and poorly electrical conducting ceramic materials are used to insulate the wires
from the pylons and the ground.
The properties of iron can be altered by adding small quantities of other metals or carbon to
make steel. Steels are alloys since they are mixtures of iron with other metals or with nonmetals like carbon or silicon.
Making Steel:
o (1) Molten iron from the blast furnace is mixed with recycled scrap iron
o (2) Then pure oxygen is passed into the mixture and the non-metal impurities such as
silicon or phosphorus are then converted into acidic oxides (oxidation process) ..
eg Si + O2 ==> SiO2, or 4P + 5O2 ==> P4O10
o (3) Calcium carbonate (a base) is then added to remove the acidic oxide impurities (in
an acid-base reaction). The salts produced by this reaction form a slag which can be
tapped off separately.
eg CaCO3 + SiO2 ==> CaSiO3 + CO2 (calcium silicate slag)
o Reactions (1)-(3) produce pure iron.
o Calculated quantities of carbon and/or other metallic elements such as titanium,
manganese or chromium are then added to make a wide range of steels with particular
properties.
o Because of the high temperatures the mixture is stirred by bubbling in
unreactive argon gas!
o Economics of recycling scrap steel or ion: Most steel consists of >25% recycled
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iron/steel and you do have the 'scrap' collection costs and problems with varying steel
composition* BUT you save enormously because there is no mining cost or overseas
transport costs AND less junk lying around! (NOTE: * some companies send their own
scrap to be mixed with the next batch of 'specialised' steel they order, this saves both
companies money!)
Different steels for different uses:
o High % carbon steel is strong but brittle.
o Low carbon steel or mild steel is softer and is easily shaped and pressed eg into a
motor car body.
o Stainless steel alloys contain chromium and nickel and are tougher and more
resistant to corrosion.
o Very strong steels can be made by alloying the iron with titanium or manganese
metal.
Steel can be galvanised by coating in zinc, this is physically done by dipping the object into a
bath of molten zinc. On removal and cooling a thin layer of zinc is left on. The zinc chemically
bonds to the iron via the free electrons of both metals - its all the same atoms to them! It can
also be done by electroplating.
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USES OF METALS
METAL
Aluminium
USES
Zinc
b) To make alloys e.g brass (Zn/Cu)
and bronze ( Zn/Sn/Cu).
Iron
a) Car batteries.
Lead
b) Solder (Pb/Sn) alloys
Copper
a) Electric cables
b) Pipes
c) Alloys
d) Coins (Cu/Ni)
Tin
Nickle
Electroplating steel
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Note on Alloy Structure
3.
ALLOY
COMPOSITION
%
Fe = 74%
Cr = 18 %
Ni = 8 %
Cu = 75%
Ni = 25%
Fe = 85 %
Mn = 13.8 %
C = 1.2
Cu = 70%
Zn = 30 %
Cu = 90 %
Sn = 10 %
Al = 90 %
Mg = 10 %
Pb = 50 %
Sn = 50 %
SPECIAL PROPERTIES
USES
Resist corrosion
Silver coins
Very hard
Springs
Aeroplanes bodies
Statues, ornaments.
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Iron (or steel) corrodes more quickly than most other transition
metals and readily does so in the presence of both oxygen (in air) and
water to form an iron oxide. You can do simple experiments to show
that BOTH oxygen and water are needed. Put an iron nail into (1) boiled
water in a sealed tube; (2) a tube of air and a drying agent; (3) an open
test tube with water. Rusting appears overnight with (3) only.
Rusting is speeded up in the presence of salt or acid solutions
because of an increased concentration of ions. Corrosion is a redox
process involving redox electron transfer and ion movement. The rusting
metal behaves like a simple cell and more ions enable the current, and hence the electron transfer, to
occur more readily.
Rusting is overall ... Fe(s) + O2(g) + H2O(l) ==> Fe2O3.xH2O(s) ie rust is a hydrated iron(III) oxide (the
equation is not meant to be balanced and the amount of water x is variable, from dry to soggy!).
o The reaction proceeds via iron(II) hydroxide Fe(OH)2 which is the oxidised further to the FeO3
o Rusting is an oxidation because it involves iron gaining oxygen (Fe ==> Fe2O3) or iron atoms
losing electrons (Fe - 3e- ==> Fe3+.
o See more examples of oxidation and reduction below.
The rusting of iron is a major problem in its use as a structural material.
Iron and steel (alloy of iron) are most easily protected by paint which provides a barrier between the
metal and air/water. Moving parts on machines can be protected by a water repellent oil or grease
layer.
This 'rusting' corrosion can be prevented by connecting iron to a more reactive metal (e.g. zinc or
magnesium). This is referred to as sacrificial protection or sacrificial corrosion, because the more
reactive protecting metal is preferentially oxidised away, leaving the protected metal intact. The picture
illustrates what might be seen after a few days.* Iron or steel can also be protected by mixing in other
metals (e.g. chromium) to make non-rusting alloys called stainless steel. The chromium, like aluminium,
forms a protective oxide layer.
* Theoretically, any iron ions formed by oxidation would be reduced by electrons from the oxidation of the
more reactive 'sacrificed' metal.
Coating iron or steel with a thin zinc layer is called 'galvanising'. The layer is produced by electrolytic
deposition by making the iron/steel the negative cathode or by dipping the iron/steel object in molten zinc
(more details). The zinc preferentially corrodes or oxidises to form a zinc oxide layer that doesn't flake off
like iron oxide rust does. Also, if the surface is scratched, the exposed zinc again corrodes before the iron
and continues to protect it.
Steel tin cans are protected by relatively unreacted tin and works well as long as the thin tin layer
is complete. HOWEVER, if a less reactive metal is connected to the iron, it then the iron rusts
preferentially (try scratching a 'tin' can and leave out in the rain and note the corrosion by the
scratch!)
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\Aluminium does not oxidise (corrode) as quickly as its reactivity would suggest. Once a thin oxide
layer of Al2O3 has formed on the surface, it forms a barrier to oxygen and water and so prevents
further corrosion of the aluminium.
Aluminium is a useful structural metal. It can be made harder, stronger and stiffer by mixing it with small
amounts of other metals (e.g magnesium) to make alloys.
Copper and Lead are both used in roofing situations because neither is very reactive and the compounds
formed do not flake away as easily as rust does from iron. Lead corrodes to a white lead oxide or
carbonate and copper corrodes to form a basic green carbonate (combination of the hydroxide
Cu(OH)2 and carbonate CuCO3 eg seen as green roof on buildings).
Both metals have been used for piping but these days lead is considered too toxic and copper is
usually used as the stronger, but equally unreactive alloy with zinc, brass. Now of course, most piping is
flowing in the plastic direction which doesn't corrode at all!
The Group 1 Alkali Metals rapidly corrode in air and need to be stored under oil.
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Apart from their structural weakness they would hardly used for any outside purpose!
DONE
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The Reactivity Series and Corrosion of Metals
The higher the metal in the series, the more reactive it is ie the faster, more vigorous and more exothermic
the reaction.
At a more theoretical level,
the more reactive a metal, the greater tendency it has to form its positive ion.
This also implies that the reverse reaction becomes more difficult ie the more reactive a metal, the more difficult it is
to extract from its ore and the metal is also more susceptible to corrosion with oxygen and water.
The reactivity series can be established by observation of the reaction of metals with water, oxygen or acids (and
also from simple cell experiments).
A metal in the series, can displace any metal below it in the series, from the less reactive metal's oxide, chloride or
sulphate compound.
o eg on heating the mixture of magnesium powder and black copper(II) oxide, white magnesium oxide is
formed with brown bits of copper:
Mg(s) + CuO(s) => MgO(s) + Cu(s)
o or adding a metal to a salt solution eg adding magnesium to blue copper(II) sulphate solution, the blue
colour fades as colourless magnesium sulphate is formed and brown bits of copper metal form a precipitate:
Mg(s) + CuSO4(aq) => MgSO4(aq) + Cu(s)
The electron transfer redox theory behind displacemet reactions is explained later.
Some general word equations where the metal does react:
o (a) metal + cold water => metal hydroxide + hydrogen (metals above aluminium)
o (b) heated metal + steam => metal oxide + hydrogen (for metals above tin?)
o (c) metal + acid => metal salt + hydrogen
if the metal is at least as reactive as lead (see reactivity series list above left)
and hydrochloric acid makes a metal chloride
and sulphuric acid makes a metal sulphate
reactions with nitric acid are complex, the nitrate is formed BUT the gas is rarely hydrogen, and
more often an oxide of nitrogen (not usually studied at GCSE level these days).
Within the general Reactivity or Activity Series of Metals there are some Periodic Table Trends
o Down Group 1 (I) the "Alkali Metals" the activity increases Cs > Rb > K > Na > Li
o Down Group 2 (II) the activity increases eg Ca > Mg
o On the same period, the Group 1 metal is more reactive than the group 2 metal, and the group 2 metal is
more reactive than the Group 3 metal, and all three are more reactive than the "Transition Metals". eg Na >
Mg > Al (on Period 3) and K > Ca > Ga > Fe/Cu/Zn etc. (on Period 4)
The reactivity of a metal has an important bearing on the method by which a metal is extracted from its ore. Since
prehistoric times, as technology has improved more and more, all metals can now be extracted and comments on
when the metals were first isolated and used are added in the table below. If the metal is above carbon, it cannot be
o
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METAL in
decreasing
reactivity order
Caesium
Cs
Rubidium
Rb
Potassium
Burns vigorously with a blue flame when heated in air to form the
white powder caesium oxide.
4Cs(s) + O2(g) ==> 2Cs2O(s)
Because it is extremely reactive, it explodes with cold water
forming the alkali caesium hydroxide and hydrogen gas.
2Cs(s) + 2H2O(l) => 2CsOH(aq) + H2(g)
Caesium was first extracted in 1860 by electrolysis of the
molten chloride CsCl.
Burns vigorously with a red flame when heated in air to form the
white powder rubidium oxide.
4Rb(s) + O2(g) ==> 2Rb2O(s)
Extremely reactive, can ignite in air, it explodes with cold water
forming the alkali rubidium hydroxide and hydrogen gas.
2Rb(s) + 2H2O(l) => 2RbOH(aq) + H2(g)
Rubidium was first extracted in 1861 by electrolysis of the
molten chloride RbCl.
Burns vigorously with a lilac flame when heated in air to form the
white powder potassium oxide.
4K(s) + O2(g) ==> 2K2O(s)
The reaction of potassium with water - the reaction is the
same as for sodium (full description below) BUT it is faster and
more exothermic AND so the hydrogen is ignited to give a purple
or lilac flame. The hydrogen flame is coloured by the excitation of
potassium atoms in the very hot flame. The very rapid reaction
with cold water forms the alkali potassium hydroxide and
hydrogen gas.
2K(s) + 2H2O(l) => 2KOH(aq) + H2(g)
Potassium was first extracted in 1807 by electrolysis of the
molten chloride KCl. [top]
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Sodium
Na
Lithium
Li
Calcium
Ca
Burns with a brick red flame when strongly heated in air to form
the white powder calcium oxide.
2Ca(s) + O2(g) ==> 2CaO(s)
Quite reactive with cold water forming the moderately soluble
alkali calcium hydroxide and hydrogen gas.
Ca(s) + 2H2O(l) => Ca(OH)2(aq/s) + H2(g)
Very reactive with dilute hydrochloric acid forming the colourless
soluble salt calcium chloride and hydrogen gas.
Ca(s) + 2HCl(aq) => CaCl2(aq) + H2(g)
Not very reactive with dilute sulphuric acid because the colourless
calcium sulphate formed is not very soluble and coats the metal
inhibiting the reaction.
Ca(s) + H2SO4(aq) => CaSO4(s) + H2(g)
Calcium was first extracted in 1808 by electrolysis of the molten
chloride CaCl2.
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Magnesium
Mg
Aluminium
Al
(Carbon C, a nonmetal)
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Zinc
Zn
Iron
Fe
Surface goes white when strongly heated in air to form zinc oxide
(yellow when hot).
2Zn(s) + O2(g) ==> 2ZnO(s)
No reaction with cold water.
When the metal is heated in steam zinc oxide and hydrogen are
formed.
Zn(s) + H2O(g) => ZnO(s) + H2(g)
Quite reactive with dilute hydrochloric acid forming the colourless
soluble salt zinc chloride and hydrogen gas.
Zn(s) + 2HCl(aq) => ZnCl2(aq) + H2(g)
Quite reactive with dilute sulphuric acid forming the colourless
soluble salt zinc sulphate and hydrogen gas.
Zn(s) + H2SO4(g) => ZnSO4(s) + H2(g)
(this reaction is catalysed by adding a trace of copper sulphate
solution)
Zinc can be extracted by reducing the hot metal oxide on heating
with carbon
2ZnO(s) + C(s) => 2Zn(s) + CO2(g)
A zinc coating (galvanising) is used to protect iron from rusting.
The more reactive zinc oxidises 1st. Blocks of zinc attached to steel
are used as 'sacrificial corrosion'.
Zinc was known and used in India and China before 1500 so it
must have been extracted like copper or iron by carbon reduction
of the oxide, sulphide or carbonate. [top]
Surface goes dark grey-black when strongly heated in air to form
a tri-iron tetroxide. When steel wool is heated in a bunsen flame it
burns with a shower of sparks - large surface area - increased rate
of reaction - so even moderately reactive iron has its moments!
3Fe(s) + 2O2(g) ==> Fe3O4(s)
No reaction with cold water (rusting is a joint reaction with
oxygen).
When the metal is heated in steam an iron oxide (unusual
formula) and hydrogen are formed. This oxide is 'technically'
diiron(III)iron(II) oxide!!!!
3Fe(s) + 4H2O(g) => Fe3O4(s) + 4H2(g)
Slow reaction with dilute hydrochloric acid forming the soluble
pale green salt iron(II) chloride and hydrogen gas.
Fe(s) + 2HCl(aq) => FeCl2(aq) + H2(g)
Slow reaction with dilute sulphuric acid forming the soluble pale
green salt iron(II) sulphate and hydrogen gas.
Fe(s) + H2SO4(g) => FeSO4(s) + H2(g)
Iron can be extracted by reducing the hot metal oxide on heating
with carbon monoxide formed from carbon in the blast
furnace eg
Fe2O3(s) + 3CO(g) => 2Fe(s) + 3CO2(g)
Fe3O4(s) + 4CO(g) => 3Fe(s) + 4CO2(g)
For the past 2500 years. iron has been extracted from pre-historic
times using charcoal (C). Known in Anglo-Saxon as 'iron' and in
Roman times in Latin as 'ferrum' hence the Fe symbol! [top]
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Tin
Sn
Lead
Pb
Hydrogen H
non-metal
Copper
Cu
Slow reaction when heated in air to form white tin(IV) oxide or tin
dioxide
Sn(s) + O2(g) ==> SnO2(s)
No reaction with cold water or when heated in steam.
Very slow reaction with dilute hydrochloric acid forming the
slightly soluble tin(II) chloride and hydrogen gas.
Sn(s) + 2HCl(aq) => SnCl2(aq) + H2(g)
Very slow reaction with dilute sulphuric acid forming the colourless
slightly soluble tin(II) sulphate and hydrogen gas.
Sn(s) + H2SO4(g) => SnSO4(s) + H2(g)
Tin can be extracted from its oxide by heating with carbon. Tin
has been known from pre-historic times. Known in Anglo-Saxon as
'tin' and in Latin - 'stannum' hence the symbol Sn! [top]
Non of the metals below hydrogen can react with acids to form hydrogen
gas. They are least easily corroded metals and partly accounts for their
value and uses in jewellery, electrical contacts etc.[top]
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No reaction when heated in air.
Silver
Ag
Gold
Au
Platinum
Pt
Iron (or steel) corrodes more quickly than most other transition metals and readily does so in the
presence of both oxygen (in air) and water to form an iron oxide. You can do simple experiments
to show that BOTH oxygen and water are needed. Put an iron nail into (1) boiled water in a sealed
tube; (2) a tube of air and a drying agent; (3) an open test tube with water. Rusting appears
overnight with (3) only.
Rusting is speeded up in the presence of salt or acid solutions because of an increased
concentration of ions. Corrosion is a redox process involving redox electron transfer and ion
movement. The rusting metal behaves like a simple cell and more ions enable the current, and
hence the electron transfer, to occur more readily.
Rusting is overall ... Fe(s) + O2(g) + H2O(l) ==> Fe2O3.xH2O(s) ie rust is a hydrated iron(III)
oxide (the equation is not meant to be balanced and the amount of water x is variable, from dry to
soggy!).
o The reaction proceeds via iron(II) hydroxide Fe(OH)2 which is the oxidised further to the
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Fe(OH)3
Rusting is an oxidation because it involves iron
gaining oxygen (Fe ==> Fe2O3) or iron atoms losing
electrons (Fe - 3e- ==> Fe3+.
o See more examples of oxidation and reduction below.
The rusting of iron is a major problem in its use as a structural
material.
Iron and steel (alloy of iron) are most easily protected by paint
which provides a barrier between the metal and air/water. Moving
parts on machines can be protected by a water repellent oil or grease layer.
This 'rusting' corrosion can be prevented by connecting iron to a more reactive metal (e.g. zinc or
magnesium). This is referred to as sacrificial protection or sacrificial corrosion, because the
more reactive protecting metal is preferentially oxidised away, leaving the protected metal intact.
The picture illustrates what might be seen after a few days.* Iron or steel can also be protected by
mixing in other metals (e.g. chromium) to make non-rusting alloys called stainless steel. The
chromium, like aluminium, forms a protective oxide layer.
* Theoretically, any iron ions formed by oxidation would be reduced by electrons from the oxidation
of the more reactive 'sacrificed' metal.
Coating iron or steel with a thin zinc layer is called 'galvanising'. The layer is produced by
electrolytic deposition by making the iron/steel the negative cathode or by dipping the iron/steel
object in molten zinc (more details). The zinc preferentially corrodes or oxidises to form a zinc oxide
layer that doesn't flake off like iron oxide rust does. Also, if the surface is scratched, the exposed
zinc again corrodes before the iron and continues to protect it.
Steel tin cans are protected by relatively unreacted tin and works well as long as the thin tin layer is
complete. HOWEVER, if a less reactive metal is connected to the iron, it then the iron rusts
preferentially (try scratching a 'tin' can and leave out in the rain and note the corrosion by the
scratch!)
o
Aluminium does not oxidise (corrode) as quickly as its reactivity would suggest. Once a thin oxide
layer of Al2O3 has formed on the surface, it forms a barrier to oxygen and water and so
prevents further corrosion of the aluminium.
Aluminium is a useful structural metal. It can be made harder, stronger and stiffer by mixing it with
small amounts of other metals (e.g magnesium) to make alloys.
Copper and Lead are both used in roofing situations because neither is very reactive and the
compounds formed do not flake away as easily as rust does from iron. Lead corrodes to a white lead
oxide or carbonate and copper corrodes to form a basic green carbonate (combination of the
hydroxide Cu(OH)2 and carbonate CuCO3 eg seen as green roof on buildings).
Both metals have been used for piping but these days lead is considered too toxic and copper
is usually used as the stronger, but equally unreactive alloy with zinc, brass. Now of course, most
piping is flowing in the plastic direction which doesn't corrode at all!
The Group 1 Alkali Metals rapidly corrode in air and need to be stored under oil.
Apart from their structural weakness they would hardly used for any outside purpose!
DONE
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times greater. The kilo Avogadro number for the count of particles in a kilomole is 6.022 x 1026.
If humans were tiny creatures (like Lilliputians) only 1/1000 our present size, milligrams would be
more convenient. This means the milligram mole would be more useful. The number of particles
handled in a milligram mole (millimole) would be 1/1000 times smaller. The milli Avogadro
number for the count of particles in a millimole is 6.022 x 1020.
+ HCl
-------------
C2H5Cl
More useful, however, is the fact that the mass ratio in grams is also 36.5 to 28.0. If we were to
combine 36.5 g HCl with 28 g ethylene in the laboratory, they would react in a 1:1 molecular ratio.
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Molar Mass for Compound
The formulas for compounds are familiar to you. You know the formula for water is H2O. It
should be reasonable that the weight of a formula unit can be calculated by adding up the
weights for the atoms in the formula.
The formula weight for water = weight from hydrogen + weight from oxygen
The formula weight for water = 2 H atoms x 1. + 1 O atom x 16. = 18.
The molar mass for water = 18. grams water.
Example 1.
What is the molar mass for sulfur dioxide, SO2 (g), a gas used in
bleaching and disinfection processes.
1. Look up the atomic weight for each of the elements in the formula.
1 sulfur atom = 32
1 oxygen atom = 16
2. Count the atoms of each element in the formula unit. .
one sulfur atom ; two oxygen atoms
3. The formula weight = weight from sulfur + weight from oxygen
4. The formula weight = 1 sulfur atom x (32 ) + 2 oxygen atoms x (16 )
5. The formula weight SO2 = 32 + 32. = 64
6. The molar mass SO2 = 64 grams SO2
Example 2: The formula for methane the major component in natural gas is CH4.
The formula weight for methane = weight from hydrogen + weight from carbon
The formula weight for methane = 4 H atoms x 1. + 1 C atom x 12. = 16.
The molar mass for methane = 16.0 grams methane
Example 3: The formula for ethyl chloride is CH3 CH2Cl.
The formula weight = weight from hydrogen + weight from carbon + weight from chlorine
The formula weight = 5 H atoms x 1.0 + 2 C atom x 12.0 + 1 Cl atom x 35.5 = 64.5
The molar mass for ethyl chloride = 64.5 grams
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2. determine the mass needed to provide 3. moles of hydrogen.
1 mole H2 = 2.0 grams H2;
2 mole H2 = 4.0 grams H2
3 mole H2 = 6.0 grams H2
The practical way is to multiply the molar mass by the number of moles. This converts
mole to grams
(3 mole H2 )(2 grams H2/ 1 mole H2 ) = 6 grams H2
Example.
How many moles of water are in a liter of water? Assume 1 liter = 1 kilogram water
1. Calculate the formula weight(mass) for water, H2O.
Look up the atomic weights in the periodic table for H and O.
The atomic weight for hydrogen is 1
The atomic weight for oxygen is 16
2. Add up the masses from all the atoms in the formula
The formula weight for water is 1 + 1 + 16 = 18
3. Determine the molar mass for water. Molar mass is a mass in grams that is
numerically the same as the formula weight.
1 mole H2O = 18.0 grams H2O
4. Convert 1000 grams of water to moles. The "conversion factor" is the molar mass.
(1000 grams H2O )(1 mole H2O/ 18. grams H2O) = 55.55 moles H2O
Example.
How many moles of sulfur dioxide, SO2 (g), are in 2000 grams of the
gas?
1. Look up the atomic weights in the periodic table for S and O.
The atomic weight for sulphur is 32
The atomic weight for oxygen is 16
2. Calculate the formula weight for SO2 . Add up the masses from all the atoms in the
formula
The formula weight for sulfur dioxide is 32 S + 2 x (16 O) = 64 SO2
3. Determine the molar mass. Molar mass is a mass in grams that is numerically the
same as the formula weight.
1 mole SO2 = 64. grams SO2
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4. Convert 2000 grams of SO2 to moles. The "conversion factor" is the molar mass.
(2000 grams SO2 )(1 mole SO2 /64. grams SO2 ) = 31.25 moles SO2,
The coefficients in the balanced equation tell the moles of each substance involved in
the equation
C :
O
:
CO
2moles : 1 mole : 2moles
The reaction between nitrogen and oxygen to produce nitrogen dioxide is analyzed
here.
The equation is N2(g) + 2 O2(g)---> 2 NO2(g)
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Exercise: What is the mol ratio for nitrogen to oxygen? Answer: 1 mole N2 : 2 moles O2
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Fe2O3(s) + 3C(s) 2Fe(l) + 3CO(g)
Step 1: Write a balanced chemical equation (or check to see that a given equation is balanced). In this
case, a balanced chemical equation was given. Organize the information in the problem. It's often
helpful to write the amounts given underneath the balanced chemical equation.
Fe2O3(s) + 3C(s) ------------2Fe(l) + 3CO(g)
100 g
?g
Step 2: Convert grams of a given substance to moles. Remember that substances react in terms of their
mole ratios, not their mass ratios. To convert grams of Fe2O3 to moles, we need to know the molar mass
of this compound.
2 x 56. g for each mol Fe + 3 x 16.0 g for each mol O
= 160 g/mol
Step 3: Use coefficients in the balanced chemical equation to find the mole ratio. Relate moles of what
you were given to moles of what you are determining using the mole ratio.
Step 4: Convert moles to grams using molar mass as a conversion factor. It's always a good idea to
check to make sure you have answered the question you were asked. Here you were asked to calculate
grams of carbon. Another step or two would be necessary if you had been asked to report your answer in
some other unit, such as kg.
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reactants involved.
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Example: What is the theoretical yield of Al2S3 when 10.0 g of aluminum is reacted with excess
sulfur according to the equation below?
Next, we relate moles of aluminum to moles of product using the stoichiometric coefficients as a
mole ratio:
Example: A student performing the reaction above collected 18.7 g Al2S3. What is her percent
yield?
Percent Yield
The percent yield is defined as
The predicted yield is determined by the masses used in a reaction and the mole ratios in the
balanced equation. This predicted yield is the "ideal". It is not always possible to get this amount
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of product. Reactions are not always simple. There often are competing reactions. For example, if
you burn carbon in air you can get carbon dioxide and carbon monoxide formed. The two
reactions occur simultaneously. Some carbon atoms end up in CO and others end up in CO2
Example:
What is the percent yield for a reaction if you predicted the formation of 21. grams of
C6H12 and actually recovered only 3.8 grams?
1. Recall
definition of
percent yield.
Example:
A reaction between solid sulfur and oxygen produces sulfur dioxide.
The reaction started with 384 grams of S6 (s). Assume an unlimited supply of
oxygen. What is the predicted yield and the percent yield if only 680 grams of
sulfur dioxide are produced?
1 S6 (s)
6 O2 (g)
6 SO2 (g)
Step 1 : Calculate the molar masses for S6 (s) and SO2(g). The oxygen has no effect on the
answer because there is more than you need.
1 mole S6 (s)= 193 grams S6 (s); 1 mole SO2(g) = 64 grams SO2(g)
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moles S6 (s) = [384 g S6 (s)][ 1 mole S6 (s)/ 192 g S6 (s)] = 2 moles S6 (s)
Step 4: Calculate the moles of SO2(g) expected using the mole ratio 6 SO2(g) / 1 S6 (s)
moles SO2(g) = 2 moles S6 (s)[6 SO2(g) / 1 S6 (s)] = 12 moles SO2(g)
Step 5: Calculate the grams of SO2(g) predicted using 1 mole SO2(g) = 64 grams SO2(g)
grams SO2(g) = 12 moles SO2(g)[64 grams SO2(g)/1 mole SO2(g)] = 768 g SO2(g)
Step 6: Calculate the percent yield using the definition
Percent yield = 100[actual yield/ predicted yield] = 100[680 grams SO2(g)/ 768 g SO2(g)]= 89%
In the laboratory, solutions are prepared according to several steps. Let's prepare 250 mL of a 0.100 M
solution of NaCl. (Unless otherwise noted, solutions are aqueous and water is the solvent.)
First, we have to do a calculation. We need to know how many grams of NaCl to weigh.
0.250 L (0.100 mol NaCl/dm3 solution)
= 0.0250 mol NaCl (58.5 g/mol)
= 1.46 g NaCl.
Next, we weigh this amount on a balance and transfer the solid to a 250 mL volumetric flaska very
precise piece of glassware designed to contain only a specific volume of liquid.
Finally, we add our solventin this case, waterto the flask. First, we add a small amount to dissolve
the solute. Then we add water up to the calibration mark on the flask and mix well.
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Solution Stoichiometry
Moles/dm3 serves as a useful link between the volume of a solution and the number of moles of a solute.
The flow diagram below summarizes the steps in stoichiometry calcuations involving solutions.
Example:
How many mL of a 0.90 M solution of HCl is
required to react with 4.16 g CaCO3, according
to the equation below?
CaCO3(s) + 2 HCl(aq)-------CaCl2(aq) +
CO2(g) + H2O(l)
In this problem, we are given the
concentration of the HCl solution. We are
given a mass in grams of one of the reactants.
So our first step is to convert mass to moles.
4.16 g CaCO3 (1 mol/100 g) = 4.16 x10-2 mol
CaCO3
Next, we relate moles of CaCO3 to moles of
HCl required using the coefficients in the
balanced equation. The reaction ratio is 2:1
respectively
4.16 x 10-2 mol CaCO3 (2 mol HCl / 1 mol
CaCO3) = 8.31 x 10-2 mol HCl
Now we can convert moles of HCl to volume of HCl using the moles/dm3.
8.31 x 10-2 mol HCl (1 dm3 solution / 0.90 mol HCl) = 9.23 x 10-2 L HCl solution
9.23 x 10-2 L (1000 mL / L) = 92.3 mL HCl solution
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The Rates of
Chemical Reactions
The phrase rate of reaction means how fast is the reaction. It can be measured as the
'rate of formation of product' or the 'rate of disappearance of reactant'.
o Rusting is a slow reaction, you hardly see any change looking at it!,
o weathering of rocks is a very slow reaction,
o fermentation of sugar to alcohol is quite slow but you can see the carbon dioxide
bubbles forming in the 'froth'!
o a fast reaction would be magnesium dissolving in hydrochloric acid,
o and an explosion and burning/combustion reactions would be described as very
fast!
The importance of "Rates of Reaction knowledge":
o Time is money in industry, the faster the reaction can be done, the more economic
it is.
Hence the great importance of catalysts eg transition metals or enzymes.
o Health and Safety Issues:
Mixtures of flammable gases in air present an explosion hazard (gas
reactions like this are amongst the fastest reactions known).
eg Methane gas in mines, petrol vapour etc. so knowledge of
'explosion/ignition threshold concentrations', ignition
temperatures and activation energies are all important knowledge
to help design systems of operation to minimise risks.
Flammable fine dust powders can be easily ignited eg coal dust in
mines, flour in mills.
Fine powders have a large surface area which greatly
increases the reaction rate causing an explosion. Any spark
from friction is enough to initiate the reaction!
A reaction will continue until one of the reactants is used up.
To measure the speed or rate of a reaction depends on what the reaction is, and can
what is formed be measured as the reaction proceeds? Two examples are outlined
below.
When a gas is formed from a solid reacting with a solution, it can be collected in a gas
syringe (see diagram below and the graph).
o The initial gradient of the graph eg in cm3/min gives an accurate measure of how
fast the gaseous product is being formed.
o If the reaction is allowed to go on, you can measure the final maximum volume of
gas and the time at which the reaction stops.
Reactions involving:
o
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o
o
o
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The rate of a reaction that produces a gas can also be measured by following the mass
loss as the gas is formed and escapes from the reaction flask.
o The method is ok for reactions producing carbon dioxide or oxygen,
o but not very accurate for reactions giving hydrogen (low mass loss).
When sodium thiosulphate reacts with an acid, a yellow precipitate of sulphur is formed.
o To follow this reaction you can measure how long it takes for a certain amount of
sulphur to form.
o You do this by observing the reaction down through a conical flask, viewing a
black cross on white paper (see diagram below).
o The X is eventually obscured by the sulphur precipitate and the time noted.
o sodium thiosulphate + hydrochloric acid ==> sodium chloride + sulfur dioxide +
water + sulphur
o Na2S2O3(aq) + 2HCl(aq) ==> 2NaCl(aq) + SO2(aq) + H2O(l) + S(s)
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Mix
Ongoing
Watch stopped
By using the same flask and paper X you can obtain a relative measure of the speed of
the reaction in forming the same amount of sulphur.
The speed or rate of reaction can expressed as 'x amount of sulphur'/time, so the rate is
proportional to 1/time for a given set
o You can investigate the effects of
(a) the hydrochloric acid or sodium thiosulphate concentration
(b) the temperature of the reactants.
Reactions can only happen when the reactant particles collide, but most collisions are
not successful in forming product molecules.
The minority high kinetic energy collisions between particles which do produce a
chemical change are called 'fruitful collisions'
The reactant molecules must collide with enough energy to break the original bonds so
those new bonds in the product molecules can be formed.
All the rate-controlling factors are to do with the frequency and energy of reactant
particle collision.
In the case of temperature, the energy of the collision is even more important than the
frequency effect.
The particle theory of gases and liquids and the diagrams below will help you understand
what is going on.
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In doing rate experiments with a solid reactant (eg marble chips-acid solution) or a solid
catalyst (manganese(IV) oxide-hydrogen peroxide solution) it is sometimes forgotten
that stirring the mixture is an important rate factor.
If the reacting mixture is not stirred evenly then the reactant concentration in solution
becomes much less near the solid, which tends to settle out.
At the bottom of the flask the reaction prematurely slows down distorting the overall
rate measurement and making the results uneven and therefore inaccurate.
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If a solid reactant or a solid catalyst is broken down into smaller pieces the rate of
reaction increases.
The speed increase happens because smaller pieces of the same mass of solid have a
greater surface area compared to larger pieces of the solid.
Therefore, there is more chance that a reactant particle will hit the solid surface and
react.
The diagrams below illustrate the acidmarble chip reaction, but they could also
represent a solid catalyst in a solution of reactants.
When gases or liquids are heated the particles gain kinetic energy and move faster (see
diagrams below).
The increased speed increases the chance of collision between reactant molecules and
the rate increases.
However this is not the main reason for the increased reaction speed.
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The effect of a Catalyst (see also light effect and graphs)
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Light energy (uv or visible radiation) can initiate or catalyse particular chemical
reactions.
o As well as acting as an electromagnetic wave, light can be considered as an
energy 'bullets' called photons and they have sufficient 'impact' to break chemical
bonds, that is, enough energy to overcome the activation energy.
Examples:
o Silver salts are converted to silver in the chemistry of photographic exposure of
the film.
Silver chloride (AgCl), silver bromide (AgBr) and silver iodide (AgI) are all
sensitive to light ('photosensitive'), and all three are used in the
production of various types of photographic film to detect visible light and
beta and gamma radiation from radioactive materials.
Each silver halide salt has a different sensitivity to light.
When radiation hits the film the silver ions in the salt are reduced by
electron gain to silver
Ag+ + e- ==> Ag, the halide ion is oxidised to the halogen molecule
2X- ==> X2 + 2e AgI is the most sensitive and used in X-ray radiography, AgCl is the most
sensitive and used in 'fast' film for cameras.
o Photosynthesis in green plants:
The conversion of water + carbon dioxide ==> glucose + oxygen
6H2O(l) + 6CO2(g) ==> C6H12O6(aq) + O2(g) requires the input of sunlight
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energy
The green chlorophyll molecules absorb the photon energy packets and
initiate the chemical changes shown above.
Photochemical Smog:
This is very complex chemistry involving hydrocarbons, carbon monoxide,
ozone, nitrogen oxides etc.
Many of the reactions to produce harmful chemicals are catalysed by light
energy.
More examples of interpreting graphical results (see two other graphs and notes)
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W might represent taking double the quantity of reactants to forming twice as much gas eg same volume
of reactant solution but doubling the concentration, so producing twice as much gas with initially double
the speed (gradient).
DONE
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Introduction to electrolysis
Electrolysis is the process of electrically inducing chemical changes in a conducting melt or
solution eg splitting an ionic compound into the metal and
non-metal.
SUMMARY OF COMMON ELECTRICAL
CONDUCTORS and what makes up the circuit?
o These materials carry an electric current
via freely moving electrically charged
particles, when a potential difference
(voltage!) is applied across them, and they
include:
o All metals (molten or solid) and the nonmetal carbon (graphite).
This conduction involves the movement of free or delocalised electrons
(e- charged particles) and does not involve any chemical change.
Any molten or dissolved material in which the liquid contains free moving ions is called
the electrolye. Compounds that dissociate to a large extent (70 to 99%) into ions when dissolved in
water are classified as strong electrolytes. Compounds that dissociate to a small extent are termed weak
electrolytes.
Ions are charged particles eg Na+ sodium ion, or Cl- chloride ion, and
their movement or flow constitutes an electric current, because a current is
moving charged particles.
What does the complete electrical circuit consist of?
There are two ion currents in the electrolyte flowing in opposite directions
+
positive cations eg Na attracted to the negative cathode
electrode,
and negative anions eg Cl attracted to the positive anode
electrode,
remember no electrons, they flow in metal wires or carbon
(graphite)!
The circuit of 'charge flow' is completed by the electrons moving
around the external circuit eg copper wire, metal or graphite
electrode, from the positive to the negative electrode
The molten or dissolved materials are usually acids, alkalis or salts and
their electrical conduction is usually accompanied by chemical changes
eg decomposition.
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The chemical changes occur at the electrodes which connect the electrolyte liquid
containing ions with the external d.c. electrical supply.
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and non-metals eg oxygen, chlorine, bromine etc. are formed from negative
ions changing on the positive electrode by electron loss (oxidation), eg in
molten sodium chloride
chloride ions change to green chlorine gas, 2Cl -2e ==> Cl2.
In a chemical reaction, if an oxidation occurs, a reduction must also occur too (and
vice versa) so these reactions 'overall' are called redox changes.
o You need to be able to complete and balance electrode equations or recognise them and
derive an overall equation for the electrolysis.
o
+ 2 electrons
----------------
Lead atoms.
+ 2 e ----------------- Pb
Br2
+ 2 electrons
+ 2e
Lead Bromide------------
Molten lead
Bromine gas
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Electrolysis of Molten Bauxite
Electrolyte:
Electrodes:
Ions present:
Raw materials for the electrolysis process: The redox details of the electrode processes:
2O2- ==> O2 + 4e
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freely moving ions which carry the
charge of the electric current.
...
o
o
o
+ 3 electrons
----------------
Molten Aluminum
3O2
+ 12 electrons
+ 12e
4Al (l)
+ 6O2 (g)
ELECTROLYSIS OF SOLUTIONS
Electrolysis of Brine
Electrolyte:
Electrodes:
Ions present:
Sodium chloride solution gives equal volumes of hydrogen gas (-) and
green chlorine gas (+) with sodium hydroxide left in solution. However in
dilute solution, oxygen gas as well as chlorine gas is produced.
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Reaction at cathode ( negative electrode)
Hydrogen ions
2H+
+ 2e
-----------------
+ 2e ---------------------
Hydrogen gas.
H2 (g)
Cl2
+ 2e
+ H2O (l)
----------------------
H2(g)
+ Cl2(g)
NaOH (aq).
Hydrogen ions
2H+
+ 2e
-----------------
+ 2e ---------------------
Hydrogen gas.
H2 (g)
Cl2
+ 2e
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Chlorine gas liberated at anode.
Over all reaction
----------------------
H2(g)
+ Cl2(g)
Hydrogen ions
2H+
+ 2e
-----------------
+ 2e ---------------------
Hydrogen gas.
H2 (g)
2H2(g)
O2(g)
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Copper(II) sulphate with copper electrodes, the copper deposits at cathode and the copper dissolves from
anode. The blue colour of the Cu2+ ions stays constant because Cu deposited = Cu dissolved. Both involve a 2
electron transfer so it means mass of Cu deposited = mass of Cu dissolving.
Copper ions
2e
-----------------
Copper atoms.
Cu2+
+ 2e ---------------------
Cu (s)
---------------------
Cu(s) --------------------
+ 2e
Cu2+(aq) + 2e
+ 2e -----------------
+ 2e ---------------------
Copper atoms.
Cu (s)
Oxygen gas
4OH-(aq) -----------------------
O2(g)
+ Water + 4 electrons
+ 2H2O (l)
+ 4e
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ELECTROLYSIS OF SOLUTIONS USING INERT ELECTRODES
ELECTROLYTE
IONS
IN
SOLUTIONS
Concentrated HCl
H+ (aq)
PRODUCT
AT
(-)
CATHODE
Hydrogen gas
Cl- (aq)
PRODUCT
(+) ANODE
AT
Chlorine gas
Hydrogen
gas Chlorine gas
from water
Hydrogen gas
Oxygen gas from
water
Copper metal
Oxygen gas from
water
PRODUCT AT CATHODE
Nickel
Lead
Hydrogen
Copper
Silver
ANION
PRODUCT AT ANODE
ClBrI-
Chlorine
Bromine
Iodine
SO42-
NO3-
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ELECTROPLATING
The coating of a metal object with another
metal object is called Electroplating. It is
carried out in a cell called plating bath. It
contains an electrolyte. For silver plating
electrolyte is a solution of silver salt. The
article to be plated is made the cathode in the
cell so that metal ions move to it when current
is switched on.
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4. Simple Cells or batteries
In electrolysis, electrical energy is taken in (endothermic) to
enforce the oxidation and reduction to produce the products.
The chemistry of simple cells or batteries is in principle the
opposite of electrolysis.
A redox reaction occurs to produce products and energy is
given out. It is exothermic, BUT the energy is released as
electrical energy and the system shouldn't heat up.
A simple cell can be made by dipping two different pieces of metal (of different
reactivity) into a solution of ions eg a salt or dilute acid.
The greater the difference in reactivity, the bigger the voltage produced. However
this is not a satisfactory 'battery' for producing even a small continuous current.
One of the first practical batteries is called the 'Daniel cell'.
o It uses a half-cell of copper dipped in copper(II) sulphate,
o and in electrical contact with a 2nd half-cell of zinc dipped in zinc sulphate
solution.
o The zinc is the more reactive, and is the negative electrode, releasing
electrons because
2+
on it zinc atoms lose electrons to form zinc ions, Zn(s) ==> Zn (aq) +
2eo The less reactive metal copper, is the positive electrode, and gains electrons
from the negative electrode through the external wire connection and here ..
2+
the copper(II) ions are reduced to copper atoms, Cu (aq) + 2e ==>
Cu(s)
o Overall the reactions is: Zn(s) + CuSO4(aq) + ZnSO4(aq) + Cu(s)
2+
2+
or ionically: Zn(s) + Cu (aq) + Zn (aq) + Cu(s)
o The overall reaction is therefore the same as displacement reaction, and it is
a redox reaction involving electron transfer and the movement of the
electrons through the external wire to the bulb or voltmeter etc. forms the
working electric current.
The cell voltage can be predicted by subtracting the less positive voltage from the
more positive voltage:
o eg a magnesium and copper cell will produce a voltage of (+0.34) - (-2.35) =
2.69 Volts
o or an iron and tin cell will only produce a voltage of (-0.15) - (-0.45) = 0.30
Volts.
o Note (i) the bigger the difference in reactivity, the bigger the cell voltage
produced and
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(ii) the 'half-cell' voltages quoted in the diagram are measured against the
H+(aq)/H2(g) system which is given the standard potential of zero volts.
Cells or batteries are useful and convenient portable sources of energy but they are expensive
compared to what you pay for 'mains' electricity.
o
5. Fuel Cells
Hydrogen gas can be used as fuel.
o It burns with a pale blue flame in air reacting with oxygen to be
oxidised to form water.
hydrogen + oxygen ==> water or 2H2(g) + O2(g) ==> 2H2O(l)
o It is a non-polluting clean fuel since the only combustion product is
water.
o It would be ideal if it could be manufactured by electrolysis of
water eg using solar cells.
o Hydrogen can be used to power fuel cells.
o
It all sounds wonderful BUT, still technological problems to
solve for large scale manufacture and distribution of 'clean'
hydrogen gas or use in generating electricity AND its rather an
inflammable explosive gas!
Fuel cells are 'battery systems' in which two reactants can be
continuously fed in. The consequent redox chemistry produces a working
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current.
Hydrogen's potential use in fuel and energy applications includes powering
vehicles, running turbines or fuel cells to produce electricity, and
generating heat and electricity for buildings and very convenient for
remote and compact situations like the space shuttle.
When hydrogen is the fuel, the product of its oxidation is water, so this is
potentially a clean non-polluting and non-greenhouse gas? fuel.
Most fuel cells use hydrogen, but alcohols and hydrocarbons can be used.
A fuel cell works like a battery but does not run down or need recharging
as long as the 'fuel' supply is there.
It will produce electricity and heat as long as fuel (hydrogen) is supplied.
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together in series to give a bigger working voltage.
o
o
o
equation
1 oxidation
2
reduction
3=1+2
DONE
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Acids, Bases and Salts
BASES eg oxides and hydroxides are substances that react and neutralise
acids to form salts and water. Bases which are soluble in water are
called alkalis.
Acids
Some common acids are listed below:
Name
Hydrochloric acid
Sulphuric acid
Nitric acid
Ethanoic (acetic) acid
Methanoic (formic) acid
Citric Acid
Formula
HCl
H2SO4
HNO3
CH3COOH
HCOOH
C6H8O7
Strong/Weak
Strong
Strong
Strong
Weak
Weak
Weak
Where is it found?
The stomach, in the lab.
Acid rain, car batteries, the lab.
Acid rain, in the lab.
Vinegar
Ant & nettle stings, descalers
Citrus fruits
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Bases
Most bases are oxides or hydroxides of metals. Not all bases fit into these categories,
however (e.g. ammonia). Some examples of bases are shown below:
Name
Sodium hydroxide (caustic soda)
Calcium hydroxide
Magnesium oxide (magnesia)
Calcium carbonate
Sodium hydrogencarbonate (bicarbonate)
Ammonia
Formula
NaOH
Ca(OH)2
MgO
CaCO3
NaHCO3
NH3
Where is it found?
Oven cleaners, in the lab.
Soil lime, limewater
Indigestion tablets
Limestone, soil lime
Baking powder
Cleaning fluids, in the lab.
Reactions of Acids
With metals
Metals above copper in the reactivity series will react with acids, giving off hydrogen
gas. The metal dissolves, forming a salt.
e.g.
This is why acids corrode metals, and must be stored in glass containers.
e.g.
e.g.
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Neutralisation
Acids are neutralised by bases. If you have indigestion (too much acid in the stomach),
you may take a tablet containing a base (e.g. magnesia, MgO). A farmer may spread lime
(calcium hydroxide, Ca(OH)2) on fields to make the soil less acidic.
What happens during a neutralisation reaction?
ACID + ALKALI SALT + WATER
e.g.
To understand why water is formed, we must consider what happens to the ions that are
present in the reacting solutions:
H+(aq) + Cl-(aq) + Na+(aq) + OH-(aq) Na+(aq) + Cl-(aq) + H2O(l)
(from HCl)
(from NaOH)
The H+ ions from the acid combine with the OH- ions from the alkali we can show this
by writing a simple ionic equation:
H+(aq) + OH-(aq) H2O(l)
Water is formed. So if equal amounts of acid and alkali are mixed, the resulting solution
will be neutral.
The Na+ and Cl- ions do not take part in the neutralisation reaction, they just remain in
solution - they are spectator ions. It is unnecessary to include them in the ionic equation.
When an acid and a base are mixed in stoichiometric proportions, their acidic and
basic properties disappear as the result of a neutralization reaction.
Because the salts that form in neutralization reaction are generally strong electrolytes,
we can write the neutralization reaction as an ionic equation.
When the spectator ions are removed, the net ionic equation is revealed.
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This net ionic equation is the same for the neutralization reaction of any strong acid
and strong base.
For the reaction of a weak acid with a strong base, a similar neutralization occurs.
Consider the neutralization of HF with KOH.
HF(aq) + KOH(aq)
KF(aq) + H2O(l)
K+(aq) + F-(aq) +
F-(aq) + H2O(l)
molecular equation
ionic equation
net ionic equation
Formation of H30+ion
The hydrogen ion H+(aq) does not exist as such in aqueous solutions. Hydrogen ions
combine with water molecules to give a more stable species, the hydronium ion H3O+,
as demonstrated in the following equation:
HCl(aq) + H2O(l)
H3O+(aq) + Cl-(aq)
Acids can contain different numbers of acidic hydrogens, and can yield different numbers
of H3O+ ions in solution.
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Oxygen combines with most other elements to form oxides of varying physical
chemical character.
o On the left and middle of the Periodic Table are the basic metal oxides which
react with acids to form salts eg Na2O, MgO, CuO etc. These metal oxides tend
to be ionic in bonding character with high melting points. The Group 1 Alkali
Metals, and to a less extent, Group 2 oxides, dissolve in water to form alkali
solutions. All of them react with , and neutralise acids to form salts.
o As you move left to right the oxides become less basic and more acidic.
o So on the right you have the acidic oxides of the non-metals CO2, P2O5,
SO2, SO3 etc. These tend to be covalent in bonding character with low
melting/boiling points. Those of sulphur and phosphorus are very soluble in
water to give acidic solutions which can be neutralised by alkalis to form salts.
o These oxides are another example of the change from metallic element
to non-metallic element chemical behaviour from left to right across
the Periodic Table.
o BUT life is never that simple in chemistry!:
Some oxides react with both acids and alkalis and are called
amphoteric oxides. They are usually relatively insoluble and have little
effect on indicators. An example is aluminium oxide dissolves in acids
to form 'normal' aluminium salts like the chloride, sulphate and nitrate.
However, it also dissolves in strong alkali's like sodium hydroxide solution
to form 'aluminate' salts. This could be considered as 'intermediate'
basic-acidic character in the Periodic Table.
Some oxides are neutral, tend to be of low solubility in water and
have no effect on litmus, and do not react with acids or alkalis. eg CO
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carbon monoxide (note that CO2 carbon dioxide is weakly acidic) and NO
nitrogen monoxide (note that NO2 nitrogen dioxide is strongly acidic in
water). There is no way of simply predicting this kind of behaviour from
periodic table patterns!
Salts
We have seen that when an acid reacts with a base, a salt is formed:
e.g.
Here sodium sulphate (Na2SO4) is the salt formed. Salts are ionic compounds.
The metal ion is provided by the base (in this case sodium ions, Na+).
The non-metal ion is provided by the acid (in this case sulphate ions, SO42-).
Note: Ammonia (NH3) is an unusual base - it does not contain a metal. It forms
ammonium salts, containing the ammonium ion, NH4+.
e.g.
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All common chlorides, except lead and silver chlorides
All common sulphates, except lead, barium and calcium sulphates
Apparatus used: (1) balance, measuring cylinder, beaker and glass stirring rod; (2)
beaker/rod, bunsen burner, tripod and gauze; (3) filter funnel and filter paper, evaporating
(crystallising) dish; (4) evaporating (crystallising) dish. (ii) A measuring cylinder is adequate for
measuring the acid volume, you do not need the accuracy of a pipette or burette required in
method (a).
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Add excess metal carbonate to acid. Wait until no more CO2 is evolved.
Filter to remove excess carbonate, then continue as in method 1
Method 4 (Acid + Alkali)
This is useful for making salts of reactive
metals, and ammonium salts. It is different
from methods 1-3, as both reactants are in
solution. This means neutralisation must be
achieved, by adding exactly the right amount
of acid to neutralise the alkali. This can be
worked out by titration
e.g.
sodium hydroxide + hydrochloric acid
sodium chloride + water
ammonia + sulphuric acid ammonium sulphate
(1) A known volume of acid is pipetted into a conical flask and universal indicator added. The
acid is titrated with the alkali in the burette
(2) until the indicator turns green.
(3). The volume of alkali needed for neutralisation is then noted, this is called the
endpoint. (1-3) are repeated with both known volumes mixed together BUT without the
contaminating indicator.
(4) The solution is transferred to an evaporating dish and heated to partially evaporate the
water.
(5) The solution is left to cool to complete the crystallisation.
(6) The residual liquid can be decanted away and the crystals can be carefully collected and
dried by 'dabbing' with a filter paper OR the crystals can be collected by filtration (below) and
dried (as above).
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Making Insoluble Salts
Insoluble salts cannot be prepared by acid-base reactions in the same way as soluble salts.
Insoluble salts are prepared by precipitation. This involves mixing solutions of two
soluble salts that between them contain the ions that make up the insoluble salt. Here is
an example:
barium chloride + magnesium sulphate barium sulphate + magnesium chloride
(soluble salt)
(soluble salt)
(insoluble salt)
(soluble salt)
BaCl2(aq) + MgSO4(aq) BaSO4(s) + MgCl2(aq)
When the two solutions are mixed, a white solid precipitate of barium sulphate is
formed.
Let us consider what happens to the ions involved in the reaction:
Ba2+
ClCl-
Ba2+ ClClMg2+
SO42-
Mg2+
SO42-
precipitate of
solid BaSO4
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The ionic equation for the reaction is:
Ba2+(aq) + SO42-(aq) BaSO4(s)
Notice this equation does not include the spectator ions, only the ions that combine to
form the precipitate.
Once the reaction is complete, the precipitate can be filtered off, washed with distilled
water and dried.
This method can also be used to prepare many insoluble metal hydroxides and
carbonates.
All common hydroxides/carbonates are insoluble except sodium, potassium and
ammonium hydroxides/carbonates.
e.g.
The ionic equation for this reaction, which shows the formation of the precipitate whilst
missing out the spectator ions is as follows:
Fe3+(aq) + 3OH-(aq) Fe(OH)3(s)
Types of Salts
Normal Salts:
Normal salts are formed when all the replaceable hydrogen ions in the acid have been
completely replaced by metallic ions.
HCl(aq)
H2SO4(aq)
+ NaOH(aq)
+ ZnO(aq)
NaCl(aq) + H2O(l)
ZnSO4(aq) + H2O(l)
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acid salt, while acid with three replaceable hydrogen ions e.g. H3PO4 will form two
different acid salts.
H2SO4(aq) + KOH(aq)
H3PO4(aq) + NaOH
H3PO4(aq) + 2NaOH(aq)
KHSO4(aq) + H2O(l)
NaH2PO4(aq) + H2O(l)
Na2HPO4(aq) + 2H2O(l)
An acid salt will turn blue litmus red. In the presence of excess metallic ions an acid salt
will be converted into a normal salt as its replaceable hydrogen ions become replaced.
Basic Salts:
Basic salts contain the hydroxide ion, OH-. They are formed when there is insufficient
supply of acid for the complete neutralization of the base. A basic salt will turn red litmus
blue and will react with excess acid to form normal salt.
Zn(OH)2(s) + HCl(aq)
Zn(OH)Cl(aq)
Zn(OH)Cl(aq) + HCl(aq)
Mg(OH)2(s) + HNO3(aq)
Mg(OH)NO3(aq)
+ HNO3(aq)
+ H2O(l)
ZnCl2(aq) + H2O(l)
Mg(OH)NO3(aq) + H2O(l)
Mg(NO3)2(aq) + H2O(l)
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INDICATORS.
Indicators are the substances that have different colors in acidic and in
alkaline solution. Some important indicators are given below
S.No. Indicator
Color in strongly
acidic solution
pH at which
color changes
Color in strongly
alkaline solution
1.
methyl orange
red
yellow
2.
bromothymol
blue
yellow
blue
3.
phenolphthalein
colorless
red
4.
screened methyl
orange
red
green
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M = Li, Na, K
[usually Group 1],
the ion is M+
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MHCO3 (hydrogencarbonate HCO3-, soluble,
mild alkali)
MO (oxide, often insoluble base)
M(OH)2 (hydroxide, often insoluble, alkali if
soluble)
MCO3 (carbonate, often insoluble)
MCl2 (chloride)
MSO4 (sulphate)
M(NO3)2 (nitrate)
the ammonium
ion in the salts
from ammonia,
NH4+
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7b. Na2CO3(s) + 2HCl(aq) ==> 2NaCl(aq) + H2O(l) + CO2(g)
8a. sodium hydroxide + hydrochloric acid ==> sodium chloride + water
8b. NaOH(aq) + HCl(aq) ==> NaCl(aq) + H2O(l)
9a. sodium hydrogencarbonate + hydrochloric acid ==> sodium chloride + water +
carbon dioxide
9b. NaHCO3(s) + HCl(aq) ==> NaCl(aq) + H2O(l) + CO2(g)
IONIC EQUATIONS
Aqueous Reactions and Net Ionic Equations
The equations written up to this point have been molecular equations. All substances have been
written using their full chemical formulas as if they were molecules. Because we now know that
strong electrolytes dissociate in water to their component ions, it is more accurate to write an ionic
equation in which all of the ionic species are shown.
In many reactions only certain ions change their 'chemical state' but other ions remain in
exactly the same original physical and chemical state.
The ions that do not change are called 'spectator ions'.
The ionic equation represents the 'actual' chemical change and omits the spectator ions.
When reactions between ions occur, at least one kind of ion is removed from the "field of action".
Simply put, its concentration decreases as the reaction proceeds.
There are three ways to remove ions:
1. Formation of an insoluble precipitate
2. Formation of a weakly ionized substance, and
3. Oxidation or reduction of an ion
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Let's examine each way individually:
1) Formation of An Insoluble Precipitate
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b) Weak electrolytes in solution, e.g.:
(1) Acid-base reactions: Acids can be defined as proton donors. A base can be defined as
a proton acceptor.
o eg any acid-alkali neutralisation involves the hydroxide ion is (base) and this accepts a
proton from an acid.
HCl(aq) + NaOH(aq) ==> NaCl(aq) + H2O(l) which can be re-written as
H+Cl-(aq) + Na+OH-(aq) ==> Na+Cl-(aq) + H2O(l)
H+(aq) + OH-(aq) ==> H2O(l)
the spectator ions are Cl- and Na+
(2) Insoluble salt formation: An insoluble salt is made by mixing two solutions of soluble
compounds to form the insoluble compound in a process called 'precipitation'.
o (a) Silver chloride is made by mixing solutions of solutions of silver nitrate and sodium
chloride.
silver nitrate + sodium chloride ==> silver chloride + sodium nitrate
Ag+NO3-(aq) + Na+Cl-(aq) ==> AgCl(s) + Na+NO3-(aq)
the ionic equation is: Ag+(aq) + Cl-(aq) ==> AgCl(s)
the spectator ions are NO3- and Na+
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(b) Silver nitrate and hydrochloric acid -- precipitate formation
Lead(II) iodide can be made by mixing lead(II) nitrate solution with potassium iodide
solution.
lead(II) nitrate + potassium iodide ==> lead(II) iodide + potassium nitrate
Pb(NO3)2(aq) + 2KI(aq) ==> PbI2(s) + 2KNO3(aq)
the ionic equation is: Pbg2+(aq) + 2I-(aq) ==> PbI2(s)
the spectator ions are NO3- and K+
o (c) Calcium carbonate forms on eg mixing calcium chloride and sodium carbonate
solutions
calcium chloride + sodium carbonate ==> calcium carbonate + sodium chloride
CaCl2(aq) + Na2CO3(aq) ==> CaCO3(s) + 2NaCl(aq)
ionically: Ca2+(aq) + CO32-(aq) ==> CaCO3(s)
the spectator ions are Cl- and Na+
o (d) Barium sulphate forms on mixing eg barium chloride and dilute sulphuric acid
barium chloride + sulphuric acid ==> barium sulphate + hydrochloric acid
BaCl2(aq) + H2SO4(aq) ==> BaSO4(s) + 2HCl(aq)
ionically: Ba2+(aq) + SO42-(aq) ==> BaSO4(s)
the spectator ions are CO32- and H+
(3) Redox reaction analysis:
o (a) magnesium + iron(II) sulphate ==> magnesium sulphate + iron
Mg(s) + FeSO4(aq) => MgSO4(aq) + Fe(s)
this is the 'ordinary molecular' equation for a typical metal displacement
reaction, but this does not really show what happens in terms of atoms, ions and
electrons, so we use ionic equations like the one shown below.
The sulphate ion SO42-(aq) is called a spectator ion, because it doesn't change in
the reaction and can be omitted from the ionic equation. No electrons show up in the
full equations because electrons lost by x = electrons gained by y!!
Mg(s) + Fe2+(aq) ==> Mg2+(aq) + Fe(s)
Mg oxidised by electron loss, Fe2+ reduced by electron gain
o (b) zinc + hydrochloric acid ==> zinc chloride + hydrogen
Zn(s) + 2HCl(aq) => ZnCl2(aq) + H2(g)
the chloride ion Cl- is the spectator ion
Zn(s) + 2H+(aq) ==> Zn2+(aq) + H2(g)
Zn oxidised by electron loss, H+ reduced by electron gain
o (c) copper + silver nitrate ==> silver + copper(II) nitrate
Cu(s) + 2AgNO3(aq) ==> 2Ag + Cu(NO3)2(aq)
the nitrate ion NO3- is the spectator ion
Cu(s) + 2Ag+(aq) ==> 2Ag(s) + Cu2+(aq)
Cu oxidised by electron loss, Ag+ reduced by electron gain
o (d) halogen (more reactive) + halide salt (of less reactive halogen) ==> halide salt (of
more reactive halogen) + halogen (less reactive)
X2(aq) + 2K+Y(aq) ==> 2K+X(aq) + Y2(aq)
X2(aq) + 2Y-(aq) ==> 2X-(aq) + Y2(aq)
the potassium ion K+ is the spectator ion
halogen X is more reactive than halogen Y, F > Cl > Br > I)
o
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DONE
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Industrial Chemistry
Limestone, is a sedimentary rock formed by the mineral and 'shelly' remains of marine organisms,
including coral, in warm shallow fertile seas. It is chemically mainly calcium carbonate and is a useful
material that is quarried and used directly as a building material. It reacts with acids - 'fizzing'
due to carbon dioxide formation - test with 'limewater' - milky white precipitate.
It is a valuable natural mineral resource and is quarried in large quantities in many countries (see
environmental impact).
Other uses of limestone rock are outlined below and it is an important raw material in the
manufacture of cement and glass and iron.
Powdered limestone can be used to neutralise acidity in lakes and soils
When limestone is heated in a kiln at over 900oC, it breaks down into quicklime (calcium
oxide) and carbon dioxide. Both are useful products. This type of reaction is endothermic and an
example of thermal decomposition (and other carbonates behave in a similar way).
o calcium carbonate (limestone) ==> calcium oxide (quicklime) + carbon dioxide
CaCO3(s)
CaO(s) + CO2(g)
This is a reversible endothermic reaction. To ensure the change is to favour the right
hand side, a high temperature of over 900oC is needed as well as the continual removal of the
carbon dioxide.
Note on other carbonates These also show a similar thermal decomposition to CaCO3 above ...
o copper(II) carbonate(green) ==> copper(II) oxide(black) + carbon dioxide
o CuCO3(s) ==> CuO(s) + CO2(g)
o zinc carbonate(white) ==> zinc oxide(yellow hot, white cold) + carbon dioxide
o ZnCO3(s) ==> ZnO(s) + CO2(g)
o FeCO3 and MnCO3 behave in a similar way
Quicklime reacts very exothermically with water to produce slaked lime (calcium
hydroxide).
o calcium oxide (quicklime) + water ==> calcium hydroxide (slaked lime)
this is a very exothermic reaction, the quicklime 'puffs' up and steam is produced!
CaO(s) + H2O(l) ==> Ca(OH)2(s)
o
o
Lime (calcium oxide) and slaked lime (calcium hydroxide) are both used to reduce the
acidity of soil on land, they are both faster and stronger acting than limestone powder. They are
also used to reduce acidity in lakes and rivers due to acid rain. They are also used to
neutralise potentially harmful industrial acid waste including sulphur dioxide in the flue gases of
power stations.
In the test for carbon dioxide, calcium hydroxide solution (limewater) forms a white milky
precipitate of calcium carbonate (back to where you started!).
o calcium hydroxide + carbon dioxide ==> calcium carbonate + water
o
Ca(OH)2(aq) + CO2(g) ==> CaCO3(s) + H2O(l)
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Calcium oxide and calcium hydroxide also react with acids to form salt.
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Contact Process
Because sulphuric acid has so many uses the industrial development of a country is sometimes
measured by the amount of sulphuric acid that is used each year. Sulphuric acid is made starting
from the element sulphur which is found in the Earth's crust.
Sulphuric acid is used as car battery acid and is used to make fertilisers, dyes
and detergents.
o eg ammonia + sulphuric acid ==> ammonium sulphate (a fertiliser salt)
o 2NH3(aq) + H2SO4(aq) ==> (NH4)2SO4(aq) => evaporation to get crystals
o Its acid action make it good for cleaning metal surfaces in industry.
Sulphuric acid is manufactured from the raw materials sulphur, air and water.
(1) Sulphur is burned in air to form sulphur dioxide (exothermic).
o In the reaction the sulphur is oxidised (O gain) S(s) + O2(g) ==> SO2(g)
Note: Sulphur dioxide itself is a useful chemical in its own right:
o It is used as a bleach in the manufacture of wood pulp for paper manufacture
o and its toxic nature makes it useful as a food preservative by killing bacteria.
(2) In the reactor the sulphur dioxide is mixed with air and the mixture passed over a
catalyst of vanadium oxide V205 at a high temperature (about 450C) and at a pressure of
between one and two atmospheres. It is a 2nd exothermic oxidation and is known as the
Contact Process.
In the reactor the sulphur dioxide is oxidised in the reversible exothermic reaction ...
o
2SO2(g) + O2(g)
2SO3(g)
The reaction forms sulphur trioxide and the equilibrium is very much to the right hand side
...
o despite the reaction being exothermic and a high temperature used (favours
reverse reaction R to L, energy change equilibrium rule)
o the reaction is favoured by high pressure (pressure equilibrium rule, 3 => 2 gas
molecules), but only a small increase in pressure is used to give high yields of
sulphur trioxide, because the right hand side is energetically very favourable (quite
exothermic)
o the use of a catalyst ensures a fast reaction without having to use too a higher
temperature which would favour the left hand side (energy change equilibrium
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rule)
(3) The sulphur trioxide is dissolved in concentrated sulphuric acid to form fuming
sulphuric acid (oleum).
o SO3(g) + H2SO4(l) ==> H2S2O7(l)
(4) Water is then carefully added to the oleum to produce concentrated sulphuric acid
(98%).
o H2S2O7(l) + H2O(l) ==> 2H2SO4(l)
o If the sulphur trioxide is added directly to water an acid mist forms which is
difficult to contain because the reaction to form sulphuric acid solution is very
exothermic!
Good anti-pollution measures need to be in place since the sulphur oxides are harmful
and would cause local acid rain! To help this situation AND help the economics of the
process, any unreacted sulphur dioxide is recycled through the reactor.
Concentrated sulphuric acid can be used in the laboratory as a dehydrating agent.
Dehydration is the removal of water or the elements of water from a compound.
o When added to some organic compounds containing hydrogen and oxygen, e.g.
sugar, concentrated sulphuric acid removes the elements of water from the
compound leaving carbon.
o When added to copper sulphate crystals concentrated sulphuric acid removes the
water of crystallisation leaving anhydrous copper sulphate
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The Synthesis of ammonia - The Haber Process
Ammonia gas is synthesised in the chemical industry by reacting nitrogen gas with hydrogen
gas.
The nitrogen is obtained from air (80% N2).
The hydrogen is made by reacting methane (natural gas) and water or from cracking
hydrocarbons (both reactions are done at high temperature with a catalyst).
o CH4 + H2O ==> 3H2 + CO
o eg C8H18 ==> C8H16 + H2
The synthesis equation for this reversible reaction is ...
N2(g) + 3H2(g)
2NH3(g)
Ammonia is oxidised with oxygen from air using a hot platinum catalyst to form nitrogen
monoxide and water.
4NH3(g) + 5O2(g)
4NO(g) + 6H2O(g)
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The gas is cooled and reacted with more oxygen to form nitrogen dioxide.
2NO(g) + O2(g)
2NO2(g)
This is reacted with more oxygen and water to form nitric acid.
4NO2(g)+ O2(g) + 2H2O(l)
4HNO3(aq)
Nitric acid is used in dye making processes and artificial nitrogenous fertilisers (see below).
ammonium sulphate
(NH4)2SO4(aq)
AND
ammonia + nitric acid
NH3(aq) + HNO3(aq)
ammonium nitrate
NH4NO3(aq)
These equations are sometimes written in terms of the ficticious 'ammonium hydroxide' which is, as
shown above, quite simply an aqueous solution of ammonia, but this is how it looks in some
textbooks! About 1% of the dissolved ammonia forms ammonium and hydroxide
o ammonium hydroxide + sulphuric acid
ammonium sulphate + water
o 2NH4OH(aq) + H2SO4(aq)
(NH4)2SO4(aq) + 2H2O(l)
o ammonium hydroxide + nitric acid
ammonium nitrate + water
o NH4OH(aq) + HNO3(aq)
NH4NO3(aq) + H2O(l)
If ammonium salts are mixed with sodium hydroxide solution, free ammonia is formed
(detected by smell and damp red litmus turning blue).
o eg ammonium chloride + sodium hydroxide ==> sodium chloride + water + ammonia
o NH4Cl + NaOH ==> NaCl + H2O + NH3
Artificial fertilisers are important to agriculture and used on fields to increase crop yields
but they should be applied in a balanced manner (see below).
o Fertilisers usually contain compounds of three essential elements for healthy and
productive plant growth to increase crop yield. They replace nutrient minerals used by a
previous crop or enriches poor soil and more nitrogen gets converted into plant protein.
nitrogen eg from ammonium or nitrate salts like ammonium sulphate, ammonium
sulphate or ammonium phosphate or urea
phosphorus eg from potassium phosphate or ammonium phosphate
potassium eg from potassium phosphate, potassium sulphate.
o Fertilisers must be soluble in water to be taken in by plant roots.
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Problems with using 'artificial' fertilisers
Overuse of ammonia fertilisers on fields can cause major environmental problems as well as
being uneconomic.
Ammonium salts are water soluble and get washed into the groundwater, rivers and streams by
rain contaminating them with ammonium ions and nitrate ions.
This contamination causes several problems.
Excess fertilisers in streams and rivers cause eutrophication.
o Overuse of fertilisers results in appreciable amounts of them dissolving in rain water.
o This increases levels of nitrate or phosphate in rivers and lakes.
o This causes 'algal bloom' ie too much rapid growth of water plants on the surface where the
sunlight is the strongest.
o This prevents light from reaching plants lower in the water.
o These lower plants decay and the active aerobic bacteria use up any dissolved oxygen.
o This means any microorganisms or higher life forms relying on oxygen cannot respire.
o All the eco-cycles are affected and fish and other respiring aquatic animals die.
o The river or stream becomes 'dead' below the surface as all the food webs are
disrupted.
Nitrates are potentially carcinogenic (cancer or tumor forming).
o The presence in drinking water is a health hazard.
o Rivers and lakes can be used as initial sources for domestic water supply.
o You cannot easily remove the nitrate from the water, it costs too much!
o So levels of nitrate are carefully monitored in our water supply.
The Industrial Electrolysis of Sodium Chloride Solution or brine made from concentrated 'rock salt' solution
OH-
positive
electrode
product
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The industrial electrodes must
be made of an inert material
like titanium which is not
attacked by chlorine or alkali.
However a simple cell using
carbon electrodes can be used
to demonstrate the industrial
process in the laboratory. The
cathode gas gives a
squeaky pop with a lit
splint - hydrogen. The anode gas turns
damp blue litmus red and then bleaches
it white - chlorine.
SODIUM
HYDROXIDE
NaOH
Chemical Economics
The greater the amount of starting materials (reactants) the greater amount of new
substances (products) formed.
However in the real world chemical processes are not 100% perfectly efficient!
o The amount that you actually make is called the yield.
o The percentage % yield = actual yield x 100 / predicted yield
o The predicted yield assumes there is no loss of product, ie no waste, and the
reaction goes 100% in the desired direction.
o If no product is obtained then the yield is 0%!
o In reality, yields can typically range from 5% to 95% for a variety of chemical
processes.
Why aren't processes 100% efficient? Typical reasons are:
o Loss in filtration of a solid product, ie some may get through as very fine
particles or more likely dissolved in the liquid residue.
o Loss in evaporation if the product is a volatile liquid.
o Loss in transferring liquids, ie traces left on the sides of containers.
o The reaction may be an equilibrium, so its impossible to get 100% yield
anyway and this means that the yield of an equilibrium reaction depends on
the conditions used.
The costs of making new substances depends on:
o Price of energy (eg gas, electricity).
o Starting materials (reactants).
o Labour (wages).
o Equipment (chemical plant eg machines, reactors, heat transfer systems).
o Speed of manufacture (time efficiency).
These cost factors can be analysed in more detail eg
o The higher the operating pressure of the reactor, the higher the cost. The
engineering is more costly due to eg thicker steel reaction vessel, higher health
and safety standards require.
o The higher the temperature the higher the energy cost. Fortunately this
cost is reduced if the reaction is exothermic and the reaction does go faster at
higher temperature.
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o
o
o
DONE
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Introduction to Oxidation and Reduction
OXIDATION and REDUCTION - REDOX REACTIONS
OXIDATION - definition and examples
(2) Fe2+ ==> Fe3+ + e- [the iron(II) ion loses (2) Fe3+ + e- ==> Fe2+ [the iron(III) ion gains an
1 electron to form the iron(III) ion]
electron and is reduced to the iron(II) ion]
(3) 2Cl- ==> Cl2 + 2e- [the loss of electrons
by chloride ions to form chlorine molecules]
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(4) iron(III) oxide + aluminium ==> aluminium oxide + iron (the thermit reaction)
o Fe2O3(s) + 2Al(s) ==> Al2O3(s) + 2Fe(s)
o iron(III) oxide is reduced and is the oxidising agent
o aluminium is oxidised and is the reducing agent
(h) Redox reaction analysis based on the electron definitions
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o
Oxidation Number
Oxidation numbers are a useful tool for determining whether a substance has been oxidized or
reduced. An element that undergoes a change in oxidation number in the course of a reaction has
been oxidized or reduced. Let's learn how to assign oxidation numbers.
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Assigning Oxidation Numbers
1. At atom in its elemental state has an oxidation number of 0.
Na H2 Cl2 S Xe
Each atom in these elements has an oxidation number of 0.
2. An atom in a monoatomic ion has an oxidation number identical to its charge.
Na+ Ba2+ Al3+ Br S2
+1 +2 +3 1 2
The oxidation number is equal to the charge on the monoatomic ion.
3. An atom in a polyatomic ion or a molecular compound usually has the same oxidation
number it would have if it were in a monoatomic ion.
a. Elements to the left on the periodic table are "cationlike" and have positive oxidation
numbers.
b. Elements to the right on the periodic table are "anionlike" and have negative oxidation
numbers.
Consider NH3.
N has an oxidation number of 3; each H has an oxidation number of +1.
c. Hydrogen
has a +1 oxidation number when bonded to nonmetals, and
has a 1 oxidation number when bonded to a metal.
NaH (H 1 oxidation number)
H2O (H +1 oxidation number)
d. Oxygen
often has a 2 oxidation number, but
can have a 1 oxidation number in the peroxide ion, O22.
H2O (O 2 oxidation number)
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HOOH (O 1 oxidation number)
e. Halogens
usually have an oxidation number of 1,
Unless bonded to oxygen, when they have a positive oxidation number.
HCl (Cl 1 oxidation number)
HOCl (Cl +1 oxidation number)
4. The sum of the oxidation numbers is 0 for a neutral compound and is equal to the net charge
for a polyatomic ion.
causes reduction
loses one or more electrons
is oxidized
oxidation number of atom increases
Oxidizing agent
causes oxidation
gains one or more electrons
is reduced
oxidation number of atom decreases
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The Activity Series of the Elements
The elements at the top of the table readily give up electrons and are stronger reducing
agents. The elements at the bottom give up electrons less readily and are weaker reducing
agents. Any element higher in the activity series will react with the ion of any element
lower in the activity series.
4.
Metallurgy is the science of extracting and purifying metals from their ores.
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5.
Undesirable oxidation reactions are termed corrosion. The rusting of iron in moist air is a familiar
process with enormous economic impact.
4 Fe(s) + 3 O2(g) Fe2O3H2O(s)
6.
Respiration is the process of breathing and using oxygen for the many biological redox reactions
that occur in living organisms.
C6H12O6(s) + 6 O2(g) 6 CO2(g) + 6 H2O(l) + energy
DONE
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ORGANIC CHEMISTRY
Crude oil is formed from organic material of the remains of plant and animal organisms that lived
millions of years ago. These remains form sediments eg at the bottom of seas, and become buried
under layers of sedimentary rock. They decay, without air (oxygen), under the action of heat and
pressure to form crude oil over millions of years.
It is a fossil fuel because it is formed from once living organisms and the Sun is the original source of
energy. It is a non-renewable and finite (limited reserves) energy resource because it takes millions
of years to form and we burn it faster than its is formed! It is also known as a finite energy resource
because it will eventually run out! We do not have unlimited oil reserves!
Coal and natural gas (mainly methane CH4 and often found with oil) are also non-renewable fossil
fuels formed from the remains of plants or animals.
When the fossil fuels are burned the 'carbon', as carbon dioxide, is returned to the living
environment, gets used up in photosynthesis, the plant material decays or is eaten by animals, so
completing the carbon cycle.
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Fuel Gas,
LPG,
Refinery
Gas
1 to 4
-160 to
20oC
Gasoline,
Petrol
5 to 11
20 to
60oC
Naphtha
7 to 13
60 to
180oC
Paraffin,
Kerosene
10 to 16
120 to
240oC
Diesel oil,
Gas oil
15 to 25
220 to
250oC
Fuel and
lubricating
20 to 70
Oils and
Waxes
Bitumen
over 70
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More on examples of relating the physical properties of the
fractions to their uses and dangers
down
the list the molecule gets bigger, more viscous, higher boiling and less flammable
The refinery gas fractions, under pressure, are conveniently pumped to burner systems, but are easily
ignited and explosive.
Vehicle fuels must be liquid for compact and convenient storage but they must be easily vapourised to mix
with air in the engine prior to ignition. The ease of vaporisation does however make them flammable!
Paraffin and kerosine are less flammable and safer, but not as easily ignited.
Fuel oil is not too viscous to pump to a central heating burner, and it is not very volatile and so not as
flammable and dangerous as petrol or diesel etc. for domestic use.
Lubricating oil must be quite viscous to stick onto surfaces. Smaller molecules might be more runny but
they would evaporate away! It is also water repellent and helps reduce corrosion on moving machine
parts.
Candle wax is very convenient as a solid for humble lamp (especially in power cuts!), but via a wick, the
heat from the flame is sufficient to vaporise the hydrocarbons to burn them.
Bitumen is a water repellent solid at room temperature but is readily melted (sometimes too easily in hot
weather). Used as base for a road chipping top surface or sometimes directly. It is also used to waterproof
roofing felt.
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The ALKANE series of hydrocarbons
Alkanes are a group of hydrocarbon molecules in which all the carbon and hydrogen atoms are only
joined by single covalent bonds (eg C-H or C-C). Alkanes are known as saturated molecules
because other atoms cannot add to them (compare alkenes further on). The first four in the series
are shown. They are not very reactive unless burned!
(1) is the molecular formula: a summary of the totals of each atoms of each element in one
molecule; (2) is a 'shorthand' version of the structural formula (3); (3) is called the structural
formula: it shows how all the atoms are linked with the covalent bonds
representation of the structural formula (3)
-; (4) is a '3D'
methane
(1)
, (3)
(main molecule
in natural gas)
, (4)
ethane
(1)
(2)
(3)
(4)
propane
(1)
(2)
(3)
butane
(1)
(2)
(3)
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The complete combustion of hydrocarbons
When hydrocarbons are burned in air a fast exothermic reaction occurs releasing heat and
forming carbon dioxide and water.
It is an oxidation reaction due to O gain by C and H.
The carbon dioxide is chemically detected with limewater - with which it forms a white
precipitate (milky appearance) of calcium carbonate.
The water is chemically detected either by (i) anhydrous white copper sulphate turning
blue OR (ii) anhydrous blue cobalt chloride paper turning pink.
A physical test for water is to measure its boiling point (should be 100oC).
Equations for the complete combustion of a hydrocarbon
hydrocarbon + oxygen => carbon dioxide + water
eg word equation: methane + oxygen => carbon dioxide + water
and the symbol equation: CH4(g) + 2O2(g) => CO2(g) + 2H2O(l)
(one CO2 for every C and one H2O for every two H's in the hydrocarbon molecule)
for ethane the symbol equation (more awkward) is ...
2C2H6(g) + 7O2(g) => 4CO2(g) + 6H2O(l)
and for pentane the symbol equations is ...
C5H12(l) + 7O2(g) => 5CO2(g) + 6H2O(l)
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The Incomplete Combustion of hydrocarbons
CO
If there is not enough oxygen present to completely burn the fuel to carbon dioxide and
water other products may form causing pollution and fuel inefficiency.
The most common partially burned products are likely to be carbon C (soot) and deadly
carbon monoxide CO.
It would appear that the hydrogen in the fuel molecules is more easily burned and usually
forms water.
There is also less heat released compared to complete combustion.
o eg CH4(g) + O2(g) => C(s) + 2H2O(l)
o or 2CH4(g) + 3O2(g) => 2CO(g) + 4H2O(l)
Therefore it is extremely important that any combustion system is as efficient as possible eg
gas heaters, furnaces etc. must all have excellent ventilation for complete combustion to
harmless water and carbon dioxide.
If there is any smell of gas, make sure (i) all appliances are turned off, (ii) all
sources of ignition are absent, and (iii) ring the gas board!
Faulty gas appliances have led to tragic deaths. Carbon monoxide is colourless and
odourless and even low concentrations in the air can be fatal.
Carbon monoxide is unfortunately emitted by all car exhausts, though catalytic converters
help reduce this by converting nitrogen monoxide (another pollutant) and carbon monoxide
into harmless nitrogen and carbon dioxide.
o
2NO(g) + 2CO(g) => N2(s) + 2CO2(l)
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The ALKENE hydrocarbons series
Alkenes are hydrocarbons containing a double bond as well as single bonds. These are called
unsaturated molecules because two atoms can join onto the bond when it opens up. The first two in
the series are shown below. They are extremely reactive and important compounds in the chemical
industry and are converted into very useful compounds eg plastics. They are made from cracking
processes (see below)
1) is the molecular formula: a summary of the totals of each atoms of each element in one
molecule; (2) is a 'shorthand' version of the structural or displayed formula (3); (3) is called the
structural or displayed formula: it shows how all the atoms are linked with the covalent bonds
ethene
(1)
, (2)
, (3)
propene
(1)
(2a)
(2b)
(1)
(3)
butene
, (2)
.... or
Alkenes are
unsaturated molecules,
atoms can add to them
via the C=C double
bond, so a reaction
occurs.
Alkanes are saturated
- no double bond - and
atoms cannot add - so
no reaction.
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.... or
propene + bromine
==> 1,2dibromopropane
CRACKING a problem!!
there isn't enough petrol in crude oil!
AND crude oil doesn't have any
alkenes in it for plastics!
When crude oil has been distilled into useful fractions it is found that the quantities produced
do not match the ratio required for commercial needs eg we have an insatiable appetite
for petrol and diesel in our cars and there are two many left-overs of the larger molecules
which do not make good fuels or have other uses. Fuel oil, naphtha and bitumen in crude oil
exceed demand.
Also, alkenes are not found in crude oil and they one of the most valuable types of organic
molecule in the chemical industry eg to make polymers (plastics) or ethanol (an alcohol).
The two deficiencies are remedied by the process of cracking which converts useless big
molecules into useful smaller ones.
CRACKING is done by heating some of the less used fractions to a high temperature
vapour and passing over a suitable hot catalyst. The cracking reaction is an example of
thermal decomposition - a reaction that breaks down molecules into smaller ones
using heat. The main products from cracking alkanes from oil are smaller alkanes (eg
for petrol or diesel) and alkenes (eg for plastics).
The equations below illustrate the process, small molecules are used to show the overall
molecular change clearly BUT in practice the 'starter' molecules are likely to be more those
shown in equations (3) and (4). The cracking involves breaking single carbon-carbon
bonds to form the alkanes (saturated hydrocarbons) and alkenes (unsaturated hydrocarbons)
products
(1)
butane
ethane
ethene.....or
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(2)
butane
methane
propene
The formation of big polymer molecules called polyalkenes from small molecules called alkenes
When catalysed and heated under pressure, alkenes link together when the double bond
opens. The spare bonds are used to join up the molecules.
The original small molecule is called the monomer and the long molecule is called the polymer,
which is the sort of molecule most plastics consist of. The polymer is now a saturated molecule
but has the same C:H ratio as the original alkene.
So lots of small molecules join up to form a big long molecule in a process called addition
polymerisation and the polymers are named as poly(name of original alkene).
Poly(ethene) from ethene is a cheap but very useful plastic used for plastic bags and bottles.
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Poly(propene) from propene is stronger and more hard wearing than polythene and is used for making
crates, fibres and ropes.
Poly(chloroethene), old name PVC, from chloroethene (vinyl chloride) is tougher than poly(ethene) and
very hard wearing and has good heat stability, so is used for covering electrical wiring and plugs. It also
replacing metals as gas and water drain pipes and has found a use as artificial leather and readily dyed to
bright colours!
Polystyrene is made from styrene (another alkene monomer) and is used in a gas expanded form for
packaging and insulation.
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Polymers or plastics cannot be easily broken down by microorganisms ie they are not
biodegradable. This leads to waste disposal problems and 'non-rotting' litter around the environment
and land-fill sites are getting full!
When plastic materials burn they can produce highly toxic gases such as carbon monoxide,
hydrogen cyanide and hydrogen chloride (particularly from PVC and other plastics containing chlorine
and nitrogen). This has caused deaths in house fires and controversial problems with alleged
inefficient waste incinerators and they will generally cause environmental problems if burning on
waste tips etc.
It is difficult to recycle plastics because of separation into the various sorts. It would be beneficial
to prolong the life of the finite crude oil reserves AND reduce pollution and space in land-fill sites.
New plastics are being developed which are more biodegradable or can be recycled, so will the
paper bag and cardboard package make a comeback? (in Eire you have to bring your own bag or buy
one, and not necessarily a plastic one!).
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Oil Products and Environment
Problems
Our economy, like many other countries has become very dependent on the extraction, sale and use
of oil based products. BUT, there is high price to be paid at times whether it be pollution effects or
warring countries with oil economics factors.
Oil rig accidents, broken pipelines, oil tanker wrecks etc. all have terrible effects on the plant and
animal life of the locality as we see from the horrible TV pictures of seabirds coated in oil, and toxic oil
slicks covering the beaches and sands.
The burning of oil and other fossil fuels is contributing to the 'Greenhouse Effect' of global warming.
The extra carbon dioxide forming absorbs and traps sunlight (or more precisely the re-radiated
sunlight energy from the Earth's surface) rather like a greenhouse. The effects are predicted to be
dramatic eg rising sea levels as polar ice melts causing flooding in low lying land regions, more energy
in the global weather system leads to more frequent violent weather patterns, ..
Fossil fuels contain the element sulphur or compounds of sulphur. When the fuel is burned the
sulphur also burns to form sulphur dioxide. This is an acidic gas and dissolves in rainwater, it then
reacts with water and oxygen to form a very dilute solution of sulphuric acid.
o Sulphur dioxide is a harmful gas and lung irritant and contributed to 5000 extra deaths in
the great 'London Smog' in the 1950's.
o The formation of acid rain has several bad effects on the environment eg
the low pH causes plant damage, particularly trees,
kills certain life forms and so damages eco cycles and food chains in rivers or lakes
harming wildlife like trout,
increases the 'weathering' corrosion rates of building stone (particularly limestone).
High temperature combustion also produces other pollutants including ...
o Nitrogen oxides, NO and NO2, which are acidic and contribute further to acid rain (above),
and are also involved in the chemistry of 'photochemical smog' - which produces chemicals
harmful to respiration and eyes. Many of the reactions are initiated by sunlight.
o Carbon monoxide CO, which is toxic, and also involved in the chemistry of 'photochemical
smog'. This is formed by inefficient combustion
o Unburned hydrocarbons, CxHy, which can be carcinogenic and are also involved in
photochemical smog chemistry.
But catalytic converters* can significantly reduced these three unwanted emissions
(see above for CO and NO removal, and CxHy gets oxidised to CO2 and H2O). * eg
using platinum-rhodium transition metal catalysts, these are dispersed on ceramic bed
to give a big surface area for the best reaction rate.
There are other indirect pollution problems to do with burning fossil fuels:
o Lead compounds are added to petrol to improve engine performance. This produces lead
compound emissions into the environment. Lead compounds are nerve toxins so it is fortunate
they are being phased out in many countries.
o Photochemical smog is mentioned in the previous paragraph.
And finally, should we using a very valuable source of organic chemicals by merely burning most
of it? AND how long will oil reserves last? AND what happens if the oil runs out?
Hydrogen gas can be used as fuel and a long-term possible alternative to fossil fuels.
o It burns with a pale blue flame in air reacting with oxygen to be oxidised to form water.
o hydrogen + oxygen ==> water or 2H2(g) + O2(g) ==> 2H2O(l)
o It is a non-polluting clean fuel since the only combustion product is water and so its use
would not lead to all environmental problems associated with burning fossil fuels.
o It would be ideal if it could be manufactured by electrolysis of water eg using solar cells.
o Hydrogen can be used to power fuel cells on the "Extra Electrochemistry" page.
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n-butane
Isobutane
Neopentane
n-butane
Isobutane
Neopentane
Isopentane
n-pentane
n-pentane
Isopentane
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Extra
ORGANIC CHEMISTRY
All organic compounds consist partly of carbon atoms. Coal, crude oil, natural gas (methane) and wood contain
organic compounds
o all are used as fuels, either directly like coal or natural gas,
o or indirectly as coke from coal or petrol from crude oil etc.,
o and apart from wood, they are finite (limited reserve) fossil (from decayed organic material) fuels.
Many hydrocarbons are fuels ie a substance burned to release heat energy.
When organic compounds are burned in a plentiful supply of air the carbon is oxidised to carbon dioxide and the
hydrogen is oxidised to water.
In a limited supply of air incomplete combustion occurs forming carbon monoxide and/ or carbon. Carbon monoxide is
poisonous because it reduces the capacity of blood to carry oxygen.
Combustion equations and tests for combustion products are all on the Oil Notes web page.
Each fossil fuel has a different cost, efficiency and cleanliness on burning. Generally speaking in 'cleanliness' the order is
methane (natural gas) > alkanes in petrol > heavy oil and from left to right there is also an increase in C/H atom
ratio in the molecule so more CO2 produced too. Some notes on other fuels (but they are designed for more advanced
level courses) and a fossil fuel survey on Oil Products Notes page
The combustion of plastics (and other organic compounds) which contain chlorine and nitrogen produce poisonous fumes
when burnt eg choking hydrogen chloride HCl and toxic hydrogen cyanide HCN respectively. Especially where there is a limited
supply of air. The combustion products of carbon (toxic CO and CO 2) and hydrogen (H2O) are also formed.
Hydrogen gas can be used as fuel.
o It burns with a pale blue flame in air reacting with oxygen to be oxidised to form water.
o hydrogen + oxygen ==> water or 2H2(g) + O2(g) ==> 2H2O(l)
o It is a non-polluting clean fuel since the only combustion product is water and so its use would not lead to all
environmental problems associated with burning fossil fuels.
o It would be ideal if it could be manufactured by electrolysis of water eg using solar cells.
o Hydrogen can be used to power fuel cells on the "Extra Electrochemistry" page.
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2. Why are there families of organic compounds?
[alkanes and alkenes are introduced on the Oil Notes page and give details of (i) alkane combustion (ii) the reaction of
bromine with alkenes and (iii) the basics of alkene polymerisation]
2a INTRODUCTION
Organic compounds belong to different families. The compounds in each family have a similar chemical structure and a similar chemical
formula. Each family of organic compounds forms what is called a homologous series. Different families arise because carbon atoms
readily join together in chains (catenation) and strongly bond with other atoms such as hydrogen, oxygen and nitrogen. The result is a
huge variety of 'organic compounds'. The name comes from the fact that most of the original organic compounds studied by
chemists came from plants or animals.
A homologous series is a family of compounds which have a general formula* and have similar chemical properties
because they have the same functional group of atoms (eg C=C alkene, C-OH alcohol or -COOH carboxylic acid).
o * Match the general formula pattern with the alkane and alkene examples shown below.
members of a homologous series have similar physical properties such as appearance, melting/boiling points, solubility etc.
but show trends in them eg steady increase in melting/boiling point with increase in carbon number or molecular mass.
The molecular formula represents a summary of all the atoms in the molecule (see examples below).
The structural or displayed formula shows the full structure of the molecule with all the individual bonds and atoms shown
(though there are different 'sub-styles' of varying detail, see below).
2b ALKANES
These are obtained directly from crude oil by fractional distillation (see oil notes).
The saturated hydrocarbons form an homologous series called alkanes with a general formula CnH2n+2
Saturated means the molecule has no C=C double bonds, only carbon-carbon single bonds, and so has combined
with the maximum number of atoms ie no atoms can add to it. The alkanes don't really have a functional group and have
quite a limited chemistry BUT they are still a clearly defined homologous series.
Alkane examples: The gases: methane CH4, ethane C2H6, propane C3H8, butane C4H10, liquids: pentane C5H12, hexane C6H14
etc. The first four alkane structures are shown on the oil notes page. Names end in ...ane
Carbon always forms 4 bonds with other atoms and hydrogen 1 bond with other atoms eg Propane: molecular formula C3H8,
structural and displayed formula styles include ...
o
or
or
Isomerism occurs when two or more compounds have the same chemical formula but have different structures. eg for the
molecular formula C4H10 there are two possibilities - one 'linear' and one with carbon chain 'branching' ...
butane:
or
or
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+ Cl2 ==>
+ HCl
2c ALKENES
These cannot be obtained directly from crude oil and must be made by cracking (see oil notes).
The unsaturated hydrocarbons form an homologous series called alkenes with a general formula CnH2n Unsaturated
means the molecule has a C=C double bond to which atoms or groups can add.
Alkene examples: Names end in ...ene
ethene C2H4,
propene C3H6,
or
or
or
o butene
or
The alkenes are more reactive than alkanes because of the presence of the carbon=carbon double bond. The alkenes
undergo addition reactions in which one of the carbon=carbon double bonds breaks allowing each carbon atom to form a
covalent bond with another atom such as hydrogen or bromine.
Examples of addition reactions are: with hydrogen under pressure and in the presence of a nickel catalyst to form an
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alkane
+ H2 ==>
o
+ H2 ==>
(propene + hydrogen ==> propane)
Alkenes react by 'addition' with bromine and decolourises the orange bromine water because the organic product is
colourless, and this is a simple test to distinguish an alkene from an alkane.
o see Oil Notes for equations for ethene and propene
Vegetable oils contain unsaturated fats and can be hardened to form margarine by adding hydrogen on to some of the
carbon=carbon double bonds using a nickel catalyst.
Alkenes can add to themselves by addition polymerisation to form 'plastic' or polymeric materials (see below or oil
notes)
Alkenes are isomeric with cycloalkanes eg C6H12 can be hexene or cyclohexane
o
o
Ethanol structure:
or
or
or
Ethanol is used as a solvent, as a fuel (can be mixed with petrol), and used to make 'ethyl esters' (see below) as well as
the 'potent' chemical present in alcoholic drinks!
o The % alcohol in wines, spirits and beer varies from 1-40%
o There are health and social issues about the medical and behavioral aspects of alcohol consumption.
o Methylated spirit is mainly ethanol but poisonous and nasty tasting chemicals like methanol are added so it is not
used as a beverage!
Ethanol can be produced by fermentation of sugars. The raw materials are mixed with water and yeast at just above
room temperature. The yeast contains enzymes which are biological catalysts. The sugars react to form ethanol and carbon
dioxide. The carbon dioxide is allowed to escape and air is prevented from entering the reaction vessel to stop oxidation of
ethanol to ethanoic acid ('acetic acid' or vinegar!). When the reaction is over the ethanol is separated from the reaction mixture
by fractional distillation.
o eg glucose ==enzyme==> ethanol + carbon dioxide
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C6H12O6(aq) ==> 2C2H5OH(aq) + 2CO2(g)
Ethanol, from a solution made from fermented sugar cane, can be concentrated by fractional distillation. In Brazil it is
blended with petrol to give an alternative motor vehicle fuel.
C2H5OH(l) + 3O2(g) ==> 2CO2(g) + 3H2O(l)
The alcohols form an homologous series with the functional group C-OH. It is the presence of this functional group that
gives alcohols their characteristic properties. The simplest homologous series of alcohols have the general formula
CnH2n+1OH eg
Ethanol is shown above and the simplest, lowest carbon number one, is methanol (shown below)
o
o
o
o
o
or
or
All the alcohols are flammable colourless liquids with a not un-pleasant odour?
They all behave chemically in the same way but the boiling point steadily rises with increase in molecule
size.
The next two are called propanol and butanol, the names end in ...ol
o CH3-CH2-CH2-OH or
and
Alcohols react, reversibly, with carboxylic acids to form esters and water. Ethyl ethanoate is formed by the reaction of
ethanoic acid with ethanol eg
o ethanoic acid + ethanol
ethyl ethanoate + water
o
+
+ H2O
o its an equilibrium, 2/3rds conversion, and catalysed by a few drops of concentrated sulphuric acid
Alcohols react with sodium to form hydrogen.
o normal fizzing is observed and the salt product is soluble in the alcohol itself.
o eg ethanol + sodium ==> sodium ethoxide + hydrogen
o 2C2H5OH + 2Na ==> 2C2H5O-Na+ + H2
Ethanol can be produced by the reaction of steam and ethene in the presence of a strong acid catalyst (Phosphoric
acid). The reversible reaction is carried out at a moderately high temperature (eg 300 oC) and a high pressure (eg 60 x
atmospheric pressure). The higher temperature and catalyst speed up the reaction and increasing pressure moves the
equilibrium to the right (side least gaseous molecules at 300 oC)
o
+ H2O ==>
Advantages and disadvantages of the two methods of making ethanol:
o advantages of fermentation: cheap and renewable resource like sugar cane (Brazil), sugar beet
o disadvantages of fermentation: slow reaction and made by an inefficient batch process, poor quality product eg
low aqueous concentration, other organic chemicals formed to and yeast cell residues to remove .
o advantages of ethene route: fast and efficient continuous process, relatively pure product, country may have local
oil supply (eg North Sea for UK, Middle East countries)
o disadvantages of ethene route: using a non-renewable finite resource (crude oil/cracking)
Ethanol can be oxidised to form ethanoic acid which is a useful organic chemical. BUT it is this oxidation of ethanol that
results in alcoholic drinks turning sour (eg cider, wine) when exposed to air. Ethanoic acid (old name 'acetic acid') is the basis of
vinegar and is also used in making esters (eg pear drop essence, or .
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+ O2 ==>
+ H2O
This oxidation can also be done by heating the ethanol with a mixture of sulphuric acid and potassium
dichromate(VI) solution. The mixture turns from orange to green.
o When burned, ethanol, like any alcohol, forms carbon dioxide and water
CH3CH2OH + 2O2 ==> 2CO2 + 3H2O
Ethanol can be dehydrated to ethene by passing the alcohol vapour over heated aluminium oxide catalyst.
o
o
==>
o
o
+ H2O
This reaction is potentially an important source of organic chemicals eg plastics from a renewable resource since the
ethanol can be made by fermentation of carbohydrates etc.
Alcohols from propanol upwards, ie from carbon number 3 or greater, will form isomers.
o You will find plenty of examples on the advanced organic chemistry page for alcohols.
The steroid, cholesterol, contains the alcohol group -OH. Cholesterol is an essential steroid to humans but if too much is
produced it can cause heart disease.
http://webbook.nist.gov/cgi/cbook.cgi?Name=cholesterol&Units=SI gives the skeletal formula structure of
cholesterol (this structure representation is only dealt with at advanced level). All the lines in the structure represent bonds
between carbon atoms except the 'dash' for the -OH alcohol group in the bottom right of the molecule. Also note the 'alkene'
double bond functional group to the right of the -OH group.
Carboxylic acids form another homologous series and have the functional group -COOH.
The structures of the first three members are given below: Names end in ...oic acid.
methanoic acid:
ethanoic acid:
or
or
or
or
o propanoic acid:
or
or
Vinegar contains ethanoic acid (old name 'acetic acid'), see above in section 3 Alcohols above. It is used as a preservative and
in food flavourings.
Ethanoic acid is used in the manufacture of the fibre, acetate rayon.
Oranges, lemons and many soft drinks contain a carboxylic acid eg citric acid.
Aspirin is a carboxylic acid. Aspirin is a drug used for pain relief and is taken regularly by those at risk from heart attacks.
Ascorbic acid (vitamin C) is another carboxylic acid and is present in fresh fruit and vegetables.
Carboxylic acids are weak acids, typically solutions are around pH3 (yellow-orange-pink with universal indicator).
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and
show the structures of other esters made from ethanoic acid: namely methyl ethanoate using methanol, and propyl
ethanoate from propyl alcohol
o and what would the structure of their original alcohols be and what would the structure of butyl ethanoate be?
Esters are usually sweet smelling and widely used as fragrances (eg perfumes) and food flavourings.
o
o
Some basic notes on polymers and plastics in the Oil Products Notes.
Some important structure, strength and 1D to 3D dimension concepts) in the "Chemical Bonding" notes.
Most polymers (plastics) are made from alkene compounds containing the -C=C- bond by addition
polymerisation.
Poly(chloroethene) is made from chloroethene (old name 'vinyl chloride), CH 2=CHCl but the polymer is generally called
polyvinylchloride, PVC. The general equation and the formation of poly(ethene) and poly(propene) are shown on the Oil notes
page. The formation of PVC is shown below.
Polymers (plastics) consist of a tangled mass of very long molecules in which the atoms are joined by strong covalent
bonds to form long chains, but there are much weaker intermolecular forces holding the material together.
In thermosoftening plastics like poly(ethene), poly(propene) or poly(chloroethene) PVC, because the inter-molecular
attractive forces between the chains are weak, the plastic softens when heated and hardens again when cooled. It also means
the polymer molecules can slide over each other. This means they can be easily stretched or moulded into any desired shape.
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However it is possible to manufacture and process plastics in which the polymer chains are made to line up. This
greatly increases the intermolecular forces between the 'aligned' polymer molecules and strong fibre strands of the
plastic can be made.
o Examples: The addition polymer poly(propene) and the condensation polymers nylon and Terylene
When a thermosetting plastic is first heated covalent bonds are formed between adjacent chains of the polymers. These
strong covalent cross-linkages give the material a high melting point and greatly increased strength and rigidity. They also
prevent thermosetting plastics from being softened with heat and therefore from being stretched or re-shaped. However it does
make a much stronger material and not as flammable. On heating strongly they do NOT melt, but tend to char, gradually giving
off gases.
o
Melamine (used in furniture) and many glues are examples of thermosetting polymers.
Problems with using plastics are on the Oil Products Notes page.
Some important structure, strength and 1D to 3D dimension concepts) in the "Chemical Bonding" notes.
Condensation polymerisation involves linking lots of small monomer molecules together by eliminating a small molecule.
This is often water from two different monomers, a H from one monomer, and an OH from the other, the 'spare bonds' then
link up to form the polymer chain.
Nylon (a polyamide) is formed by condensation polymerisation, the structure of nylon represented as ... (the rectangles
represent the rest of the carbon chains in each unit)
(3 units etc.)
This is the same linkage (-CO-NH-) that is found in linked amino acids in naturally occurring macromolecules called proteins,
where it is called the 'peptide' linkage.
Terylene (a polyester) is formed by condensation polymerisation and the structure of Terylene represented as
(3 units etc.)
This is the same kind of 'ester linkage' (-COOC-) found in fats which are combination of long chain fatty carboxylic acids and
glycerol (alcohol with 3 -OH groups, a 'triol').
Terylene and nylon are good for making 'artificial' or 'man-made' fibres used in the clothing and rope industries. In
the manufacturing process the polymer chains are made to line up. This greatly increases the intermolecular forces between the
'aligned' polymer molecules and strong fibre strands of the plastic can be made.
Some important structure, strength and 1D to 3D dimension concepts in "Chemical Bonding" notes.
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5. Naturally Occurring Molecules
Small Molecules <=> Natural Polymers = Macromolecules
Carbohydrates, Proteins and Fats are the main nutrient constituents of food.
5a. Carbohydrates
Carbohydrates are a whole series naturally occurring molecules based on the elements carbon, hydrogen and oxygen.
Historically the name 'carbohydrate' comes from the fact that all their formulae seemed to be based on Cx(H2O)y (see key
above) BUT this is not the way to think of their formula.
They range from relatively small molecules called monosaccharide (means one basic unit), or disaccharide (two basic
units combined) to very large natural polymers or macromolecules called polysaccharides (many units combined). A
summary of them is shown in the key diagram above along with some familiar names from biology.
Glucose is one of the simpler sugar
molecules. The structural formula is shown
on the left and you should be able to see that
there are 4 bonds to each carbon, 2 to each
oxygen and just 1 bond to each hydrogen
atom. The right-hand 'shorthand' skeletal
formula version uses short straight lines to
represent bonds. Most H's and their bonds are
not shown, and at AS-A2 level it is assumed
you can interpret these structures 'back to' a
full structure!, but they are handy for
describing large 'biochemical' molecules (see
polysaccharide below)
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Sucrose is a disaccharide made from combining two monosaccharide molecules, glucose and fructose by the
elimination of a water.
o On hydrolysis sucrose reforms the glucose and fructose.
o 2C6H12O6 <=> C12H22O12 + H2O
This diagram of starch or cellulose is in 'skeletal formula' style and both are polymers of glucose - can you see the connection
between each 'unit' and the structure of glucose itself?
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The hydrolysis products from polysaccharides can be analysed with paper chromatography.
Amino acids are carboxylic acids (like ethanoic acid) but one of the hydrogen atoms of the 2nd carbon atom is substituted
with an amino group (a nitrogen + two hydrogens gives -NH2). Another hydrogen on the same 2nd carbon can be substituted
with other groups of atoms (R) to give a variety of amino acids.
or
Oils and Fats are an important way of storing chemical energy in living systems and are also a source of essential longchain fatty acids.
Most of them are esters of the tri-alcohol ('triol') glycerol (systematic name propane-1,2,3-triol, but that can wait until AS-A2
level!).
The carboxylic acids which combine with the glycerol are described as 'long-chain fatty acids'.
The resulting ester is called a 'triester' or 'triglyceride'.
The 'long-chain fatty acids' can be saturated, with no C=C double bonds, and so forming saturated oils or fats (1st diagram
below of the triglyceride formed from palmitic acid).
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The 'long-chain fatty acids' can be unsaturated, with one or more C=C double bonds, and so forming unsaturated oils
or fats (2nd diagram below of the triglyceride formed from oleic acid).
Some sub-notes on Oil and Fat Structure: (health issues dealt with further down)
o They have the same linkages as Terylene but with different units.
o They are not as big as polymer molecules, but a lot bigger than a single petrol or sugar molecule.
o There can be 1 to 3 different saturated or unsaturated fatty acid components, so lots of variation possible in
structure of the oil or fat. The diagrams just assume three molecules of the same 'fatty' acid.
o Monounsaturated fats have one C=C double bond in them, polyunsaturated fats usually have at least
three C=C bonds in their molecular structure.
o For the same molecular size in terms of carbon number, unsaturated fats have slightly lower intermolecular
forces because the C=C double bond produces a kink in the carbon chain and they can't pack as closely together as
the saturated molecules.
This gives unsaturated fats a lower melting point and so they tend to occur as eg vegetable oils rather
than saturated low melting solids from meat and dairy products.
o However, this means these unsaturated oils are not as conveniently 'spreadable' as 'butter'.
To overcome this problem, 'margarine' was invented. The vegetable oils are reacted with hydrogen using the
gas and a nickel catalyst.
This reaction adds hydrogen atoms to the double bonds making a more saturated and more 'spreadable' solid
fat we call 'margarine'.
The reaction for any double bond is: >CH=CH< + H2 == Ni ==> -CH2-CH2 BUT it does mean that it is more like animal fat now but various blendes have been developed to suit your
dietary needs or desires!
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5d. Chromatography
Hydrolysis means breaking down a molecule with water to form two or more products.
o Hydrolysis is accelerated if the substance is heated with acid or alkali solutions.
When proteins are heated with aqueous acid they are hydrolysed to amino acids.
Acid hydrolysis of complex carbohydrates (eg. starch) gives simple sugars.
Chromatography is useful in separating and identifying the products of hydrolysis of carbohydrates and proteins.
o The hydrolysis can be done by boiling the carbohydrate or protein with hydrochloric acid.
o The hydrolysed mixture is then 'spotted' onto the pencil base line of the chromatography paper.
Known sugars or amino acids are also spotted onto the base line too.
The prepared paper is then placed vertically in a suitable solvent, which rises up the paper.
o Since the products are colourless, the dried chromatogram is treated with another chemical to produce a coloured
compound.
Ninhydrin produces purple spots with amino acids
and resorcinol makes coloured spots with sugars.
o You can then tell which amino acids made up the protein or the sugars from which the carbohydrate was formed.
The number of different spots tells you how many different amino acids or sugars made up the natural
macromolecule.
Spots which horizontally match the standard known molecule spots confirm identity.
Starch gives one spot because only glucose is formed on hydrolysis.
(C5H10O5)n + nH2O ==> n C6H12O6 (where n is a very large number)
o More details on chromatography.
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6. Vitamins, Drugs and Food Additives (NOT FINISHED)
Vitamins are particular essential molecules with particular roles in living systems which are
NOT proteins, carbohydrates, fats or mineral salts.
One of the most important ones in any diet is Vitamin C or Ascorbic Acid. Its structure is related to 'simple' sugars but
humans are one of the few mammals that are unable to synthesise vitamin C.
o It is essential for healthy tissue and one of its functions is the removal of dangerously reactive chemical species called
free radicals (see further on).
o Vitamin C is present in fruit and vegetables but the amount is reduced by prolonged storage and
cooking..
o 250 years ago, as many as 2/3 of a ship's crew died from vitamin C deficiency causing scurvy. In 1747 it was decided to
give sailors citrus fruits to recover from scurvy but wasn't until 200 years later that vitamin C was recognised.
o In contrast to the other water-soluble vitamins, vitamin C has no clear cut role as a catalyst or part of an enzyme. It
does, however, have a range of other important functions:
Collagen formation. Vitamin C in collagen formation which is found wherever tissues require strengthening,
especially in tissues with a protective, connective, or structural function. Collagen is critical to the maintenance
of bone and blood vessels and is essential in wound healing.
Antioxidant activity. Ascorbic acid can act as an antioxidant by donating electrons and hydrogen ions, and
reacting with reactive oxygen species or free radicals.
Iron absorption. Vitamin C is important for the effective absorption of iron and reduces iron(III) Fe 3+ to iron(I)
Fe2+.
It helps in the synthesis of vital cell compounds. During times of physical and emotional stress, as well as
during infection, there is increased production of oxygen radicals. Therefore there is increased reliance on
vitamin C's activity as an antioxidant.
Vitamin C is vital for the function of the immune system, but the effectiveness of large doses of vitamin C in
preventing and alleviating the symptoms of the common cold is still a matter of debate.
o Two of the earliest signs of deficiency (prevention of collagen synthesis) relate to its roles in maintaining the integrity of
blood vessels. The gums around the teeth bleed more easily, and the capillaries under the skin break spontaneously
producing tiny haemorrhages. If you are short of vitamin C for say 20 days, scurvy can develop and is characterised by
further haemorrhaging, muscles depletion, rough-brown-dry-scaly skin, deep bruising. Wounds fail to heal properly and
bone fails to rebuild properly too and you are further likely to suffer from anaemia and infections.
o SO EAT yer fruit and veg 'guys' (as well as a few crisps!) AND keep yer health and still pass those dreaded
exams!!!!
Drugs can be defined as an externally administered substances which modifies or affects chemical reactions in the body,
usually for the bodies greater well-being. Poisons can be defined in the same way, but hopefully not intentionally and have
undesired effects!
o An analgesic is a drug used to reduce pain and is type of anti-inflammatory agent.
o The molecular structure of three well known analgesics are shown in the diagram below.
o All are used for 'headache' treatment, and hopefully using this website and others will help minimise their use!
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The central hexagonal ring of 6 carbon atoms is called a 'benzene' or 'aromatic' ring. The 4th outer electron of carbon
(group 4) is delocalised, so the expected 4th bond per C atom forms part of a 'communal' system (more on this at
advanced level, but the covalence rule of 4 for carbon is not broken!, you have seen this situation before, check out
graphite. You can show a benzene ring as a simple hexagon with a circle in it
from
+ NaOH ==>
+ H2 O
The modern pharmaceutical industry has its origins in herbal and other traditional medicine.
eg An extract of willow herb extract can be made from the leaves, bark and seeds of the willow tree. Amongst other
ailments it was given to help curing feverish headaches and relief of pain in childbirth. When ingested the body
hydrolyses and oxidises the naturally occurring 'precursor' molecule to form salicylic acid* which is the 'active'
molecule in the body. in the 1890's the German chemist Hoffmann experimented with various chemical modifications of
salicylic acid and found the best and chemically stable form was 'aspirin' (shown below). He tried the variations on
his own father! who survived to provide valuable 'clinical trials' - hardly acceptable these days! * 'Oil of winter
green' from certain plants is the methyl ester of salicylic acid and has similar 'medicinal effects'.
Aspirin (and the others shown) are not very soluble in water. Soluble aspirin is made by neutralising the carboxylic
acid with the alkali sodium hydroxide to make the much more soluble sodium salt of the acid. The reaction, using
skeletal formula, is shown in the diagram below the three analgesic drug structures.
New drugs and testing them:
It costs a lot of money to develop a new medicine so the price charged by the pharmaceutical company must cover the
cost of research, production and marketing.
Patents are taken out to protect the company's commercial interests in the new medicine.
There can be a range of formulations of a particular medicine when you buy it over the counter eg tablet of
100% aspirin, soluble aspirin (via Na + salt of the acid from neutralisation) and aspirin might form part of a
mixture including substances that have other beneficial effects.
The main point here is that aspirin, like many drugs, can have multi-functional effects, hopefully all beneficial.
BUT this, sadly, is not always the case, because with any new drug there is always the danger of
unknown side-effects.
Therefore there is a tremendous responsibility on pharmaceutical companies to ensure the development of safe
and effective drugs.
Lots of time and money spent on discovering and developing new drugs and there are lots of
factors to consider:
o From the discovery of a potentially useful molecule, sometimes called the 'lead molecule', which can be
from natural source or produced in some other project etc.
o Is there room in the commercial market place for it?
o Do research to see if its safe, otherwise further development is a waste of time and money or if
not safe, can its molecular structure be modified?
o Can the modification be safe? and more effective?
o In what form, can it be/needs to be, administered in? for clinical trials.
o Carefully clinical trials in various phases, noting particularly if any side-effects which may
be harmful.
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o
o
o
o
Do you test new drugs on animals? - an emotive issue, can non-animal testing always
allow the safe development of new products?
Do you test new drugs on patients in a life threatening situation, give them a last chance
at some risk?
Patient health and safety issues versus very big drug company commercial interests are a
matter of public concern.
Any new drug must finally pass all the tests before legally licensed for patient consumption ...
sadly, the 'drug companies' and the 'powers to be' do not always get it right (eg
phthalidomide), but do not the benefits outweigh the occasional tragedy which we
should do our best to avoid?
Food additives are chemicals added to food to give particular effects eg colourings, flavourings, preservation and
sweetening.
o Colourings to make food more attractive, to fit in with the consumers perception of what it should look like.
o Flavourings to make food more 'tasty', less 'bland', and to fit in with the consumers perception of what it should taste
like.
o Preservatives are to increase the 'shelf-life' of packaged food, decrease risk of food poisoning.
o Sweeteners counter bitterness or pander to our taste!
E-numbers are reference numbers used by the European Union to help identification of food additives.
o All food additives used in the European Union are identified by an E-number.
o The "E" stands for "Europe" or "European Union".
o Normally each food additive is assigned a unique number, though occasionally, related additives are given an extension
(eg a,b,i or ii etc.) to another E-number.
o The Commission of the European Union assigns E-numbers after the additive is cleared by the Scientific
Committee on Food (SCF), the body responsible for the safety evaluation of food additives in the European
Union. A summary is given below.
E100-199
food colours
E200-299
preservatives
E300-399
E400-499
E500-599
E600-699
flavourings
E700-899
not used for food additives (used for animal feed additives!)
E900-999
E1000-1399
E14001499
miscellaneous additives
starch derivatives
E-numbers are only used for substances added directly to food products, so contaminants, enzymes and processing
aids, which may be classified as additives in the USA, are not included in the E-number system.
There is an EU directive on food labeling which requires food additives to be listed in the product ingredients whenever
they are added for technological purposes.
o This includes colouring, sweetening and favor enhancement as well as for preservation, thickening, emulsifying
and the like.
o Ingredients must be listed in descending order of weight, which means that are generally found close to the
end of the list of ingredients.
o However, substances used in the protection of plants and plant products, flavorings and substances added as
nutrients (e.g., minerals, trace elements or vitamins) do not need to be included in the ingredient list.
o Because of this, some substances that are regulated as food additives in other countries may be exempt from
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the food additive definition in the EU.
If enough energy is supplied by heat or by visible/uv electromagnetic radiation, or the is weak enough, a covalent bond
can break in two ways. This illustrated with the molecule chloromethane CH3Cl.
o Unevenly where the electron bond pair can stick with one fragment and a positive and negative ion form.
eg CH3Cl ==> CH3+ + Cl- (at AS-A2 level this is called heterolytic bond fission)
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o
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