Professional Documents
Culture Documents
uk/Images/171720-specific
ation-accredited-a-level-gce-chemistry-a-h432.
pdf
Jade Hartley
1
Module 2
FOUNDATIONS IN CHEMISTRY
2
2.1.1 Atomic Structure and isotopes
Nucleus contains
Particle Relative Relative neutrons and protons
Mass Charge (positively charged)
Proton 1.0 1+
Neutron 1.0 0
Electron 1/1836 1- Orbits contain electrons,
which have opposite
spins
5
NB:
Definitions
of EF and MF
not required Determination of formulae
E.g. What is the molecular formula of a compound
Empirical Formula: the simplest whole containing 40.0% Carbon, 6.7% Hydrogen, 53.3%
number ratio of atoms of each element Oxygen with a molar mass of 180.0?
present in a compound
Carbon Hydrogen Oxygen
7
Percentage Yield
• The maximum possible amount of products formed by a
reaction is called the theoretical yield
• However, the actual yield of a reaction is usually lower for
reasons including the following
– The reaction may not be fully complete
– Side reactions may have taken place alongside the main reaction
– Reagents may be impure
– Purification of the product may result in loss of some product (E.g. in
separating or distillation) or in transferring between vessels (minimise
loss using rinsing)
8
Atom Economy
• The atom economy of a reaction is a measure of how well atoms have been
utilised. This is based solely on the balanced equation for a reaction and
assumes a 100% yield; therefore no experimental results are needed.
• Reactions with high atom economies:
– Produce a large proportion of desired products and few unwanted waste products
– Are important for sustainability as they make best use of natural resources. A
process that produces several worthless by-products may have a high yield but will
have a low atom economy
– Improving atom economy makes processes more efficient, preserves raw
materials and reduces waste.
9
A salt is defined as a compound Acids release H + ions in
formed when one or more H+ aqueous solutions.
ions in an acid are replaced by a
metal or ammonium ion. 2.1.4 Acids Alkalis release OH - ions in
aqueous solutions
Acid formulae Acid names Alkali formulae Alkali names
HCl Hydrochloric acid NaOH Sodium hydroxide
HNO3 Nitric acid KOH Potassium hydroxide
CH3COOH Acetic (Ethanoic)acid NH3 Ammonia
Even though the 3d orbitals were filled last, the electrons are lost from the 4s
orbitals because they have a higher value of n.
13
2.2.2 Bonding and structure - Ionic
• Ionic bonding is the electrostatic attraction between positive and negative ions (between
metal and non-metal)
• The structure of giant ionic lattices is a result of oppositely charged ions being strongly
attracted in all directions e.g. NaCl
• Almost all ionic structures are solid at room temperature as there is insufficient energy to
overcome the strong electrostatic forces of attraction. Therefore most ionic compounds have
high melting and boiling points. These are even higher for lattices with greater ionic charges;
the attraction also depends on the size of the ions.
• Many ionic substances are soluble in polar solvents as the polar molecules surround each ion
and break down the lattice. In compounds with large charges the ionic attraction may be too
strong for water to break down the lattice so it won’t be as soluble.
• When solid ionic compounds don’t conduct electricity. However, ionic compounds do
conduct electricity when molten or in solution as the ions are free to move and act as mobile
charge carriers.
14
Covalent bonding
• A covalent bond (2 non-metals) is the strong electrostatic attraction between a shared pair
of electrons and the nuclei of the bonded atoms
• Multiple covalent bonding is where more than one pair of electrons are shared E.g. O 2
• Dative covalent (coordinate) forms when both the electrons in the bonding pair are provided
by the same bonding atom E.g. in NH4+
• Average bond enthalpy is a measurement of covalent bond strength (the larger it is, the
stronger the covalent bond)
• Note: ‘-ide’ is used in binary compounds, ‘-ate’ when there’s oxygen, and ‘-ite’ when there’s
less oxygen. E.g. S is sulfide, SO4 is sulfate, sulfite is SO3
15
Shapes of simple molecules and ions
104.5°
16
Electronegativity
Electronegativity is the ability of an atom Non-polar bonds result from molecules made from atoms
to attract the bonding electrons in a of the same element or with similar electronegativity
covalent bond values. The bonded pair of electrons are shared equally.
Pauling electronegativity values increase In polar bonds the bonded atoms are different and have
towards F in the periodic table as nuclear different electronegativity values. This results in a polar
charge increases and atomic radius covalent bond where the bonded electron pair is shared
decreases unequally between the bonded atoms.
Polar substances dissolve in polar solvents whilst non-polar substances dissolve in non-polar solvents as intermolecular
forces form between the molecule and the solvent, weakening the intermolecular forces in the molecular lattice and
breaking them, causing it to dissolve. The intermolecular forces formed when a polar substance is added to a non-polar
solvent are not strong enough to overcome the intermolecular bonding in the lattice.
17
Intermolecular forces
• Intermolecular forces are weak interactions between dipoles of different
molecules
• They are mainly responsible for the physical properties of a compound,
including boiling point (also depends on number of electrons) and fall into
3 main categories:
– Induced dipole-dipole interactions (London forces)
– Permanent dipole-dipole interactions
– Hydrogen bonding
The term Van der Waals’ forces is used to describe both induced and
permanent dipole-dipole interactions.
An idea of their weakness is shown to the right, compared with a
covalent bond.
18
Induced dipole-dipole interactions (London
forces)
• London forces are temporary forces that exist between The more electrons in each molecule:
all molecules • The larger the instantaneous and
• The movement of electrons produces a changing induced dipole
dipole in any molecule • The greater the induced dipole-
• At any instant an instantaneous dipole will exist, but dipole interactions
its position is constantly changing • The strong the attractive forces are
• The instantaneous dipole induces a dipole on its between the molecules
neighbouring molecule
• The induced dipole induces further dipoles on
neighbouring molecules, which then attract one
another
19
Permanent dipole-dipole interactions
• Permanent dipole-dipole forces arise from the attraction
between opposite partial charges on polar bonds
• They are stronger than London forces so require a greater
energy to overcome and break therefore molecules with
permanent dipole-dipole will have a higher boiling point
• This explains the difference in boiling points between F2 and
HCl as HCl has a higher b.p. despite the molecules being of
similar sizes and having the same number of electrons
20
Hydrogen bonding
A hydrogen bond is a special type of permanent dipole-dipole
interaction found between molecules containing an
electronegative atom with a lone pair of electrons – this includes
oxygen, nitrogen and fluorine only – bonded to a hydrogen atom.
The bond, shown by a dashed line,
acts between the hydrogen on one
molecule and the lone pair of
electrons on another. The shape
around the hydrogen atom is
linear.
Hydrogen bonds are the strongest
type of intermolecular interaction.
21
Hydrogen bonding in water
PERIODIC TABLE
AND ENERGY
24
The Periodic Table
The periodic table is an
arrangement of all the
elements:
• by increasing
atomic (proton)
number
• in periods showing
repeating trends in
physical and
chemical
properties
(periodicity) –
number of shells
• in groups having
similar chemical
properties – number of outer electrons
Across a period the general trend is that the 1 st ionization energy increases as nuclear charge
Ionization energies are affected by three increases, similar shielding (same shell), nuclear attraction increases and atomic radius decreases.
factors which influence the attraction Down a group the general trend is that the first ionization decreases. This is due to increased
between the nucleus and outer electron atomic radius, more inner shells so shielding increase and so nuclear attraction on the outer
electrons decreases.
of an atom. These are:
- Atomic radius: the greater the
distance between the nucleus and
outer electron, the less the nuclear
attraction
- Nuclear charge: the more protons
there are in the nucleus, the greater
the attraction between the nucleus
and the outer electrons
- Electron Shielding: as all electrons
are negatively charged the inner-
shell electrons repel outer-shell
electrons, reducing the attraction
between the nucleus and outer 1st ionization energy drops at aluminum because its outer electron is in a p sub-level. This is higher
electrons in energy than the outer electron in magnesium, which is in an s sub-level, so less energy is
needed to remove it. The same idea explains the drop between boron and beryllium in group 2.
It also drops between phosphorous and sulfur because the 3p electrons in phosphorus are all unpaired. In Sulphur, two of the 3p electrons
are paired. There is some repulsion between paired electrons in the same sub-level. This reduces the force of their attraction to the nucleus,
so less energy is needed to remove one of these paired electrons than is needed to remove an unpaired electron from phosphorus. 26
Similarly, the same goes for the drop between Nitrogen and oxygen.
Structure and Melting points
o All metals have metallic bonding and a giant metallic lattice
structure. This is the strong electrostatic attraction between a lattice
of cations (positive ions) and a sea of delocalized electrons.
o The solid giant covalent lattices of carbon (diamond, graphite and
graphene) and silicon are networks of atoms bonded by strong
covalent bonds
Melting and High boiling and melting points as high High melting and boiling
boiling points temperatures are necessary to provide points as high
sufficient energy to overcome the strong temperatures are needed
electrostatic attraction between the to provide the large
cations and electrons. This strength quantity of energy needed
increases with ionic charge to break the strong
covalent bonds. Diamond
o Across period 3: Melting points increase between sodium, magnesium and aluminum because they are giant metallic
structures and the ions go from Na+ to Mg 2+ to Al 3+. The increase in ionic charge leads to greater attraction between the
lattice of cations and the sea of delocalized electrons (as there are more of them), so requires greater energy to break these
bonds. There is a decrease to Silicon as it is a giant covalent structure with strong covalent bonds between atoms, requiring
a large amount of energy to break, but not as much to fully vaporize the aluminum metal. There is a large drop to the other
four as they become simple molecular structure with just weak London forces between molecules to break. The only
increase is between S8 and P4, as S8 is a larger molecule with more electrons so has larger London forces leading to more
energy required.
28
Group 2
Group 2 elements:
• All group 2 elements act as reducing agents because they reduce another series (give them their
electrons) and are themselves oxidised
• The reactivity increases down group 2 because in redox reactions they lose 2 electrons to form 2+
ions.
• Therefore their reactivity depends on their first and second ionization energies. These decrease as
you go down the group because the (nuclear) attraction between the outer electrons and the nuclear
decreases as a result of increasing atomic radius and increasing shielding from Mg → Ba.
• This is shown by their redox reactions with:
– Oxygen ( to produce a metal oxide)
– Water (to produce a metal hydroxide and hydrogen)
– Dilute acids (to produce a salt and hydrogen)
29
As you go down the Halogens, the
boiling points increase due to there
being more electrons in the diatomic
The Halogens
molecules lower down the group, so The reactivity of the halogens decreases down the group because atomic
larger instantaneous dipoles and radius increases and there are more inner shells so shielding increases so
stronger London forces which there is less nuclear attraction to capture the incoming electron.
require more energy to break.
This trend in reactivity is shown by the displacement reactions with other halogens, indicated by
the colour change in aqueous and organic solutions.
A solution of one halogen is added to an aqueous solution of a different halide. If the halogen
added is more reactive than the halide present, a reaction takes place and the solution changes
colour. Because iodine and bromine appear similar colours in water, an organic non-polar solvent
such as cyclohexane is added because the non-polar halogens dissolve more readily in this than
water and their colours are much easier to tell apart. The colours in each solution are shown
below.
Chlorine Bromine Iodine
Solution in water
Pale green Orange Brown
Solution in cyclohexane (top layer)
Disproportionation is a redox reaction in which the same element Pale green Orange Violet
(note: not species as it refers to its oxidation state) is both oxidised
and reduced. Some examples of this are shown below:
• The reaction of chlorine with water as used in water
treatment Chlorine is beneficial in water treatment to kill
• The reaction of chlorine with cold, dilute aqueous sodium bacteria and prevent diseases like typhoid and
hydroxide, as used to form bleach cholera.
However, chlorine gas is toxic and can lead to
respiratory irritation, or even death in large
concentrations.
Furthermore it can react in water with
hydrocarbons to form chlorinated
hydrocarbons, which are suspected of causing 30
cancer.
Ammonium cation test:
Qualitative analysis •
•
Add aqueous sodium hydroxide
Ammonia gas is produced (but very soluble so unlikely to be
seen)
(observations rather than measurements •
•
Heat the solution to release the gas
Smell of ammonia given off, test with moist indicator paper (turn
such as in titrations) •
blue as ammonia is alkaline)
NH4+ (aq) + OH- (aq) → NH3 (g) + H2O (l)
When choosing solutions, use cations from
group 1 compounds as these are soluble. Correct order for testing anions:
1. Carbonate test
2. Sulphate test
Carbonate Test: 3. Halide test
• Add dilute nitric acid You have to undertake the tests in this order because both BaCO3 and Ag2SO4 are
• Bubbles of CO2 gas will be formed both insoluble so would form precipitates in other tests and confuse the results. If
done in this order, neither sulphate nor halide ions produce bubbles with dilute
(test with lime water to check)
acids, no carbonates will be present in the sulphate test and silver sulphate or
• CO32–(s) + 2H+(aq) ==> H2O(l) + CO2(g) silver carbonate precipitates won’t be formed in the halide test as they will have
been removed.
If testing a mixture of ions then carry out each reaction in excess until no further
reaction occurs and remove the precipitates using filter paper. Furthermore make
Sulfate Test: sure to use cation solutions that do not contain any anions you are testing for I.e.
• Add a solution containing Ba2+ ions (E.g. Use nitric acid for carbonates (not sulphuric acid or hydrochloric acid) and use
barium nitrate) barium nitrate in the sulphate test (not barium chloride).
• Looks for a white precipitate of barium
Often, nitric acid solution is added in the test for halides to remove other ions such
sulphate
as carbonate and hydroxides that may form precipitates too.
• Ba2+(aq) + SO42–(aq) ==> BaSO4(s)
In the sulphate test, the barium chloride may similarly be acidified with
hydrochloric or nitric acid to react and remove any carbonate ions.
Halide Colour of Solubility in Solubility in
Halide Test: precipitate dilute ammonia concentrated
• Add aqueous silver nitrate ammonia
• Look for different coloured precipitates
Chlorine White Soluble Soluble
• Add aqueous ammonia (concentrated or
dilute) to tell the colours apart Bromine Cream Insoluble Soluble
• Ag+(aq) + X–(aq) ==> AgX(s) 31
Iodine Yellow Insoluble Insoluble
Enthalpy
• Enthalpy is a measure of the heat energy in a chemical system (atoms, molecules or ions making
up the chemicals). It cannot be measure but enthalpy changes can as heat is given out/taken in
from the surroundings
• Enthalpy change, ΔH = ΔH products - ΔH reactants
• Law of conservation of energy: Energy cannot be destroyed or created but only transferred
from one form to another. The total energy of a system of reacting chemicals and surroundings
remains constant.
• The minimum energy required for a reaction to take place is known as the activation energy, Ea
An exothermic reaction is one in which:
• Energy is transferred from the
chemical system to the surroundings
• ΔH is negative
• The temperature of the
Negative Exothermic
surroundings increases
34
Bond enthalpies
• As well as being a measurement of covalent bond strength, the average
bond enthalpy is the energy required to break 1 mol of a specified bond
in a gaseous molecule (not the specified bond in 1 moles of molecules!)
• Energy is always required to break bonds
• Bond enthalpies are always endothermic and have a positive value
• The actual bond enthalpy can vary depending on the chemical
environment of the bond. The average bond enthalpy is calculated from
the actual bond enthalpies in different chemical environments.
E.g.
• C—H = 439 kJ/mol
• C—H = 420 kJ/mol
• C—H = 422 kJ/mol
• C—H = 411 kJ/mol
• Average C—H = 413 kJ/mol
35
Bond enthalpies continued
• Energy is required to break bonds: bond breaking is
endothermic (∆H positive)
• Energy is released when bonds are formed: bond making is
exothermic (∆H negative)
The difference between the energy required for bond breaking
and the energy released when forming bonds determines
whether an overall reaction is exothermic or endothermic.
36
Hess’ law
• Hess’ law states that, if a reaction can place by two routes,
and the starting and finishing conditions are the same, the
total enthalpy is the same for each route. This comes from the
idea of the conservation of energy
• Using enthalpy changes of combustion:
∆rH = ∑ ∆cH (reactants) - ∑ ∆cH (products)
• Using enthalpy changes of formation:
∆rH = ∑ ∆fH (products) - ∑ ∆fH (reactants)
See the next couple of slides for examples
37
Example enthalpy changes from ∆fH
• The reaction between ethene and hydrogen chloride gases to
make chloroethane gas
• In using the values from the enthalpies of formation, we have
to write the elements as the bottom line of the cycle
• B + A = C, so A = C – B = ∆H
• ∆H = -109 –( 52.2 – 92.3) = -68.9 kJ/mol
B C
38
Example enthalpy changes from ∆cH
The standard enthalpy change of formation of benzene was impossible to measure
directly. That is because carbon and hydrogen won't react to make benzene.
Therefore, we have to use an enthalpy cycle to work out the enthalpy change.
For enthalpy of combustion, the way we draw the diagrams is we put the equation for
the reaction we want to find on the top line and underneath we write the combustion
products (NB: oxygen isn’t written as a reactant as it is in excess anyway and confuses
the diagram).
Next draw on the different routes to get to the same products
A
• In this case A + C = B so A = B – C = ∆rH
• B = 6(-394) + 3(-286) C
B
• C = -3267
• ΔH = 3267 + 6(-394) + 3(-286) = +45 kJ mol-1
Remember to always write the correct sign for the reaction and write the
arrows the correct way round for combustion cycle! This value is slightly
different from the data book due to rounding errors. I
39
Reaction rates and
The rate of a chemical reaction (moldm^-3/s) measures how fast a reactant
is being used up/how fast a product is being formed.
The rate of a reaction is always fastest at the beginning of a reaction as each
reactant is at its highest concentration; this then slows down as reactants are
used up
collision theory
To increase the rate of reaction you can: An effective collision will occur if, and only if,
• Increase concentration (/pressure if particles collide with the correct orientation
reactants are gases) and have sufficient energy to overcome the
• Increase temperature activation energy
• Use a catalyst
• Increase the surface area of solid
reactants or change the state of a reaction
• An increase concentration (/pressure if reactants are gases): more particles in the same volume so are therefore
closer together and collide more frequently; In a given period of time there will therefore be more effective collisions
(correct orientation and sufficient energy) leading to an increased rate of reaction
• Increasing surface area: more particles are exposed on the solid reactants and therefore have a greater area for
collisions to take place. In a given amount of time there will therefore be more effective collisions (correct
orientation and sufficient energy) leading to an increased rate of reaction.
• Further to this, the state of reagents affects the rate as if reactant molecules exist in different phases, as in a
heterogeneous mixture, the rate of reaction will be limited by the surface area of the phases that are in contact.
At a higher temperature:
• The distribution is stretched over a greater range of x-values and the
peak is lower on the y-axis and at a greater energy. The area under the
curve stays the same, though, as no molecules are added.
• More molecules have an energy greater or equal to the activation
energy, as represented by the Boltzmann distribution shown to the right
• A greater proportion of collisions will lead to a reaction, increasing the
rate
• Less importantly, collisions will also be more frequent as they are
moving faster
42
Equilibrium and Le Chatelier’s principle
• A dynamic (both forward and backwards reactions occurs) equilibrium exists in a closed system when the rate of
the forward reaction is equal to the rate of the reverse reaction and the concentrations of reactants and products
do not change
• It is important to the chemical industry to have a compromise between chemical equilibrium and reaction rate in
deciding the operational conditions. Although a low temperature, in the Haber process for example, may produce a
high yield it will do so very slowly. Furthermore, though concentration may increase yield and the rate of reaction
they require very strong containers and large quantities of energy. Not only is this costly but safety is also a concern.
Therefore, a compromise must be reached between reasonable rates and an economic yield.
• Adding a catalyst will not change the position of equilibrium as it will speed up the rate of the forwards and
backwards reactions equally. It will, however, increase the rate at which an equilibrium is established.
• NB: Note that both the forwards and backwards reactions have the same enthalpy change with opposite signs
Investigating pressure:
As you increase the pressure of the reaction
below the position of equilibrium will favour the
products as it has fewer gaseous molecules and
will minimise the pressure
Decreasing the pressure will make the position
shift to the left so brown colour will deepen.
44
Module 4
CORE ORGANIC
CHEMISTRY 45
4.4.1 Basic concepts of Organic chemistry
Homologous series: a series of organic compounds having the same functional
group but with each successive member differing by CH2
Functional group: a group of atoms responsible for the characteristic reactions of
a compound
Saturated: contain only single carbon–carbon bonds
Unsaturated: the presence of multiple carbon–carbon bonds, including C=C,
triple carbon bonds and aromatic rings
Structural isomers: compounds with the same molecular formula but different
structural formulae
Aliphatic – hydrocarbon arranged in a straight
chain, branched chain or non-aromatic rings
47
Nomenclature and common functional groups
50
Boiling point of the alkanes
Fractional distillation of alkanes is possible due to their variation in boiling
points. The b.p. increases with chain length due to London forces that act
between close surface contact. As chain length increases, so does surface
area so the London forces will be greater and require more energy to
overcome. Branched isomers have lower boiling points as they decrease the
number of surface points of contact between molecules and get in the way of
the molecules moving closer together.
51
Reactivity of alkanes
Alkanes aren’t very reactive as:
• High bond enthalpy: The C-C and C-H σ-bonds are strong
• Low polarity: C-C bonds are non-polar, and so too can be
considered C-H bonds as they have a similar electronegativity
• Initiation:
• Propagation (chain reaction):
Step 1
Step 2
• Termination:
1-chloropropane 2-chloropropane
® ® ®
54
Alkenes
• Unsaturated hydrocarbons (C-C double bond)
• Aliphatic alkenes with only one double bond have the general formula
CnH2n (but can be cyclic or have more than one double bond)
• Contain sigma bonds and a pi bond (formed by the sideways overlap of
two p-orbitals) – electron density in a pi-bond is concentrated above and
below the line joining the nuclei and the bonding atoms. This locks them
into position and prevents rotation – therefore different to the tetrahedral
arrangement of alkanes and forming a trigonal planar shape around the C-
C double bond
55
Stereoisomers have the
same structural formula
but a different Stereoisomers
arrangement of the atoms
in space Cis-trans isomerism – a special case of E/Z isomerism
where one of the attached groups on each carbon
E/Z Isomers – arises due to must be hydrogen. The cis isomer is the Z isomer
restricted rotation around the (both hydrogens on same side) and the trans isomer
double bond (fixed relative to is the E isomer (hydrogens on opposite sides)
each other). A molecule will have
E/Z isomerism if it contains a C-C
double bond and has different
groups attached to each carbon
atom of the double bond
C-C single bond (sigma bond) in ethene has a bond enthalpy of 347
kJ/mol
C-C double bond (sigma and pi bond) has a bond enthalpy of 612
kJ/mol
Therefore the pi-bond in an alkene can be calculated as 612-347 = 265
kJ/mol (weaker than sigma bond and therefore more readily broken)
57
Reactions of alkenes
• Hydrogenation of alkenes – when mixed with hydrogen and passed over a nickel catalyst at
423K, an addition reaction takes places to form an alkane (1 mole of hydrogen is needed for
each double bond present)
• Halogenation of alkenes – they undergo a rapid addition reaction with the halogens Cl or Br
at room temperature. Bromine water is therefore used to test for unsaturation as because
the bromine reacts and is taken out of solution, it turns from orange to colourless.
• Addition reactions of alkenes with halogen halides – Alkenes react with gaseous hydrogen
halides at room temperature to form haloalkanes (either by mixing gases, bubbling gas
through liquid alkene or mixing two solutions). If the alkene is unsymmetrical, and so too is
the halogen halide, there will be two possible products.
• Hydration reactions of alkenes – alcohols are formed when alkenes react with steam in the
presence of a phosphoric acid catalyst (or conc. Sulphuric acid). As with the previous reaction
there are normally two possible products.
58
Electrophilic addition in alkenes
When alkenes undergo addition reactions they do so by a
mechanism called electrophilic (negative-loving) addition.
This is because the double bond represents a region of high
electron density due to the pi electrons, attracting
electrophiles – atoms/groups of atoms that are attracted to
an electron-rich centre and accepts an electron pair –
usually a positive ion or a molecule containing an atom with
a partial positive (d+) charge.
59
Electrophilic addition
1. Hydrogen bromide is polar
2. Electron pair in pi-bond attracted to partially positive
H atom, causing double bond to break With a non-polar molecules the
3. A bond forms between the H and one of the carbon same steps happen but to begin
atoms with as it approaches the pi
electrons interact with it –
4. The H-Br bond breaks by heterolytic fission (both repelling the molecules electrons
electrons from bonded pair go to Bromine) and inducing a dipole at one end –
5. Br- ion and a carbocation (containing a positively which is then attracted to the pi
charged carbon atom) are formed bond, causing the double bond to
break and so on.
6. Finally Br- ion reacts with the carbocation to form
the addition product
60
Markownikoff’s rule
• The more stable a carbocation is, the more likely it is to be reacted with
• Alkyl groups (represented by R) donate and push electrons towards the
positive charge on a carbocation (i.e. alkyl groups are slightly e- donating)
• The more alkyl groups there are on a carbocation, the more the positive
charge is spread out, making the ion more stable – leading to more
reactions
Therefore when a hydrogen halide reacts with an unsymmetrical alkene, the
hydrogen attaches itself to the carbon atoms with the greatest number of
Hydrogen atoms (smaller number of carbon atoms) - therefore the halogen
bonds with the carbon with the most alkyl groups (becomes major product).
61
Polymers – extremely large molecules with thousands of
repeat units (arrangement of atoms that repeats over and
over again in the polymer structure) formed from
Polymerisation in
monomers (small molecules that combine with others to
form a polymer).
Alkenes
Addition polymerisation requires high temperatures and
pressures using catalysts
• At present, most plastic waste ends up in a landfill site where it is buried in a dark hole in the
ground. Under these conditions, photo degradation cannot take place and there is also limited
oxygen and water so the breakdown of biodegradable polymers becomes very slow.
64
Alcohols
• Contain –OH (hydroxyl) functional group CnH2n+1OH)
• Polar due to –OH bond (difference in electronegativity)
• Greater water solubility, boiling point and lower volatility (tendency to evaporate
at normal temperatures) than the corresponding alkanes (with the effect of the –
OH decreasing with chain length) due to polarity and hydrogen bonding
• They can be classified into primary, secondary or tertiary depending on where the
–OH group is placed
– Primary: -OH attached to carbon bonded to 2 H atoms and 1 alkyl group (-OH at end of
chain)
– Secondary: carbon bonded with 1 H atom and 2 alkyl groups (Middle of chain)
– Tertiary: carbon bonded with 3 alkyl groups (Middle of chain on a branch)
65
Naming Alcohols
1. Count for the longest chain (E.g. 4 = butane)
2. Count –OH groups and use suffix (E.g. 2 = diol)
3. Number which carbon –OH groups are on and use infix (E.g. on 2 &3 = -
2,3-)
4. If –OH group suffix starts with vowel then shorten alkane chain name
(E.g. –diol doesn’t start with vowel so use butane, not butan)
5. Count branches and name (E.g. Methyl group on 2 = 2-methyl)
6. Add prefix, infix and suffix together (E.g. 2-methylbutane-2,3-diol)
66
Reactions of Alcohols
• Combustion of alcohols: Exothermic
(increasing quantity of heat per mole
with increasing chain length)
• Dehydration of alcohols (removal of
water): if heated under reflux with an
acid catalyst, such as conc sulfuric
acid or conc phosphoric acid, it forms
an alkene and water. This is an
elimination reaction
• Substitution reactions: heated under
reflux with conc sulphuric acid and a
sodium halide – to form hydrogen
halide in situ (in place) – to form
haloalkanes
67
More Reactions of alcohols -
Oxidation
Oxidation of alcohols with potassium dichromate (VI) acidified by dilute sulphuric acid. When
oxidised the solution turns from orange (Cr2O7 2- ions) to green (Cr 3+ ions):
– Primary alcohols (Distilled – to prevent further reaction - gentle heating with oxidising agent)
Aldehyde
– Primary alcohols (Reflux – ensures any aldehyde formed is condensed back into reaction mixture -
heated strongly with excess oxidising agent) Carboxylic acid
– Secondary alcohols (Reflux) Ketone
– Tertiary alcohols No reaction
You should use [O] to represent the oxidising agent, 1 mole of [O] for every 2 moles of hydrogen
removed or every oxygen required. [H] is needed, 2 for every mole of oxygen that’s removed or
for every hydrogen that’s required. Note: If the solution remained orange at the end it suggests
dichromate is in excess as if all had been reduced it would have turned green.
68
Compounds containing the elements
carbon, hydrogen and at least one
halogen.
Add prefix:
o F fluoro- Haloalkanes
o Cl chloro-
o Br bromo-
o I iodo-
Due to the difference in electronegativity between the carbon and halogen, the electrons are slightly closer to the
halogen so the bond is polar. This means the carbon is slightly positively charged and attracts nucleophiles (an electron
pair donor; an atom or group of atoms attracted to an electron deficient carbon atom).
When a haloalkane reacts with a nucleophile, it replaces the halogen in a substitution reaction under a mechanism
called nucleophilic substitution.
Hydrolysis is a chemical reaction involving an alkane and water or an aqueous alkali heated under reflux that causes
the breaking of a bond in a molecule . This is an example of nucleophilic substitution.
1. A nucelophile approaches the carbon atom on the opposite side of the molecule to the halogen (minimises
repulsion)
2. Lone pair of electrons on the hydroxide ion is attracted and donated to the d+ of the carbon atom
3. A new bond is formed between the carbon atom and the oxygen atom from the OH-
4. The carbon-halogen bond breaks by heterolytic fission
5. The new organic product is an alcohol. A halide is also formed.
+
69
Hydrolysis
• The rate of hydrolysis depends on the strength of the carbon-halogen bond in the
haloalkane
• The C-F bond is the strongest so requires high quantities of energy to break and is
relatively unreactive
• Iodoalkanes react faster than all others, followed by bromoalkanes and then
chloroalkanes
• To carry out: In 3 test tubes put 1cm of ethanol in each with 2 drops of a haloalkane. Then
in 3 others place equal volumes of aqueous silver nitrate and place all test tubes in a
water bath at 60 degrees (quicker reaction so can observe for 5 minutes rather than over
longer period of time) and allow to reach a constant temperature. Then, quickly add the
silver nitrate to the haloalkane and start a stopwatch immediately.
71
Photodissociation
• CFCs are very stable due to the strength of their carbon-halogen bond. This means they have a
long residence time in the troposphere and after years may reach the stratosphere where UV
radiation provides sufficient energy to break the carbon-halogen bond by homolytic fission to
form radicals. C-Cl has the lowest bond enthalpy in a CFC so this is the bond that breaks.
• As radiation initiates the breakdown, this process is called photodissociation
• The breakdown occurs in two steps:
– Propgation step 1:
– Propogation step 2:
– Overall: O3 + O 2O2
• In step 2 another chlorine radical is created which can then repeat the process, forming a chain
reaction. This is how the ozone layer is depleting and holes within it are created.
• Other radicals also catalyse the breakdown of ozone, such as nitrogen oxide radicals (formed
naturally during lightning strikes and by air travel in the stratosphere):
– Propgation step 1:
– Propogation step 2:
– Overall: O3 + O 2O2
72
Quickfit Apparatus
Note:
• Alcohols cannot be refluxed in an
open round-bottom flask as they are
volatile and would evaporate
Screw-tap adaptor Condenser • For heating flammable liquids a
heating mantle is used so that no
naked flame is present as an added
Still head (3-way adaptor) layer of safety should the apparatus
leak or crack
• You need to add bumping-granules
to reflux an organic liquid to ensure
it boils smoothly. Otherwise, large
Receiver bubbles will form at the bottom of
the liquid and make the glassware
vibrate or jump violently
Round bottom or • Add grease to ground-glass joint of
pear-shaped flask condenser and rotate gently back
and forth to provide a good seal and
ensure it comes apart at the end
• You should never put a stopper in
the top of a condenser under reflux
as you would then form a closed
system where pressure would build
up as the heated air expanded and
the apparatus could explode
violently
• Condensers should be clamped only
loosely as the outer jacket is very
fragile and easily broken
• Water always enters the condenser
in the lower outlet and leaves the
top so the jacket fills completely with
water with no air bubbles 73
Practical techniques in organic chemistry
You can use a separating funnel to remove an
organic layer from an aqueous layer. Re-distillation is commonly
1. To do this ensure the tap is closed and add used to separate two
liquids, allowing them to separate into their organic compounds with
layers. Then add water to identify aqueous similar boiling points. The
layer (it is the one that increases in volume). second time around, only
Remove the lower layer by opening the tap. collect the product with the
2. To remove acid impurities add NaCO3 (aq), boiling point of the desired
any acid present will react with it when compound. The narrower
mixed and produce carbon dioxide (release the boiling range, the purer
pressure by holding upside down and slowly the product. Then remove
opening the tap). Then the sodium any impurities after.
carbonate layer can be removed
3. Finally wash the organic layer with water
and run both layers into separate flasks
mechanisms
75
Mass spectrometry
• Mass spectrometry can be used to determine the molecular mass of a compound
• This can be identified by the molecular ion peak – the clear peak at the highest
m/z value
• A small peak will usually also be seen to its right. This exists due to the fact that
1.1% of carbon is present at the carbon-13 isotope
• Fragmentation will occur as some molecular ions break down into smaller pieces
known as fragment ions. The simplest fragmentation is when a molecular ion
breaks down into two species – a positively charged fragment ion and a radical.
The uncharged radicals will not be accelerated so won’t be detected. Each
compound fragments in slightly different ways so each compound’s mass spectrum
is unique.
Fragment ion m/z
CH3+ 15
C2H5+ 29
C3H7+ 43
OH 18
76
Infrared spectrometry
• Infrared radiation causes molecules to vibrate more and absorb energy
• Greenhouse gases including water vapor, carbon dioxide and methane absorb infrared radiation due to containing
C=O, O–H and C–H bonds. Eventually, the molecules re-emit this energy as radiation that increases the temperature
of the atmosphere close to earth, leading to global warming
• Due to the above there is a need to reduce emissions of these atmospheric gases and so there have been changes
to renewable sources of energy for many householders
• Depending on the compound when put inside an Infrared spectrometer, only certain values of radiation are
absorbed depending on which bonds it contains – shown by ‘peaks’ (the dips in the graph)
• Below 1500 cm-1 (wavenumber) is known as the fingerprint region as it contains many unique peaks close together
that can be used to determine a compound
• Although its difficult to predict the identity of a functional group within this region, peaks outside this region are
clearer
• Most organic compounds produce a peak at approximately 3000 cm–1 due to absorption by C–H bonds. Other
types of bonds can be seen below
Bond Location Wavenumber (cm-
1)
O-H Carboxylic acids 2500-3300 (broad
78
Physical chemistry and transition
elements
Module 5
79
Rate =
Reaction Rates
The rate of a reaction is proportional to the concentration of a particular
reactant raised to a power, this power is called the order of a reaction with
respect to that reactant. Rate ∝ [A] k
• If the order is 0: The concentration doesn’t influence the rate The rate constant k is the proportionality constant from the rate
• If the order is 1: If [A] is doubled, so is the rate equation (above) , the number that converts between rate and
• If the order is 2: If [A] is doubled, the rate is quadrupled concentration, like an ‘exchange rate’. The units depend on the
The overall order of a reaction gives the overall effect of the concentration of concentration terms of the reaction.
all reactants on the rate of a reaction. It is the sum of orders with respect to Determining k:
each reactant. • Use a tangent to the curve at a particular concentration and use
k= rate/concentration
• K= (ln2)/t1/2 where t1/2 is the half life. This is much more accurate
than a tangent taws they are difficult to draw accurately.
K = gradient of the rate-time
graph for 1st order
80
Rate determining step
You need to be able to propose a mechanism for reactions giving the rate
equation. As this equation contains the molar quantities of the species that
are in the rate determining step, or before the slow step (!), you can work out
a possible mechanism (note: there will be more than one).
A hard example of this would be where the rate equation seems to provide a
1 step mechanism. However, the key is to realise that the slow step would
come second.
81
The clock reaction
• The initial rate is the instantaneous rate when t=0.
• The clock reaction is a more convenient way to find the initial rate by obtaining a
single measurement of the time taken to reach a specific point in a reaction , e.g. a
visual change (such as the time taken for a precipitate to form, a solid to disappear
or a change in colour). The time measured should be such that the reaction hasn’t
progressed too far. • This assumes that the reaction
proceeds at a constant rate (no
significant change) to the point it is
measured – even though the rate
decreases as reaction goes on, it is
enough to determine an integer order.
• The rate is assumed to be proportional
to 1/t (=k/T) and is repeated for several
different concentrations to work out k
(gradient when plotted against []).
82
NB: If a reaction is quenched, it is stopped
Collecting by gas: use a gas syringe, downward delivery (if denser than Using a calorimeter: This measure s colour change by absorbing light wavelengths
air, upward if less) or collection over water (if not very soluble, e.g. using a filter complementary to colour being absorbed in a reaction.
oxygen and hydrogen). 1. Prepare solution of known concentration
Some errors: 2. Pick complementary colour (normally given, e.g. blue/green for iodine)
1. Some gas may escape when replacing the bung (to reduce this use 3. Zero calorimeter with water
a string to hold reactant in place and shake to start reaction) 4. Measure absorbance for different known concentrations
2. When the stopper is replaced the volume of the bund displaces 5. Plot curve of concentration and absorbance
the same volume of air into the syringe/cylinder (again use a small
6. Carry out reaction and use calibration curve to convert absorbance to
test tube and shake to start reaction)
concentration
3. The gas syringe will always contain some air pushed into it by gas
7. Plot graph of concentration against time
generated in reaction, but this will not affect the result since total
volume of gas and air collected will be identical to volume
produced
4. You can only use collection over water if the gas is insoluble, i.e. Titrating:
you can’t collect carbon dioxide using this method as it is soluble
You can take various samples throughout the
(Nb: oxygen much less soluble but some may still dissolve).
course of a reaction by quenching it at various
times, e.g. by rapid cooling, adding a chemical
to remove a reactant which isn’t being
monitored, or adding a large known volume of
water to the sample. This may then be titrated
to find the concentration of the reactant or
product and a graph may be produced from
this. 83
The Arrhenius Equation
When temperature increases the rate and rate constant both increase. These are affected because:
• Increasing the temperature shifts the Boltzmann distribution to the right, increasing the proportion of particles that exceed
the activation energy, Ea
• As the temperature increases, particles move faster and collide more frequently
With increasing temperature, the increased frequency of collisions is comparatively small compared with the increase in
proportion of molecules that exceed Ea from the shift in the Boltzmann distribution. Therefore the change in rate is mainly
determined by Ea.
The exponential relationship between the rate constant k and temperature T is described by the Arrhenius equation.
The exponential factor represents the proportion of molecules that exceed Ea and have sufficient energy for a reaction to take place.
The pre-exponential term, or the frequency factor, takes into account the frequency of successful collision (those with correct
orientation). This term is essentially constant over small temperature ranges, although is does slightly increase with temperature. This
essentially gives the rate if there were no activation energy.
The exponential form of the equation is more useful as it allows us to determine both Ea and A
graphically by giving a linear graph in the form y=mx +c. In this case by plotting lnK against 1/T, it gives a
downward straight line with: gradient of –Ea/R and an intercept of lnA on the y axis. Note that lnK can be
positive or negative so the graph may come either side of the origin.
84
Note: all equations given in situation where
Equilibrium constants
A mole fraction of a gas is the same as its proportion by Kc is the equilibrium constant in terms of
volume to the total volume of gases in a mixture. All mole equilibrium concentrations. It is given by the law
fractions in a gas mixture must equal one.
stated – the concentrations of products at
equilibrium raised to the power of stoichiometry
in the equation divided by that of the reactants.
The units are dependent on the concentration
terms and need to be worked out.
In heterogeneous equilibria (where not all the
equilibrium species have the same state/phase),
The partial pressure, p, of a gas is the contribution that the gas the concentration of solids and liquids are
makes towards the total pressure, P. The sum of all partial essentially constant, therefore are omitted from
pressures equals the total pressure. the Kc expression as they are automatically
incorporated within the equilibrium constant. Kc
only includes species that are (g) or (aq).
85
Working out the number of moles at
Equilibrium
86
When do equilibrium constants change?
Equilibrium constants are stated at a set temperature, so won’t change despite any
modifications in concentration or pressure, or adding a catalyst. The only thing that But why does a change in concentration not affect Kc?
affects the equilibrium constant is temperature. When writing explanations for change
of Kc in terms of temperature, you may assume that Kc decreases to then explain why, as
Well, consider the equilibrium below for ammonia (hyperlinked to
Kc no longer equals the ratio and it isn’t in equilibrium, the concentrations changes. For useful YouTube video explanation).
explaining in terms of concentrations, you may assume that K stays constant, so to restore If we increase the concentration of H2(g):
the equilibrium and keep it at the same value, the new equilibrium is established - Even though at the instant we add the hydrogen, if we could
calculate a value for Kc it would have decreased, Kc can only be
calculated when the system is in equilibrium so we have to
calculate it once any change has occurred
If the forward reaction is exothermic, the equilibrium position shifts to the left so the
- Initially, the concentration of hydrogen increases, but according
equilibrium constant decreases and so does the yield of products.
to Le Chatelier’s principle, the system will try to readjust itself
If the forward reaction is endothermic, the opposite happens as the equilibrium and regain its equilibrium by producing more ammonia
position will shift to the right, the equilibrium constant will increase and so will the
- By producing more ammonia, the hydrogen and nitrogen get
yield of products.
used up and consequently their concentrations decrease, as
To explain the equilibrium shift in endothermic reaction for Kc: ammonia’s increases, returning the system to equilibrium
– When the equilibrium system is heated, by Le Chatelier’s principle, the - Hence, Kc stays constant even though the ratio of reactants to
endothermic reaction is favoured to reduce the effect of the change products is now different.
– Therefore the position of equilibrium shifts to the right The same explanation goes for a change in pressure; because even
– As this happens, the concentration of the products increases, whilst that of though originally the rate of both reactions increases
the reactants decreases
– Therefore Kc will increase as the ratio p(C.)/p(A)p(B) gets bigger
For Kp:
– When the equilibrium system is heated, it is no longer in equilibrium
– From given values we know that Kp increases
– The ratio p(C.)/p(A)p(B) is now less than Kp
– The partial pressure of the product, C, must increase, whilst that of A and B
must decrease
– The position of equilibrium will shift to the right
–
87
A new equilibrium is established where the ratio p(C.)/p(A)p(B) is equal to Kp
19 More on equilibrium constants
The image bellow summaries the effect of increasing pressure and is
useful for explaining why the equilibrium shifts, given that K remains
the same. It also describes how the addition of a catalysts doesn’t
What if I add more calcium carbonate in this affect equilibrium constants, nor the position of equilibrium.
example? Since Kc solely relies on the
concentration of CO2, surely using the principle
from the last explanation that means that Kc will
increase?
Wrong. Since CaCO3 is a solid, it doesn’t have a
concentration, therefore when adding more of it
we aren’t changing that and so Le Chatelier’s
principle says nothing about it increasing the yield
of CO2; hence, the concentration of CO2 is
unchanged and Kc stays the same.
88
20.1 Bronsted-Lowry Acids and bases
• A Brønsted–Lowry acid is a species that donates a proton and a Brønsted–Lowry
base is a species that accepts a proton
• Conjugate acid–base pairs:
– In the forward direction, a conjugate acid will donate/release a proton to form its
conjugate base, which in the reverse direction will accept a proton to form its conjugate
acid (and vise versa if there is a second conjugate-acid base pair)
• Acids can be monobasic (=monoprotic), dibasic or tribasic, with the prefix referring
to how many hydrogen ions that can be replaced per molecule in an acid-base
reaction E.g. HCl is monobasic whilst H2SO4 is dibasic, and H3Bo3 is tribasic
• H+ in the reactions of acids with metals and bases (including carbonates, metal
oxides and alkalis) can be represented using ionic equations. This shows how the
acid does not matter – it is the same ion that plays a part and the cl- or SO42- etc.
are spectator ions
89
20.2/3 pH and acid dissociation constant
• The pH scale is a logarithmic scale to the base 10 where a low value of [H+] matches a high
pH, and visa versa. A pH of 1 has 10 times the [H+] than a pH of 2.
• pH=-log[H+(aq)] (log to the base 10)
• Whilst strong acids fully dissociate, weak acids only partially do, hence, as they form an
equilibrium, the acid dissociation constant, Ka, can be calculated. Ka is the same as Kc but
applied to the dissociation as an acid, but whose units are always mol/dm3
• The stronger the acid, the larger the value of Ka (and smaller pKa)
• Due to the very small numbers of Ka, to put it into nicer numbers: pKa = -log(Ka)
• For strong acids we assume complete dissociation, so the [H+]=the [HA] at beginning, so just
use pH=-log[H+(aq)]
• Percentage dissociation is [H+] divided by the concentration of CH3COOH
90
20.4 Acid dissociation constant & Weak
Acids
• [H+] depends on the concentration of the acid and the acid dissociation constant.
• Using equilibrium concentrations, Ka can be calculated as shown below. However, this involves quite a bit
of working and can be greatly simplified by using 2 approximations:
– From figure 1 below, HA dissociates to produce equilibrium concentrations of H+ and A- that are
equal. There will also be a very small concentration of H+ from the ionisation (dissociation) of water
but this will be very small and negligible compared with that from the acid. Therefore, we assume
that
[H+] at equilibrium =[A-] at equilibrium
– From figure 1, the equilibrium concentration of HA is smaller than the undissociated concentration
(as some dissociates to produce H+ ions). As only a very small proportion of HA dissociates, the
amount of dissociated acid is assumed to be the same as the initial concentration of [HA (aq)]
Hence, this simplifies the expression to or:
Determining Ka:
• Prepare a standard solution of the weak acid of known concentration
• Measure the pH using a pH meter and use the equations to work out Ka
91
20.5 Ionisation of water
• Water ionises very slightly, acting as both an acid and a base
• In water, only a very small proportion of molecules dissociate into H+ and OH- so the
equilibrium lies very much to the left. Treating water as a weak acid we can rearrange the
equation to give Ka x [H2O] = [H+][OH-]
• 1000cm cubed of water is mainly undissociated H2O, so [H2O] = 1000/18 = 55.6 mol/dm3, a
constant
• Kw is called the ionic product of water, and it varies with temperature. It is simply the
constant: Ka x [H2O] = [H+][OH-]
• Kw has a value of 10^-14 mol2/dm3 at 25 degrees, which is the value which sets up the
neutral point in the pH scale (pH 7).
• On dissociation water is neutral – meaning it produces the same number of H+ and OH- ions
• Hence, Kw = [H+]^2 and we can work out its pH
92
20.5 PH of aqueous solutions and strong
bases
• At 25 degrees, [H+][OH-]=10^14
• We can use the above to work out concentrations of [H+] or [OH-] given its pH, or visa versa
• Strong bases completely dissociate into [OH-] ions in solutions, hence concentrations can be
assumed the same of [OH-] and the base
• The pH of a strong base can be calculated from its concentration and using Kw
• To do this we take the [OH-] and use Kw value to find [H+], then use a calculator to work out
pH
• For weak bases a similar method can be used to weak acids, but it is not needed for this
syllabus.
93
21.1 Making buffer solutions
• A buffer solution is a system which minimises pH changes on
addition of small amounts of an acid or base
• A buffer solution is the mixture of a weak acid and its conjugate
base (HA and A-). It has a high [HA] and of [A-] but a low [H+]
• To prepare a buffer solution you can mix a weak acid with its salt,
e.g. ethanoic acid and sodium ethanoate. The weak acid partially
dissociates, but the [A-] is still very small, so it provides the
source of the weak acid component of the buffer, whilst when
added to water, the salt completely dissolve and provides the
conjugate base component
• Another way to produce a buffer is to add an aqueous solution of
an alkali to an excess of the weak acid. The weak acid is partially
neutralised by the alkali, forming the conjugate base. Some of the
weak acid is left unreacted and so resulting solution contains a
mixture of the salt of the weak acid and the unreacted weak acid
• Two reservoirs to remove added acid and alkali: In ethanoic acid,
the position of equilibrium lies well to the left. Adding ethanoate
ions shifts it even further to the left, reducing the already small
[H+] and leaving a solution containing mainly the two buffer
components, which act as two ‘reservoirs’ that are able to act
independently to remove added acid or alkali by shifting
equilibrium either to the left or to the right
94
21.1 Action of buffer solutions
• When H+ ions are added:
– [H+] increases
– H+ ions react with conjugate base A-
– Equilibrium position shifts to the left removing most of the added [H+] ions
– Hence pH remains roughly constant
• When OH- ions are added:
– [OH-] increases
– The small amount of H+ ions react with the OH- ions to produce water
– [H+] decreases
– Equilibrium position shifts to the right as more HA dissociates
– Hence pH remains roughly constant
• Different weak acids results in buffer solutions that operate over different pH ranges
• A buffer is most effective when [HA (aq)] = [A- (aq)]:
– The pH of the buffer solution is the same as the pKa value of HA
– The operating pH is typically over about two pH units, centred at the pH of the pKa value
• Although for weak acids we assume that [H+]= [A-], for buffers this is no longer true as we have added A-
(aq). Therefore, use the normal Ka expression, which you can rearrange to be:
– Ka[acid]/[salt]=[H+]
• When [HA] and [A-] are the same, Ka=[H+] so pKa = pH
95
21.2 Buffer solutions in the body
• Blood plasma in the body needs to maintain a pH between 7.35 and 7.45
(for enzymes to function properly – otherwise leads to either a condition
called acidosis (if below), causing fatigue and shortness of breath and in
extreme cases, shock or death, whilst alkalosis can cause muscle spasms,
light headedness and nausea)
• To maintain blood plasma pH, there is a carbonic acid–hydrogencarbonate
buffer system (H2CO3/HCO3–)
• As the body produces more acidic materials than alkaline, to prevent the
buildup of H2CO3, it is converted to CO2 and exhaled by the lungs
(increased breathing to get rid of acid)
96
21.3 pH and indicators
• Indicators change colour with a change in pH
• Most indicators are weak acids, represented as Hin
• The weak acid HIn, and its conjugate base, In-, have different colours
• The end point of a titration is when the indicator changes colour, so when Hin and In- are
equal in concentration ([HA]=[A-])
• Equivalence point – the point at which the volume of one solution has reacted exactly with
the volume of the second solution
• The pH of the endpoint is when [HA]=[A-], hence Ka=[H+], so pKa = pH
• You must choose indicator carefully as all have different ranges, most over 2 pH units
• The ideal indicator would have an end point that would coincide with the equivalence point,
but if not then it is only suitable when the pKin value is within the pH range of the near
vertical section of the curve
• When adding a basic solution (adding OH- ions), they react with H+ ions, so equilibrium
shifts to right to produce more H+ ions, hence producing more In- ions
• When adding H+ ions, equilibrium shifts to left and more Hin colour can be seen
Using a pH meter:
• Before using a pH probe, calibrate it against a buffer solution of known pH
• Match the temperature setting of the probe (if there if one) to that of the
solution (pH is temperature dependent)
• Then place probe vertically into the solution, waiting until the pH reads steadily
before taking measurement
• Wash the probe with de-ionised water before making another measurement.
*Measuring pH of a known concentration of an acid or base would indicate if it was
strong or weak. 97
21.3 Acid-base titration curves
Type of pH Methyl Phenolph
titration range orange thalein
suitable? suitable?
98
5.2.1 Lattice Enthalpy
• Lattice enthalpy (∆LEH) is the formation of 1 mole of an ionic lattice from its
isolated gaseous ions. It is used as a measure of strength of ionic bonding in a giant
ionic lattice
• Lattice enthalpy is always exothermic as it involves the ionic bond formation from
the separate gaseous ions
• The higher the lattice enthalpy, the higher the melting point of an ionic compound
• The greater the charge densities of ions, the greater the attraction in the lattice
and hence the larger the lattice enthalpy:
– Smaller ions will have greater attraction for each other as there is smaller atomic radii so
will create a higher charge density, so will have larger lattice enthalpies and melting
points
– Ions with a greater charge will have greater attraction and charge density so larger
lattice enthalpy
99
Born-Haber cycles
• You cannot directly measure lattice enthalpy so need to construct a Born-Haber cycle to indirectly calculate it using other
enthalpy changes
• Enthalpy of atomisation: enthalpy change accompanying the formation of 1 mole of gaseous atoms from an element in standard
conditions
• First Electron affinity: enthalpy change accompanying the addition of 1 electron to each atom of a mole of gaseous atoms to
form 1- ions (opposite to 1st ionisation energy), always exothermic as incoming electron is attracted towards nucleus. (Extension
of applied knowledge: Electron Affinity becomes more exothermic across the period because effective nuclear charge increases
across the period therefore the shells of electrons are pulled closer to the nucleus so the electron must lose more energy to
move closer to the nucleus.)
• Second electron affinity: addition of 1 electron to each atom of a mole of gaseous 1- ions to form 2- ions. It is always
endothermic as incoming electron is repelled by the negative ion so requires force
• Watch out for: instances where you require 2 of each atom (E.g. in MgCl2 will require 2 of the chlorine’s enthalpy changes), and
instances where you requires 2 electron affinities or ionisation energies (E.g. in MgCl2, where Mg is 2+ ion)
• Also note that the value for the bond enthalpy of a molecule is the value of atomisation for each of the atoms (E.g. if enthalpy of
atomisation of chlorine is +150kJ/mol, the bond enthalpy of Cl-Cl is 2x150 = 300kJ/mol)
100
Enthalpy changes in solution
The enthalpy change of solution is the
enthalpy change that takes place when one
The enthalpy change of hydration is the
mole of a solute dissolves in a solvent. When
enthalpy change when dissolving 1 mol of
the solvent is water, the ions from the lattice
gaseous ions in water, ΔhydH. It is always
end up as aqueous ions surrounded by water
exothermic
molecules. ΔsolH can either be exothermic or
endothermic.
As the size of the ions increases: As the size of the ions increases:
• Ionic radius increases • Ionic radius increases
• Attraction between ions • Attraction between ion and
decreases water molecules decreases
• Lattice enthalpy is less negative • Hydration energy is Iess
• Melting point decreases negative
102
5.2.2 Entropy
• Entropy is a measure of the dispersal of energy in a system. It increases the more
disordered the system is
• Entropy increases as molecules become more disordered, so as you go from solid
to liquid to gas, with gases having the largest entropies
• Melting and boiling increase the randomness of particles as the energy is more
spread out so the change in entropy is positive
• Production of a gas increases the disorder of the particles, so increasing the
number of gas molecules results in an increase in randomness of particles, energy
is more spread out so change in entropy is positive
• Standard entropies: the entropy of one mole of substance under standard
conditions (100kPa, 298K), in J K−1mol−1 , always positive (always has some disorder
as its above 0K)
Note: that there isn't very big jump in entropy when ice turns to water
because the hydrogen bonding between the liquid molecules imposes a fair 103
amount of order on them even in the liquid.
Free energy
• The term feasibility is used to describe whether a reaction is able to happen and is energetically feasible
(spontaneous). This can be used to explain why some endothermic reactions take place at room
temperature.
• This depends upon the overall energy change during a chemical reaction, called free energy change (∆G),
made up of both the entropy change at the temperature of the system (dispersal of energy within the
system itself), T∆S, and the enthalpy change of the system (the heat transfer between the chemical system
and the surroundings), ∆ H
• In order to be feasible there must be a decrease in free energy, so ∆G<0 (worked out using equation given
top right)
• Typically ∆H is much larger than ∆S, so given in kJ/mol rather than J/mol. Hence, ∆H normally dominates
the equation but it depends upon the temperature (effects given in table). You must remember to convert
∆S into kJ/mol before using the Gibbs’ equation
• Temperature must be in K and both ∆H and ∆S must be consistent
• When ∆G = 0 it gives the minimum temperature for the reaction to be feasible
Limitations:
• Some reactions have a negative ∆G yet still do not seem to take
place, this is because it does not take into account the kinetics
or rate of a reaction
• A very large activation energy results in a very slow rate, so may
take place is the reactants are left for long enough but normally
require a catalyst
104
5.2.3 Redox reactions
• Oxidising agents oxidise another species, taking their electrons and
contain the species that is reduced
• Reducing agents contain the species that is oxidised and reduce
another species by giving them electrons
• Even though HNO3 is a strong oxidising agent, in a reaction only the
nitrogen atom is reduced in oxidation state, hence be careful with
the language used!
105
Redox titrations Fe2+/MnO4 – (Analysing
reducing agents)
Potassium manganate of The reaction is self-indicating; The solution reacts and is
known concentration is decolourised as it is added. The end point is when there is an
added to burette (an excess of MnO4- ions present so on the first permanent pink
oxidising agent) colour
Acidified manganate
(VII) ions are reduced
so they oxidise the
reducing agent, such as
Iron (II) ions or
ethanedioic acid
108
Basics of voltaic cells
• Voltaic cell: an electrochemical cell that converts chemical
energy into electrical energy, can be made by connecting
together two different half-cells which then allows the electrons
to flow
• Half-cell: contains the chemical species present in a redox half
equation. The two half-cells need to be kept apart, else if the
chemicals could mix, the electrons would flow in an
uncontrolled way and heat energy would be released rather
than electrical
– Metal/metal ion half cells are the simplest type and consist of a metal rod
dipped into the solution of its metal ion, represented using a vertical line for
the phase boundary between the two. At this boundary an equilibrium will be
set up, which by convention is written so the forward reaction is a reduction
– Ion/Ion half cells contain ions of the same element in different oxidation
states, made by mixing aqueous solutions of both and using an inert platinum
electrode to transport the electrons
109
Standard electrode potentials
• The tendency to be reduced and gain electrons is measured as a standard
electrode potential. This is describe as the e.m.f (electromotor force) of a
half-cell compared with a standard hydrogen half-cell under standard
conditions (All solutions have a concentration of exactly 1 mol/dm3 (or
are equimolar), and at a temperature of 298K (25 degrees c) and a
pressure of 100kPa)
• The hydrogen half cell consists of hydrogen gas and H+ solution with a
platinum electrode. By definition, the standard hydrogen electrode is
exactly 0V, the sign of a E shows its relative tendency to gain electrons
compared with this. It is always drawn on the left of a diagram
• To measure a standard electrode potential, prepare two standard
solutions, connect the two electrodes by a wire to allow a controlled flow
of electrons to a high resistance voltmeter (as it has a low current so
won’t affect the reading) and add a salt bridge, record the standard cell
potential from the voltmeter.
• A salt bridge creates a complete circuit (therefore make sure it’s drawn in
the solution!) so the electrons will flow. It allows the movement of ions
across the cells. Normally it is a strip of filter paper soaked in KNO3 or a
tube containing KCl (provided half-cell doesn’t contain Ag otherwise the
latter would react to form a precipitate)
110
Electrode potentials
• The more negative the E value, the more reactive the metal and the greater the tendency to lose
electrons and undergo oxidation
• The oxidation electrode is the negative electrode, and goes on the LHS
• Right Reduction
• The standard cell potential = E (the positive electrode, reduction) - E (the negative electrode)
• If E cell comes out negative, the reaction would not occur
• In a table of standard electrode potentials, the strongest reducing agent is on the top at the right
(most negative) and the strongest oxidising agent is the bottom on the left
• Limitations of predictions using E values
– Reaction rate, doesn’t take into account the rate of a reaction, even if it indicates the
thermodynamic feasibility
– Concentration, any change to concentration will affect the value of the electrode potential
and hence the overall cell potential. E.g. if the concentration of Zn2+ ions is reduced (e.g. if
water added!), the equilibrium will shift to the left so will increase the number of electrons
in the system and the electrode potential will be more negative. Similarly if the
concentration of Zn2+ ions is greater than 1 mol/dm3, the system will shift to the right and
become less negative (less electrons).
– Actual conditions may be different to the standard conditions used to record the E values
111
Storage and fuel cells
Primary cells: Secondary cells: Fuel cells:
• • • Uses the energy from the reaction of a fuel with
Non-rechargeable, single use Rechargeable
oxygen to create a voltage
• Energy produced by redox at • Reaction is reversed when charging, • Changes take place at the electrodes
electrodes regenerating the chemicals • Reactants flow in, products flow out and electrolytes
• Reactions cannot be reversed • Examples include lead-acid batteries remain inside
• As the chemicals are used up, the in cars and lithium-ion cells in laptops • Can operate continuously if provided a constant
supply of fuel and O2
voltage will fall
• Don’t have to be recharged
• Used in low-current, long-storage • Hydrogen is the most common fuel (stored on the
devices such as wall clocks and smoke surface of a solid, within a solid or in a liquid under
detectors pressure, in a tank away from the cell)
• It doesn’t produce carbon dioxide, only water.
• Hydrogen fuel cells use either an alkali or acid
electrolyte, which despite different redox systems
have the same cell potential (+1.23V)
Disadvantage:
• Hydrogen is a gas (volatile) so
hard to store and transport
• H2 is flammable/explosive
112
Electronic configuration of transition metals
All transition metals are d-block elements (i.e. the All fill up the 4s subshell before the 3d subshell
highest energy level is the d-subshell) There are two exceptions to the above rule:
• Chromium which has configuration [Ar] 3d5 4s1
• Copper which has configuration [Ar] 3d10 4s1
This is because the half-filled and fully filled d10
orbital is more stable
113
Properties of the Transition metals
All d-block elements are metallic, so display the typical physical Transition metals also have these characteristics, that
properties of a metal: they are shiny in appearance and exist in solid differentiate them from other metals:
form as a giant metallic structure with delocalised electrons so • They form compounds in which the transition element
conduct electricity and heat. Due to their small radii they pack has different oxidation states
closely together and have strong bonds, giving them high melting • They form coloured compounds
and boiling points.
• The elements and their compounds can act as catalysts
As catalysts:
• In the Haber process to produce ammonia, iron catalyses the process: N2(g) + 3H2 (g)
2NH3(g)
• In the Contact process to produce sulfuret trioxide, vanadium (V) oxide catalyses the
process: SO2 (g) + O2(g) 2SO3(g)
• During the manufacturing of margarine, vegetable fats undergo hydrogenation using a
nickel catalyst: alkene + H2 water + oxygen
• The catalytic decomposition of hydrogen peroxide uses manganese (IV) oxide (MnO2)
2H2O2(aq) 2H2O (l) + O2(g)
• The reaction of zinc metal with acids is catalysed by the presence of Cu2+ ions: Zn(s)
+H2SO4 (aq) ZnSO4 (aq) + H2(g)
Although you don’t need to know the details of the catalytic processes, they are all important
in industry as they increase the rate of reaction and lower the activation energy. The lower
energy requires less electricity or fossil fuel use, which in turn cuts the emissions of carbon
dioxide which is linked to global warming. Producing it faster and using less energy cuts costs
and increases profitability.
114
Coloured compounds and oxidation states
Variable oxidation states and coloured compound formation
All transition metals form compounds with more than one oxidation state e.g. FeCl2 and FeCl3
The number of states for each element increases across the series to manganese then decreases
All form 2+ ions as they lose electrons from the 4s orbital
A species with a transition element in its highest state is often a strong oxidising agent, ones with them in low states are often reducing
agents.
Each state often has a characteristic colour, which can be produced by dissolving the solid in solution. This colour is linked to the
partially filled d-orbitals of the ions
115
Complex ions
• A ligand is a molecule or ion that donates a pair of electrons to a central metal ion to form a
coordinate bond. They can be neutral, like water, or negatively charged, like a hydroxide ion
• A coordination number indicates the number of coordinate bonds attached to the central
metal ion
• A complex ion is formed when one or more negatively charged ions (ligands) bond to a central
metal ion. This is a property of the transition and all d-block elements, though not restricted
to these, for example aluminium can form complex ions.
• Ligands can either be monodentate, bidentate or poly/multi-dentate. This depends on how
many electron pairs it is able to donate to the central ion.
116
Shapes of complex ions
Complexes with a coordination number For coordination number of four:
of six form an octahedral shape, with 90 • Tetrahedral is the more common shape with bond angles of 109.5 E.g. many
degree angles E.g. many hexaaqua tetrachloro complexes, CuCl 42– and CoCl 42–
complexes, [Cu(H2O)6]2+, [Fe(H2O)6]3+ • Square planar shape occurs in the complex ions of transition metals with 8 d-
electrons in the highest energy d-subshell, so Platinum (II), Palladium (II) and gold
(III). They are arranged at the corners of a square, similarly to the octahedral shape
but without the ligands above and below the plane. E.g. platin: Pt(NH3)2Cl 2
117
Shapes of complex ions
Some complex ions exhibit stereoisomerism, of either cis-trans or Optical isomerism only occurs in octahedral complexes with
optical form. two or more bidentate ligands, where the two enantiomers
are non-superimposable mirror images of each other. This is
Cis-trans isomers in complex ions does not require a C=C, as the shape the case with the two forms below. Only the cis-isomer version
of the complex holds groups in different orientations. It occurs in some can form optical isomers as the mirror images are exactly the
square planar and octahedral complexes. same
• In square planar complexes, with no more than two identical
ligands attached to the central ion, a cis-isomer is where the two
identical groups are adjacent to each other (are 90 degrees apart)
and the trans-isomer occurs when the coordinate bonds between
the identical ligands are 180 degrees apart
• It is also found in octahedral complexes with four of one type of
ligand (or two bidentate ligands) and two of another. Again, the cis-
isomer occurs where the two identical ligands are 90 degrees apart,
and the trans when they are 180 degrees apart.
118
Ligand substitution
Ligand substitution reactions occur when one ligand is replace by another (duh). Sometimes the coordination number may change during this reaction,
causing a change in shape. This occurs as some ligands are larger in size than others so fewer can fit around the central ion, although the oxidation state of
the metal stays the same. For example, When substituting chloride ligands for water ligands, the chloride ligands are larger in size so the coordination
number will change from +6 to +4.
120
Precipitation reactions
Precipitation reactions occur when two aqueous solutions containing ions react together to form an insoluble ionic solid. Transition metal ions form
precipitates with sodium hydroxide and ammonia, though some dissolve in an excess to form complex ions.
When ammonia is added a two stage reaction takes place. Firstly it acts as a base and as it is aqueous, the OH- ions react to form a precipitate (as if
NaOH were added). In the second stage, this precipitate may dissolve in excess, though some precipitates formed are insoluble
Cu2+ Pale blue Blue precipitate of Cu(OH)2 (or Precipitate dissolves in excess
Cu(OH)2(H2O)4) forms ammonia to form dark blue
Insoluble in excess solution of
[Cu(NH3)4(H20)2]2+
121
Qualitative analysis using redox
MnO4- oxidises Fe2+ to Fe3+ I- reduces Fe3+ to Fe2+.
Colour change: Purple colourless Colour change: orange-brown green but obscured by
This can be explained in terms of standard electrode potentials brown iodine
122
Redox reactions
Cu2+ can be reduced to Cu+ using iodide
ions
Colour change: Pale blue white
precipitate in brown solution
You can use the reactions on this slide and the previous two to distinguish between pairs of compounds.
E.g. to distinguish between copper (I) oxide and copper (II) oxide, heat with dilute sulfuric acid. CuO would form a blue solution of
CuSO4, whereas Cu2O would form a blue solution and brown solid
If asked why a certain reducing/oxidising agent may not be suitable, consider the colour changes of both reagents. E.g. In the
reduction of Fe3+ to Fe2+, I- is oxidised to I2. This colour change is orange-brown and colourless to pale-green and brown. Thus,
although you may wish to see a colour change orange-brown to green, it will end up appearing brown to brown, though perhaps
different shades 123
Organic chemistry and analysis
Module 6
124
25.1 Benzene and Kekulé's model
Kekulé suggested benzene was a structure based on a six membered ring of carbon atoms joined
by alternate single and double bonds. Not all chemists accepted this model though due to the
following reasons:
• The lack of reactivity in benzene; If it contained C=C bonds it should undergo electrophilic
addition reactions and decolourise bromine under normal conditional, however, it does not.
• The lengths of Carbon-Carbon bonds in benzene; As shown by X-ray diffraction, the bonds
length of all the carbon-carbon bonds were between that of a single and double bond
• Hydrogenation enthalpies; Due to the 3 carbon-carbon double bonds Kekulé suggested
(cyclohexa-1,3,5-triene) it should have 3 times the enthalpy change of hydrogenation of
cyclohexane however its value is less exothermic than expected meaning the structure of
benzene must be more structured than this.
Hence, the delocalised model of benzene was proposed by those that thought the evidence
above was enough to disprove his structure. The de-localised model has the following features:
• Benzene is a planar, cyclic, hexagonal hydrocarbon with 6 Cs, each of which use 3 electrons
bonding to two other carbons and a hydrogen atom, the fourth is delocalised
• Each carbon atom has one electron in a p-orbital at right angles to the plane of the bonded
carbon and hydrogen atoms
• Adjacent p-orbitals overlap sideways, in both directions, to form a ring of electron density
above and below the plane of carbon atoms. This creates a system of pi-bonds which
spread over all the six carbon atoms in the ring structure formed of 6 electrons said to be
delocalised.
• This accounts better than Kekulé’s model for the lack of reactivity as compounds with
delocalised electrons are more stable than those without.
125
Naming aromatic compounds
Compounds with one substituent group (monosubstituted):
• The benzene ring is often considered to be the parent chain.
• When it is attached to an alkyl chain with a functional group of a chain with seven or more carbon atoms,
the benzene is considered a substituent and phenyl is used as a prefix to represent it.
• Some exceptions to this include benzoic acid (benzenecarboxylic acid), phenylamine and benzaldehyde
(benzenecarabldehyde)
When the compound has more than one substituent group, the ring is numbered like a carbon chain starting at
one of the substituent groups and listed in alphabetical order.
2-bromophenylamine 126
Nitration of benzene
Nitration of benzene:
• Reacts with concentrated nitric acid in the presence of a concentrated sulfuric acid catalyst, to form
nitrobenzene. Heated to 50 degrees to speed up reaction but temperature control is important as if it rises
above this, further substitution may occur (producing dinitrobenzene).
• In this reaction the nitronium ion (produced by reaction of nitric acid and sulphuric acid, which also forms
water) acts as an electrophile, reacting with benzene in an electrophilic substitution reaction
• The electrophile is attracted to the electron density of benzene and accepts a pair of electrons to form a
dative covalent bond. The structure is then unstable so releases a H+ ion, which goes on to react with the
HSO4- ion to regenerate the catalyst.
127
Halogenation of benzene
• Halogens do not react with benzene unless an anhydrous halogen carrier catalyst
is present, because benzene is too stable to react with the non-polar halogen
molecule, so requires a halogen ion (e.g. bromonium ion, Br+) which is generated
when the halogen carrier catalyst reacts with bromine in the first stage of the
mechanism
• Common halogen carriers include iron, iron halides and aluminium halides (e.g.
AlCl3, FeCl3, AlBr3 and FeBr3, Fe) which can be generated in situ from the metal
and the halogen
• At room temperature in the presence of a halogen carrier bromine reacts with
benzene in an electrophilic substitution reaction, as with nitration
128
Electrophilic substitutions of benzene:
Alkylation and Acylation
Alkylation of benzene a hydrogen atom is substituted by
an alkyl group by reacting benzene with a halo alkane in
the presence of a halogen carrier such as AlCl3 (halogen
carrier catalyst which generates the electrophile). This
increases the number of carbon atoms in a compound
and is sometimes called a Friedel-crafts alkylation after
the chemists who first carried it out
129
Comparative reactivity of alkenes with
Arenes
• Arenes are aromatic (contain benzene ring) hydrocarbons
• Alkenes decolourise bromine by an electrophilic addition reaction (as the pi-bond electrons
are localised above and below plane of the 2 carbon atoms in the double bond so has a high
electron density, inducing a dipole in the Bromine molecule and so on) .
• Unlike alkenes, benzene does not react with bromine unless a halogen carrier catalyst is
present because it has delocalised pi-electrons spread above and below the plane of carbon
atoms in its ring structure. Therefore the electron density around any two carbons is less than
that of the C=C bond in an alkene. When a non-polar molecule approaches the benzene ring
it hence has insufficient electron density to polarise the molecule, preventing a reaction
• Alkenes react with bromine by electrophilic addition, benzene by electrophilic substitution
130
Phenols
• Phenols are a type of organic compound containing a hydroxyl group bonded to an aromatic ring.
The simplest member is named phenol (C6H5OH)
• Although alcohols and phenols share some common reactions, many are different as the proximity
of the delocalised ring influences the –OH group. As an example, 2-hydroxybenzoic acid is a phenol
but 2-phenylethanol is not as the group is not directly bonded to the aromatic ring
• Phenol is less soluble in water than alcohols due to the presence of the non-polar benzene ring. It
partially dissociates to produce a phenoxide ion and a proton so is classed as a weak acid.
• Phenols are weakly acidic (more acidic than alcohols, but less so than carboxylic acids). This is
shown by the neutralization reaction with NaOH but absence of reaction with carbonates or can be
seen by comparing the acid dissociation constant Ka of an alcohol with that of a phenol and a
carboxylic acid:
Carboxylic acids Will react with aqueous NaOH Strong enough to react
• Phenol reacts with sodium hydroxide to form the salt, sodium phenoxide, and water in a
neutralisation reaction
131
Electrophilic substitution reactions of
phenols
• Phenols decolourise bromine water at room temp. without a catalyst, producing a white
precipitate of 2,4,6-tribromophenol.
• Phenols react readily with dilute nitric acid at room temperature to form a mixture of 2-
nitrophenol and 4-nitrophenol Phenol reacts more readily with bromine and nitric acid
(requiring dilute rather than conc. Nitric acid and not needing a catalyst, sulphuric acid).
• This increased reactivity is caused by the lone pair of electrons from the oxygen p-orbital
from the oxygen being donated/partially delocalised into pi-system, therefore increasing
the electron density of the benzene ring in phenol and is more susceptible to attack from
electrophiles
132
25.4 Directing groups
• Normally, bromine requires a halogen catalyst to react with benzene. Meanwhile, bromine reacts rapidly
with phenylamine, and with nitrobenzene reacts slowly with bromine, requiring both a halogen carrier
catalyst and a high temperature. Hence, the ring in nitrobenzene is less susceptible to attack
• Therefore, we can say the –NH2 group activates the ring as it reacts more readily with electrophiles, whilst
the –NO2 group deactivates it. Not only does the rate and extent of substitution differ but also the
position of substitution
• A directing effect is the effect a group can have on the position of any second substituent
group on the benzene ring in electrophilic substitution of aromatic compounds .
• Electron donating groups, including OH and NH2, have a 2- and 4-directing effect whilst
withdrawing groups have a 3-directing effect, e.g. NO2
• This is very important when planning an organic synthesis and you may need to consider the
order in which the reactions are carried out to ensure the correct pattern for the required
product is prepared
133
26.1 Recap on Carbonyls
Carbonyls contain a C=O group
In aldehydes:
– The functional group is attached to the end of the chain (written as R-CHO)
– To name add suffix –al to longest chain shorted e.g. Octanal
– Can be oxidised to carboxylic acids with acidified dichromate ions, changing solution from orange to green (Cr6+ to
Cr3+)
In ketones:
– Functional group is found in the middle of the chain(written as RCOR)
– To name the number of the carbon atom and –one as suffixes to shorted name of longest chain e.g. pentan-2-one
– Cannot be oxidised (no colour change with acidified dichromate ions)
Carbonyls reactivity is influenced by the nature of the carbon-oxygen double bond. Whereas the C=C bond in
alkenes is non-polar, C=O in carbonyls is polar due to the difference in electronegativity. Therefore, carbonyls
react with some nucleophiles which are attracted to the carbon atom and results in a nucleophilic addition
reaction. This is different from the electrophilic addition reaction that occurs with the non-polar C=C bond in
alkenes. Read more on next slide.
134
Nucleophilic addition reactions of carbonyls
• Carbonyls can be reduced to form alcohols by reacting with NaBH4 in a nucleophilic addition reaction (where nucleophile
can be considered as being the hydride, H-, ion (with subsequent protonation of the organic intermediate from H2O). To do
this they are warmed with the reducing agent in aqueous solution. Aldehydes are reduced by NaBH4 to form primary
alcohols, whilst ketones produce secondary alcohols (using [H] to represent the reducing agent)
• They also react in this way with HCN to form hydroxynitriles (contain –OH and a nitrile group, C triple bonded to N) . HCN is
a colourless, poisonous liquid which boils slightly above room temperature, so cannot be used safely in an open lab. Instead,
HCN is formed in situ by using sodium cyanide and sulphuric acid (though it is still potentially very hazardous). Again, this
reaction is useful as it increases the length of the carbon chain. Although the Cyanide ion is usually written as CN-, the
negative charge is actually on the carbon atom and it is important to show this as –CN in the mechanism
• In nucleophilic addition, the lone pair of electrons from the nucleophile (-Cn or –H) are attracted and donated to the
positive carbon atom of the C=O, forming a dative covalent bond, the pi-bond of C=O then breaks by heterolytic fission and
the negatively charged O- intermediate donates a lone pair to H+ (from H2O or HCN) and is hence protonated to form an
alcohol.
135
Identifying aldehydes and ketones
To detect carbonyls we use Brady’s reagent (2,4-dinitrophenyldrazine dissolved in
methanol and sulphuric acid as a pale orange solution). Note: 2,4-DNP when solid
can be very hazardous because friction/a sudden blow can cause it to explode.
When a few drops of the unknown substance is added to 5cm of 2,4-DNP a
yellow/orange precipitate will form in the presence of a carbonyl group (NB: if no
crystals form at first, add a few drops of sulphuric acid).
The precipitate can then be analysed to identify the carbonyl compound by being
filtered, recrystallized and then recording its melting point, which can be compared
to a database to identify the original.
137
26.4 Carboxylic Acid derivatives
All carboxylic acid derivatives can be hydrolysed to form the parent carboxylic acid and
all contain a common acyl group
139
Acyl Chlorides and their reactions
• Preparation: anhydrous Thionyl chloride (SOCl2)
(otherwise both acyl chloride and SOCl2 would react
with water!!) reacts with carboxylic acids to form acyl
chlorides. This produces SO2 and HCl gases, which are
harmful so the reaction should be carried out in a
fume cupboard
• As they are very reactive it is useful in organic
synthesis as are easily converted into different
carboxylic acid derivatives with good yields. They
react with nucleophiles, losing the chloride ion and
retaining the C=O bond
• Acyl chloride + Alcohol Esters
• Acyl chloride + Phenol/phenoxide ion esters
Carboxylic acids aren’t reactive enough to form esters
with phenols, but acid chlorides and anhydrides are
and neither need an acid catalyst
• Acyl chloride + Water Carboxylic acid + Hydrogen
chloride gas Violent reaction which results in dense
steamy HCl fumes
• Ammonia and amines act as nucleophiles by donating
the lone pair of electrons on the nitrogen atom to an
electron-deficient species:
• Acyl chlorides + Ammonia Primary amide
(nitrogen attached to one carbon atom)
• Acyl chlorides + Primary amine Secondary amide
(nitrogen attached to two carbon atoms)
140
Nucleophilic addition-elimination (not
required knowledge)
With nucleophiles, acyl chlorides react via a mechanism called nucleophilic
addition-elimination as follows:
• Step 1: Lone pair of nucleophile is attract to and donated to positive carbon atom, forming a
dative covalent bond and a negatively charge on the oxygen on the intermediate
• Step 2: A lone pair of electrons on oxygen reforms the doubled bond, causing a chloride ion
to be removed. A proton (H+) is also then lost to complete the elimination (shown on
diagram as one step)
141
Acid anhydrides and their reactions
• Acid anhydrides react in a similar way to acyl chlorides with alcohols,
phenols, water, ammonia and amines.
• They are less reactive than acyl chlorides and more useful for some lab
preparations where acyl chlorides may be too reactive.
• You can produce esters by reacting acid anhydrides with alcohols
142
27.1 Amines and Amides
• Amines are compounds derived from ammonia where one or more of the hydrogen atoms have been
replaced by a carbon chain. They can be classified as below. (typically as -NH2)
• They are basic as the lone pair of electrons on the nitrogen accept protons. When the nitrogen accepts a
proton, a dative covalent bond forms between the nitrogen and the hydrogen. Due to this property they react
with dilute acids to form salts.
• Amides contain an amine group bonded to the same carbon as C=O group (careful: this is not a ketone as the
C=O is not in the middle of a carbon chain as the C is bonded to N directly). They are the products of reactions
of acyl chlorides with ammonia and amines. They can be primary, secondary or tertiary as with amides. (-NH
next to =O)
143
27.1 Formation of Amines
Primary amines: react a haloalkane with ammonia to form a Secondary and tertiary amines:
salt and then react the salt with sodium hydroxide to form react a primary amine with a
an aliphatic amine, NaCl and water. For this, ethanol is used haloalkane and then with sodium
as a solvent to prevent substitution of the haloalkane by hydroxide. Tertiary amines can be
water to produce alcohols and excess ammonia is used to formed by further substitution of
reduce further substitution of the amine group to form secondary amines.
secondary and tertiary amines.
144
27.2 Amino acids
• An α-amino acid is one in which the amine group is bonded to the same
carbon as the -COOH group: General formula RCH(NH2)COOH
• Therefore they undergo the same reactions as amines and carboxylic acids
that we have already learnt:
– As amino acids contain amines, which are basic, they, too, react with acids to make salts
– Carboxylic acid group of the amino acids can react with aqueous alkali to form esters by
producing the ethanoate salt and water
– As amino acids contain carboxylic acid group, they are also easily esterified by heating
with an alcohol in the presence of sulfuric acid. The acidic conditions protonate the basic
amine group.
145
27.2 Optical Isomerism
• Optical isomerism is a type of stereoisomerism that occurs in molecules
containing a chiral centre – a carbon attached to four different groups of
atoms (often marked by an asterisk *)
• This leads to the presence of two non-superimposable mirror image
structures, known as optical isomers or enantiomers, like a pair of hands
* *
146
Unlike addition polymerisation (from alkene monomers to form a continuous Polyesters and polyamides are
carbon chain backbone), these condensation polymers contain ester or amide both condensation polymers
linkages (made by the joining of
Two monomers:
One monomer containing both –OH • A diol (2 –OH groups) and a dicarboxylic acid (2 –COOH groups)
and –COOH (or –COCl) • OR one a diacyl chloride (Two –COCl groups) the other diol
(producing HCl rather than H2O)
Notice that
reacting n moles
of each
monomer results
in (2n-1) moles
of H2O
147
Polyesters and polyamides are
both condensation polymers
(made by the joining of
amide linkages).
148
Hydrolysing Condensation Polymers
Polyesters and polyamides can be hydrolysed, like esters, by using hot
aqueous alkali (e.g. NaOH) or by hot aqueous acid (e.g. HCl)
Recrystallization:
You can purify remove impurities by recrystallization if they have a different solubility to the desired product in the
chosen solvent.
6. Pour solvent into a flask and either warm using a Bunsen or over a water bath if its flammable
7. Slowly add the solvent to the impure sample (this way round to ensure highest yield) until it dissolves. Add
the minimum volume of solvent needed
8. Allow solution to cool until no more crystals form
9. Filter under reduced pressure using ice cold solvent
151
6.2.5 Further practical techniques
Melting point determination:
Pure substances have a sharp melting range (1 or 2 degrees) close to the data book value, impure
samples melt over a much wider range, at a lower temperature than the data book value.
1. Ensure the sample is completely dry and free flowing
2. Take a glass capillary tube and hold over the hot Bunsen flame, rotating until the end of the tube
is sealed
3. Allow the tube to cool, then fill with crystals to about 3mm depth by pushing the open end of the
tube into the solid sample, forcing it in
4. Once prepared use on of the next two methods
Using an oil bath or Thiele tube method: The shape of the Thiele tube allows for formation
of convection currents in the oil when it is heated. These currents maintain a fairly uniform temperature
distribution throughout the oil in the tube. The side arm of the tube is designed to generate these convection
currents and thus transfer the heat from the flame evenly and rapidly throughout the heating oil.
1. Set up Thiele tube or oil bath
2. Attach capillary tube containing the sample to a thermometer using a rubber band
3. Insert the thermometer into a hole in the cork fir Thiele method or clamp it for the oil bath so that the
ends of the thermometer and capillary tube dip into the oil
4. Using a micro-burner, slowly heat the side arm of the Thiele tube or the oil bath whilst observing the
solid. When it starts to melt, remove from the heat and record when all the solid has melted. It’s
important to heat the oil slowly when approaching the melting point and advisable to repeat a second
time to ensure an accurate value is obtained
152
Year 1 Synthetic routes recap
153
Synthetic routes
154
Synthetic routes
155
6.2.1. Chromatography
Terms not expected to know but listed because the textbook has them and I’m pedantic and it may further
understanding:
• Chromatography: used to separate individual components from a mixture of substances. All forms have a
stationary and mobile phase
• Stationary phase: does not move, normally a solid or a liquid supported on a solid
• Mobile phase: does move, normally a liquid or gas
• Adsorbent surface: a solid adsorbent surface is what coats a plastic sheet or glass in a TLC, it is usually
silica, and is the stationary phase in a TLC
• Adsorption: the process that occurs when a gas or liquid or solute is held to the surface of a solid
• In gas chromatography the stationary phase is a high boiling liquid adsorbed onto an inert solid support
and the mobile phase is an inert carrier gas such as helium or neon
• External calibration offers a method for converting between two things not directly done. E.g. created a
calibration curve in gas chromatography
156
6.2.1. Thin Layer Chromatography
• Quick, inexpensive analytical technique to indicate how many components/which ones are in a mixture.
• This works as different components will have different affinities for the absorbent and bind with different
strengths, hence they are separated as each will move up the plate by different amounts
• Intensities shows the amount of the substance present
• TLCs are analysed by calculating the retention factor, Rf, for each component. The components can then be
identified by comparing the Rf values with data books
• Rf = distance moved by component/distance moved by solvent front
• Not pure if it shows spots similar to those of reactants or impurities that don’t show when compared with a
pure solid.
• It’s necessary to wear gloves to prevent transfer of amino acids from skin which could interfere with results
To carry out:
• Draw pencil line (insoluble) as a base line about 1cm from bottom of a TLC plate
• Use capillary tube to place small amounts of solution of sample onto base line
• Pour solvent to a depth about 0.5cm (lower than base line) in a beaker
• Place TLC plate into solvent, cover with a watch glass (ensures solvent doesn’t evaporate
and instead moves up the plate. Sealed atmosphere allows solvent to saturate the
atmosphere inside) and allow solvent to rise up plate until about 1cm from the top
• Remove the plate from beaker and mark the solvent front with a pencil
• Allow plate to dry (in fume cupboard if solvent is toxic or flammable) before circling any
visible spots
• If no spots can be seen, place under a UV lamp and circle, or spray with a chemical or a
locating (developing) agent such as ninhydrin or place in beaker in fume cupboard with
iodine crystals 157
Gas chromatography
• Components are identified by their retention times: the time taken for each component to travel through the column
• Peak integrations can be used to determine the concentrations of components in the sample
• A mobile gas carrier (an inert gas such as nitrogen or helium) carries the components through the gas chromatograph. The
more soluble the component is in the liquid phase, the slower it moves through the column, hence they reach the detector
at different times depending on their interactions with the stationary phase. Therefore the number of peaks determines the
number of different compounds in the substance, but this is not certain as one or more could have the same retention time.
• The concentration of components is determined by comparing its peak integration with values obtained from standard
solutions of that component. Hence to calculate them, you need to obtain a calibration curve of peak area against
concentration by obtaining gas chromatograms for different prepared standard solutions of known concentrations
158
NMR Spectroscopy
Nuclear Magnetic Resonance (NMR) is a technique for analysing Resonance – occurs when the nucleus rapidly flips between two spin states due
compounds by combining a very strong magnetic field and radio to absorbing energy, when under the right combination of strong magnetic field
frequency radiation. The nuclei of some atoms absorb this and radio frequency radiation.
radiation and the energy for the absorption is measured and
recorded as an NMR spectrum. NMR Spectroscopy is mainly used Nuclear Spin – significant if there is an odd number of nucleons (protons and
as proton NMR (detects 1H) and 13C NMR, but it can also detect neutrons). In other atoms (such as 12C) the spins of subatomic particles are
isotopes of elements with odd numbers of nucleons, such as 19F paired against each other, such that the nucleus of the atom has no overall spin
and 31P. (happens when the number of neutrons and the number of protons are both
even).
159
Carbon-13 NMR Spectroscopy
You can use carbon-13 NMR to make predictions about:
• The number of carbon environments in the molecule
• The different types of carbon environments present, from chemical shift values
• Possible structures for the molecule
There are 4 main types of carbon atoms that absorb over different chemical shift ranges, as given in the formulae booklet. The chemical
environment of a carbon atom is determined by the position of the atom within the molecule, thereby carbon atoms bonded to different
atoms or groups of atoms will have different environments and therefore will absorb at different chemical shifts. If two carbon atoms are
positioned symmetrically within a molecule then they are equivalent and have the same chemical environment, contributing to the same
peak.
160
Proton NMR
Spectroscopy
This provides the same information as 13C NMR but for protons (hence the number of different proton environments and the types of these
environments present) along with two extra pieces of information, the relative numbers of each type of proton (from integration traces or
ratio numbers of the relative peak areas) and the number of non-equivalent protons adjacent to a given proton (from the spin-spin splitting
pattern).
Spin-spin coupling: A proton NMR peak can also be split into sub-peaks/splitting patterns caused by the proton’s spin interacting with the
spin states of nearby protons in different environments. The number of sub-peaks is one greater than the number of adjacent protons
causing the splitting (hence it is called the n+1 rule). This occurs in pair as each proto splits the signal of the other.
Some organic compounds contain protons not bonded to carbon atoms, such as –OH or –NH protons and the other functional groups listed
here:
These are difficult to identify as they occur at variable chemical shifts because they may be involved in hydrogen bonding when in solution
(apart from –COOH protons which are more predictable). Broadening peaks mean they’re not usually involved in spin-spin coupling. To
identify these protons you need to run a proton NMR as normal then add D 2O (deuterium oxide) and run the NMR a second time. D 2O
replaces the OH/NH protons in the sample with Deuterium atoms, which don’t absorb in the chemical shift so the peaks will disappear,
deducing a functional group they contain.
161
Practical Chemistry
162
Empirical formula determination
For compounds like Magnesium oxide it can be determined by
heating a sample of magnesium in air then accurately measuring
the mass of the product.
For this you need to:
1. Measure the mass of crucible and lid
2. Add magnesium filings and remeasure mass
3. Place crucible on pipe clay triangle on a tripod and heat
strongly with a Bunsen, raising the lid at intervals to
allow air to enter the crucible (lid is needed to prevent
contents escaping)
4. Allow the crucible to cool and reweigh all contents
Sources of error: Not all the magnesium may have reacted,
when lid is lifted some of the product MgO may escape
Concentrated sulphuric acid is corrosive so should be In filtration: Filtrate – the liquid collected
handled with care using gloves and safety goggles.
Organic substances such as ethanol are flammable so It is possible to find the order of a reaction for a particular reagent by
should be kept away from naked flames and electric plotting a concentration against time graph (or rate against
heating mantle or water bath should be used instead. concentration and using shape – flat is zero, linear positive is first and
curved is second). This method works if there is only one reagent
involved in the reaction. Alternatively, the reaction can be set up so
Anti-bumping granules prevent dangerous splashing and
that the rate depends solely on one reagent by making sure the others
bumping.
are in such large excess their concentration is practically constant and
have little affect on the reaction rate. The graph for zero order is linear,
Substances such as ethanal (21 C) that have a low boiling for first order has constant half-lives and for 2nd has unequal half-lives,
point close to room temperature should be collected but this would need to be checked by finding the rate at different
(when as a liquid) in a flask surrounded by ice to avoid points because some reagents may have fractional orders.
evaporation. 164
Procedures
Making standard solutions: For titrations:
1. Weight out an accurate mass of a solid in a clean, dry 1. Rinse burrete with solution you are going to use,
beaker discard the rinsings and fill the burrette
2. Add enough deionised water to dissolve the solid, 2. Repeat for the pipette, and transfer the 25cm to a
stirring with a glass road conical flask
3. Transfer solution to a 250cm3 volumetric flask using a 3. Add 2-3 drops of indicator to the flask
funnel 4. Add the solution from the burrette with constant
4. Wash the beaker and glass rod and pour rinsings into swirling until the indicator changes colour.
the flask 5. Use that result as a trial titration (record to two
5. Make up to the mark by adding deionised water until decimal places, with last digit either a 0 or 5) and
the bottom of the meniscus is n the mark repeat until you achieve 2-3 concordant results, adding
6. Stopper the flask and invert several times slowly to mix dropwise near the end point
through 6. Calculate the mean titre from concordant results
Use a chemical that is pure, doesn’t absorb or lose moisture (within 0.1cm3)
to environment and has a relatively high formula mass so Tips: Remove funnel used to fill burette before starting,
that weighing errors are minimised. E.g. NaOH isn’t a keep the solution from the first accurate titration to achieve
suitable solid for making standard solutions as it absorbs consistency by colour matching, uncertainty in burettes is
moisture from the air x2, ensure to swirl the sides and include all solution that
may just be running down the side of the conical flask
(alternatively in titrations you may rinse sides with
Indicator Acidic Alkaline Titrations
colour colour deionised water, as although it dilutes the solution, the
amount in moles of the pipetted solutions won’t change,
Methyl orange Red Yellow Strong acid-strong base and that is what’s being titrated).
Strong acid-weak base
166
Experimental enthalpy of neutralisation
To carry out experiment:
1. (Place a polystyrene cup in a glass beaker for support)
2. Rinse a measuring cyclinder with acid then add 25cm3 of it into cup
3. Stir acid with a thermometer and record temperature
4. Rinse a second measuring cyclinder with a base and measure 25cm3 of it
5. Add the base to the acid, stir and record highest temperature reached to calculate temp change (see cooling curve extrapolation
below)
6. Calculate the amount of moles of acid used, to calculate the moles of water formed (as enthalpy of neutralisation is in the formation
of one mole of water) and use q = mc∆T
7. Multiply it to calculate the enthalpy of neutralisation per mole of water
167
Preparing an Organic Liquid
Preparing by reflux:
1. Add reactants slowly to the reaction flask with cooling (as reactions are often exothermic, so
this dissipates the heats and prevents the temperature increasing and avoids dangerous
splashing or the formation of side products)
2. Attach a water-cooled condenser vertically to the reaction flask. This prevents vapour escaping
when they’re boiled for long times, note there is not a thermometer or stopper at the top of the
apparatus (pressure would build up) and that the water inlet is the bottom one so that the
condenser is completely filled with no bubbles for more effective cooling.
3. Anti-bumping granules (such as silica pieces or unglazed pottery) are added to ensure smooth,
even boiling (preventing large bubbles formed at the bottom abruptly moving upwards and
causing splashing by providing a rough surface on which small bubbles can grow)
4. Most organic compounds are flammable so often a flameless heating method is required, such
as a water bath (up to 100 degrees), sand bath or electric heating mantle.
Separating by distillation:
1. Remove the condenser and inset a still heat into the flask, with a thermometer and
condenser attached sideways connected to a receiver (with a vent so that the apparatus is not
closed or using an open measuring cylinder). Make sure the bulb of the thermometer is level
with the condenser so it measure the temperature of the vapour exiting and so the boiling
point of the product you’re collecting can be recorded
2. Anti-bumping granules are also needed for distillation to prevent liquid splashing into the
condenser and causing inpure product or the apparatus being blown apart
3. Joints need to be secure to prevent volatile chemicals escaping
168
Purifying an organic liquid
Solvent extraction using a separating funnel:
1. Add the product into a separating funnel (with tap closed) and add an aqueous solution such as sodium
hydrogen carbonate solution (which will also remove acidic impurities (e.g. any unreacted reactants in
esterification))
2. Stopper and shake, releasing the pressure by inverting and opening the tap (caused by build up of carbon
dioxide when the above reacts with acids). The impurities are more soluble in the aqueous solution so will
move into it
3. Allow it to stand so the layers separate (as they’re immiscible) and settle. Whichever is denser will be on the
bottom – but to check add some more water and whichever layer grows in size is the aqueous
4. Remove the stopper and tap off the unwanted layer until the organic layer is at the mark then tap into
another beaker
5. Repeat the process using another portion of the aqueous solution (more effective to do twice with small
portions than once with a large portion)
Drying:
6. Add a spatula of drying agent, such as anhydrous calcium chloride, or magnesium sulphate, to the organic
liquid in a beaker
7. Swirl
8. Add more of the drying agent until the liquid changes from cloudy to clear (signifies water has been
removed and the product is dry)
9. Filter or decant the liquid into a clean, dry flask
Final re-distillation:
Redistillation indicates the identity and purity of the liquid. If the boiling point is sharp and close to the data book
value it is correct product and purer than if it covered a range. Impurities….If the boiling points of products and
reactants are similar than fractional distillation may be used instead, by having a fractionating column before the
distillation equipment (so vapour becomes richer in the most volatile liquid present each time) 169
Synthesis of an organic solid
• Preparation Separation by filtration under pressure Purification by recrystallization
Drying with filtration and oven Purity check
• Once prepared, separate the product by filtering under reduced pressure by using a
Buchner funnel and flask. This is faster and leaves the solid quite dry.
• To purify the product, choose a solvent in which the product is soluble at high temperatures
but only slightly soluble at lower temperatures. This is often water, but it may be another
such as ethanol. Dissolve the solid in the minimum amount of hot ethanol, filter normally to
remove any insoluble impurities (with fluted paper and a hot filter funnel to prevent solid
precipitating out) then leave to cool and it will crystallise out as its solubility drops.
Impurities will remain dissolved in the solution. However, if crystallised too fast, some
soluble impurities may become trapped in the crystals, so slow crystallisation is preferred.
Finally, filter the crystals using suction filtration and wash by pouring over some ice-cold
solvent to remove any aqueous impurities.
• Dry by sucking air over the crystals in the Buchner flask then placing in a desiccator
• To check the purities of the organic solid, measure the range of temperatures over which it
begins to melt until it has completely melted. A pure substance will melt over a narrow
range (less than 2 degrees) at a temperature close to that given in the data books (verifies
its identity), whereas impure will melt at a lower temperature and over a greater range. To
test this, place the solid in a melting point tube which has been sealed at one end by
twisting over a Bunsen burner, then place in the melting apparatus and heating slowly.
Record the range of temperatures, let apparatus cool sufficiently then repeat to get an
average (If it’s a high temperature may want to use rapid heat to speed up process until
close to predicted range then repeat).
170
Electrochemical Cells
• A high-resistance voltmeter is used as it draws very little current
• The potential difference between two half-cells is maximum when no current is flowing and is
called the cell potential (or e.m.f.)
• Salt bridge (E.g. filter paper soaked in potassium nitrate solution as all potassium and nitrate
salts are soluble so won’t produce any precipitates with any ions in half cells) – allows
electrons to flow by completing the circuit while preventing the two solutions mixing. It
allows ions to move between half-cells to keep the charge f each container zero and allow the
flow of electrons to continue.
• A salt-bridge must be used instead of a wire because in a wire the conducting species are
electrons and in the salt-bridge it is ions. Thus, no current could flow in the wire so it would
not form a complete circuit and cell potential couldn’t be measured.
• When an electrochemical cell is set up, if the reading is positive then the metal connected to
the positive terminal is the positive electrode, if it’s negative, the one connected to the
negative terminal is the positive electrode.
• Electrodes used when both ions are in solution, such as carbon (graphite) or platinum, must
be unreactive with those ions and be a good conductor.
• Changes in concentration of electrons and ions…
171
Salt bridges deeper understanding
The purpose of a salt bridge is to maintain the charge balance. As electrons are produced by the Zinc, they move from the anode to the
cathode through the wire (the path of lowest resistance) and into the other cell. This would leave just positive ions in the Zn half-cell so the
salt bridge provides negative ions to move into this cell and balance it. The same but opposite happens in the cathodic cell, where ions are
being consumed so neutrality is maintained by the migration of the counter ions (E.g. if copper solution is actually CuSO4, the SO42- ions will
move into the salt bridge to keep RHS at 0 too).
It is important to use salts with inert ions, ones that won’t form insoluble salts with the ions in the half-cell, to keep the charge flowing.
If the charge wasn’t kept neutral, the solution in one half cell would accumulate negative charge and the solution in the other half cell would
accumulate positive charge as the reaction proceeded, so electrons would stop flowing before the reaction was up as one side would become
to negative. Thus, it prevents the cell from rapidly running its reaction to equilibrium.
At the beginning because there are both types of ions (the ions that we look at and the counter ions) in each cell, the net charge is 0. As zinc
oxidises, its cell becomes positively charged and the copper becomes negatively charged because it’s lost a Cu2+ ion. This would create a
potential difference in the opposite direction to that of the electrons in the wire, so this affect builds up and will nullify that between the
metals so electrons will stop flowing.
Salt bridge is an ion conductor. It will not conduct electrons.
Hence, salt bridge allows ions to flow in opposite direction to electrons in order to maintain the cell EMP (electro-motorforce).
The same is needed in commercial cells, where the salt bridge is replaced by membranes that allow ions to flow.
172