Chemistry EA Notes

Unit 3: Equilibrium, acids and redox reactions

Chemical equilibrium

• recognise that chemical systems may be open (allowing matter and energy to be
exchanged with the surroundings) or closed (allow energy, but not matter, to be exchanged
with the surroundings)
- Open system  allows matter and energy to be exchanged with the surroundings
- Closed system  allows energy but not matter to be exchanged with
the surroundings.

• understand that physical changes are usually reversible, whereas only some
chemical reactions are reversible

Ie. Physical conditions such as state changes

• appreciate that observable changes in chemical reactions and physical changes can
be described and explained at an atomic and molecular level

- On the molecular level, there is a lot of activity. Equilibrium is not static, but rather a
highly dynamic system.
- Think of the escalator analogy, the rate of the forward reaction is equal to the rate
of the reverse reaction, ultimately appearing as static.

• symbolise equilibrium equations by using ⇌ in balanced chemical equations

- The state where the concentration of all the reactants and products remain constant
with time
- Two reactions are occurring – a forward reaction and a reverse reaction.
- Both reactions are occurring at the same rate
- As a reaction is used up in the forward reaction it is also produced in the
reverse reaction

• understand that, over time, physical changes and reversible chemical reactions reach a
state of dynamic equilibrium in a closed system, with the relative concentrations of products
and reactants defining the position of equilibrium

- Rate of dissociation = rate of association

- Physical systems, eg. Water has enough energy to change state and evaporate, it then
collides with the container wall and condenses.
• explain the reversibility of chemical reactions by considering the activation energies of
the forward and reverse reactions

- When particles collide, the energy associated with collisions can break bonds
in reactants, allowing them to form new products. This is the activation energy.
 - If the products collide with enough force to break their bonds (equal to the
activation ergy of reverse reaction), then the reactants may re-form.

• analyse experimental data, including constructing and using appropriate graphical

representations of relative changes in the concentration of reactants and product against time,
to identify the position of equilibrium

Factors that affect equilibrium

• explain and predict the effect of temperature change on chemical systems at equilibrium by
considering the enthalpy change for the forward and reverse reactions
 - If a system is in equilibrium then the forward and reverse reactions are occurring
at the same rate
- Any imposed change which affects the rate of either the forward or reverse
reaction can therefore changes the system
- Le Chatelier’s principle states – “if a change is imposed on a system at
equilibrium, the position of equilibrium will shift in a direction that tends to reduce
that change.”

• explain the effect of changes of concentration and pressure on chemical systems

at equilibrium by applying collision theory to the forward and reverse reactions

- The system will shift away from the added component, therefore and increase in
the concentration of a reactant will push the equilibrium towards the product.
- Addition of an inert gas does not affect the equilibrium position
- Decreasing the volume shifts the equilibrium toward the side with fewer moles.
- If the temperature is increased, an increase in temperature will push this
equilibrium towards the products.

• apply Le Châtelier’s principle to predict the effect changes of temperature, concentration

of chemicals, pressure and the addition of a catalyst have on the position of equilibrium and
on the value of the equilibrium constant.

- Complete questions applying these rules to determine the position of equilibrium

Equilibrium constants
• understand that equilibrium law expressions can be written for homogeneous and
heterogeneous systems and that the equilibrium constant (Kc), at any given
temperature, indicates the relationship between product and reactant concentrations at
equilibrium
- Homogenous vs heterogeneous equilibra:
- Homogenous reactions – all reactants and products are in the same phase
- Heterogeneous – all reactants and products are in different phases
- The concentration of a pure liquid or a pure solid is considered a constant,
and therefore is removed from the equilibrium expression.

• deduce the equilibrium law expression from the equation for a homogeneous reaction and
use equilibrium constants (Kc), to predict qualitatively, the relative amounts of reactants
and products (equilibrium position)

Consider this reaction: aA + bB ⇌ cC + dD

The rate of for forward reaction can be expressed as: Rf =
kf[A]a[B]b Rate of reverse can be expressed as: Rr = kr[C]c[D]d
Therefore, if the forward rate is equal to the reverse rate, the following relationship occurs:
 [𝐶]𝑐[𝐷]𝑑
𝐾=
[𝐴]𝑎[𝐵]𝑏

[𝐶]𝑐[𝐷]𝑑
𝐾𝑐 =
[𝐴]𝑎[𝐵]𝑏

- The value of an equilibrium constant indicates:

o The extent of reaction at equilibrium (how far the forward reaction
prtoceeds before equilibrium is established)
o The equilibrium yield (the number of moles of products present at
equilibrium)
- When Kc is very large- the numerator must be large compared to the denominator,
e.g. Large amounts of products relative to the reactants
- When Kc is very small -0 the numerator must be small compared to the denominator,
e.g large number of reactants relative to products.

• deduce the extent of a reaction from the magnitude of the equilibrium constant
The reaction quotient:
- Q, relates to the amount of products and reactants in a chemical reaction at a given
point in time. If the reaction quotient is compared with the equilibrium constant,
the direction of the reaction may be known.
- Q is calculated the same way as Kc
- Q uses the current or initial concentrations instead of the equilibrium
concentrations used to calculate Kc
- Once found, the reaction quotient is compared to the equilibrium constant.
- If Q < K, then there are more reactants present than at equilibrium and the
reaction will shift to the right
- If Q > K, then there are more products present than at equilibrium and the reaction
will need to produce more reactants shifting the reaction to the left
- If Q=K, then the reaction is already at equilibrium and there will be no shift.
-

• use appropriate mathematical representation to solve problems, including

calculating equilibrium constants and the concentration of reactants and products.

- To calculate Kc for a reaction at a

given temperature, we use initial
concentrations and equilibrium
concentrations.
1. Deduce balanced chemical reactions
2. ICE method
o I: initial concentration of reactants.
Products = 0
o C: Change in concentration. Consistent
with stoich. Ratios in balanced equation.
o E: Equilibrium concentration. E = I +/- C
3. Substitute values into equilibrium constant expression to determine Kc.

Properties of acids and bases

• understand that acids are substances that can act as proton (hydrogen ion) donors and can
be classified as monoprotic or polyprotic depending on the number of protons donated by
each molecule of the acid

- An acid is defined as a substance that is ionised in water to produce hydrogen ions

𝐻𝐶𝐿 → 𝐶𝑙− + 𝐻+
- A base is defined as as substance that dissociates in water to form hydroxide ions.

𝑁𝑎𝑂𝐻 → 𝑁𝑎+ + 𝑂𝐻−

- When a solution of HCL or NaOH are tested with conductivity, apparatus,
the movement of these ions results in the flow of current
- They both conduct electricity
The position of equilibrium defines the strength of an acid, if equilibrium lies to the right,
acid has dissociated fully and is a strong acid. If equilibrium lies to the left, acid has
dissociated partially, and it is a weak acid.

- Strong = complete dissociation

- Weak = very little dissociation

• distinguish between
strong and weak acids
and bases in terms of the
extent of dissociation, reaction with water and electrical conductivity and distinguish between
the terms strong and concentrated for acids and bases.
Reactions in water:
- Strong acids and bases ionise completely in water
Electrical Conductivity:
- Acids of equal concentrations can have different abilities to conduct electric current
- Strong acids have a greater number of ions in solution compared to weak acids,
therefore, have higher electrical conductivity.
Distinguishing between strong and concentrated:
- Concentrated and dilute refers to the concentration of an acidic or basic substance in a
solvent. Eg. 16M HCl is more concentrated than a 0.5M solution of the same acid.
- Strong and weak refer to the ability of an acid or base to dissociate, a strong acid will
dissociate completely in water to form hydronium ions. A weak acid or base will only
dissociate to a certain percentage.

pH scale

Kw = [H+ ][OH– ].
pH = –log10[H+ ]
pOH = –log10[OH– ]

• understand that water is a weak electrolyte and the self-ionisation of water is

represented by Kw = [H+ ][OH– ]; Kw can be used to calculate the concentration
of hydrogen ions from the concentration of hydroxide ions in a solution
- Water has been experimentally determined to ionize, that is 1 molecule in every
10 billion, dissociates and breaks up with itself.
- A Kw equation can be used to express this.
[𝐻3𝑂+][𝑂𝐻−]
- 𝐾 = [𝐻20]2
- Since water is a pure liquid, the H2O does not essentially change. Since the water
cannot change concentrations this term is not included in the above expression and
the equation becomes:
- 𝐾𝑤 = [𝐻3𝑂+][𝑂𝐻−]
- The value of Kw at 25C has been determined to be 1 × 10−14
-

• understand that the pH scale is a logarithmic scale and the pH of a solution can be
calculated from the concentration of hydrogen ions using the relationship pH = –log10
[H+ ]

- pH = -log[H+]
- the antilog of pH gives the concentration (10n)
- pH + pOH = 14

• use appropriate mathematical representation to solve problems for hydrogen ion

concentration [H+ (aq)], pH, hydroxide ion concentrations [OH– (aq)] and pOH.

Brønsted-Lowry model

• recognise that the relationship between acids and bases in equilibrium systems can be
explained using the Brønsted-Lowry model and represented using chemical equations that
illustrate the transfer of hydrogen ions (protons) between conjugate acid-base pairs

Bronsted Lowry: Acids are H+ donors, bases are proton acceptors.

 HA + H2O H3O+ + A-
Conj acid 1 Conj base 2 Conj acid 2 Conj base 1

Conjugate Base: everything that remains of the acid molecule after the proton is lost.

Conjugate Acid: formed when the proton is transferred back to the base.

• recognise that amphiprotic species can act as Brønsted-Lowry acids and bases
 An amphoteric substance is one which can act as either an acid or a base
 They have reactions as both acids and bases.
 An amphoteric substance is one which can both donate hydrogen ions
(protons) and also accept them.
• identify and deduce the formula of the conjugate acid (or base) of any Brønsted-Lowry
base (or acid)
Complete practice questions

• appreciate that buffers are solutions that are conjugate in nature and resist a change
in pH when a small amount of an acid or base is added; Le Châtelier’s principle can be
applied to predict how buffer solutions respond to the addition of hydrogen ions and
hydroxide ions.

Dissociation constants

• recognise that the strength of acids is explained by the degree of ionisation at

equilibrium in aqueous solution, which can be represented with chemical equations
and equilibrium constants (Ka)

 The position of equilibrium determines the strength of the acid

 If equilibrium lies to the right, acid has dissociated (ionised) completely and is a
strong acid.
 If equilibrium lies to the left, acid has partially dissociated (ionised) and is a
weak acid.

• determine the expression for the dissociation constant for weak acids (Ka) and
weak bases (Kb) from balanced chemical equations

 Ka
o Fixed value for particular acid at specified temperature
[𝐻30+][𝐴−]
o Equilibrium constant expression
[𝐻𝐴]
o Depends on position of equilibrium
o Measure if the strength if the acid
 High Ka  greater dissociation  stronger the acid
 Low Ka  less dissociation  weaker the acid

 Kb
[𝐵𝐻+][𝑂𝐻−]
o Equilibrium constant expression
[𝐵]
o Measure of strength of base
 • analyse experimental data to determine and compare the relative strengths of acids
and bases
 Ka and Kb give measure of strength, but negative components and very
small numbers make it clumsy
 So similar to what is done with [H+] or [OH-] to find pH, Ka and Kb converted
into their negative log  pKa and pKb.
 pKa = -log[Ka]
 pKa and pKb numbers are usually positive and have no units (mostly useful for
weak acids and bases)

• use appropriate mathematical representation to solve problems, including

calculating dissociation constants (Ka and Kb) and the concentration of reactants and
products.

 The relationship between Ka and pKa is inverse (same for bases)

 Weak acids with low Ka have higher values for pKa (same for bases)
 A change of 1 unit of pKa represents 10-fold change in Ka (similar to pH)
 pKa must be quoted at a specified temperature
 Ka x Kb = Kw
 pKa + pKb = pKw
 Weak acid – strong conj. Base
 Strong acid – weaker conj. Base
Eg. Question:
The concentration of CH3COOH at 25C is 1.00molL-1. Calculate the concentration of
ethanoate ions at this temperature. (Ka = 1.75 x 10-5)

CH3COOH  H+ + CH3COO-

[𝐻+][𝐶𝐻3𝐶00−]
𝐾𝑎 =
𝐶𝐻3𝐶𝑂𝑂𝐻
CH3COOH H+ CHCOO-
Initial 1.00 0 0
Change -x +x +x
Equilibrium 1.00-x X X

Acid-base indicators
• understand that an acid-base indicator is a weak acid or a weak base where the
components of the conjugate acid-base pair have different colours; the acidic form is of a
different colour to the basic form

 An indicator is typically a WA or WB that displays a different colour in acidic

or alkaline environments
 The acid and its conjugate base have different colours. At low pH, the concentration
of H+ is high and so the equilibrium lies on the left. The equilibrium solution has the
colour (1 acid)
 At high pH, the concentration of H+ is low and so the equilibrium position thus lies to
the right and the equilibrium solution has colour 2 (base)
Hind  Ind- + H+
Acid form base form
Colour 1 colour 2

• explain the relationship between the pH range of an acid-base indicator and its pKa value
 An indicator is most effective if the colour change is distinct and over a low pH
range. For most indicators, the range is within ±1 of the pKIn value


• recognise that
indicators change colour
when the pH = pKa and identify an appropriate indicator for a titration, given equivalence
point of the titration and pH range of the indicator.
  Half way through the colour change the concentrations of the acid and its ion are
equal. In that case, they will cancel out of the Kind expression.
 Pick an indicator that sits within the range of
the equivalence point

Appreciate that buffers are solutions that are conjugate in nature and resist a
change in pH when a small amount of an acid or base is added; Le Chatelier’s
principle can be applied to predict how buffer solutions respond to the addition
of hydrogen ions and hydroxide ions.

 A buffer solution which resist a change in pH upon the addition of

small amounts of a strong base of strong acid, or upon the dilution of
the buffer through the addition of water.
 A buffer may be comprised of
o A weak acid and its conjugate base
o A weak base and its conjugate acid
How buffers work:
 For effective control of changes in pH, the weak acid and its conjugate base are
mixed in equimolar concentrations.
 Eg. CH3COOH + H2O CH3COO-+H3O+
 The buffer capacity depends on the molar concentration of the acid and conj base
 The higher the concentration, the more effective the buffer is at resisting changes in
pH.
 Adding acid increases H3O+ so le chateliers principle will cause reaction to shift
left favouring reverse reaction and mopping up additional H3O+.
  Adding base causes OH- to react with H3O+ which decreases H3O+. Causes reaction
to shift right and favours forwards reaction to replenish H3O+

Volumetric analysis
• distinguish between the terms end point and equivalence point
 A titration curve is the plot of pH of the analyte solution versus the volume of the
titrant added as the titration progresses.
 Equivalence point – point in titration at which the amount of titrant added is just
enough to completely neutralise the analyte solution. At the equivalence point in acid
base titration, moles of base = moles of acid and the solution only contains salt and
water.
 End point refers to the point at which the indicator changes colour in an acid-base
titration.

• recognise that acid-base titrations rely on the identification of an equivalence point by

measuring the associated change in pH, using chemical indicators or pH meters, to reveal an
observable end point

 Identify the indicator that sits in the range of the equivalence point in order to
associate the equivalence point with a colour indication

• sketch the general shapes of graphs of pH against volume (titration curves) involving strong
and weak acids and bases. Identify and explain their important features, including the
intercept with pH axis, equivalence point, buffer region and points where pKa = pH or pKb =
pOH

• use appropriate

mathematical representations and analyse experimental data and titration curves to solve
problems and make predictions, including using the mole concept to calculate moles, mass,
volume, and concentration from volumetric analysis data.

Eg. Question:
Titrate 50.0mL of 0.100M HC2H3O2 (Ka = 1.80 x 10-5) with 0.100M NaOH. Determine the
pH after 0.00, 10.0, 25.0, 40.0, 50.0 and 60.0mL of NaOH has been added.
Calculate the initial pH of weak acid using ICE table
CH3COOH H+ CH3COO-
Initial 0.1 0 0
Change -x +x +x
Equilibrium 0.1-x X x

Topic 2:Oxidation and reduction

Redox reactions
• recognise that a range of reactions, including displacement reactions of metals, combustion,
corrosion and electrochemical processes, can be modelled as redox reactions involving
oxidation of one substance and reduction of another substance

 Reduction + oxidation = redox

 Redox reactions occur everywhere, eg. Cellular respiration, corrosion, combustion,
and batteries

• understand that the ability of an atom to gain or lose electrons can be predicted from
the atom’s position in the periodic table, and explained with reference to valence
electrons, consideration of energy and the overall stability of the atom
 Oxidation = loss of electrons
 Reduction = gain of electrons
 A redox reaction involves the loss and gain of electrons by the reactants which can be
represented as 2 half equations
 There is no overall loss of electrons, but a transfer of electrons from one atom to
another
 If an atom, ion or molecule loses electrons, there must be another atom, ion
or molecule that gains electrons.
 Metals have relatively low electronegativity values and relatively low ionisations
energies.
 Metals have low tendency to draw valence electrons to themselves and tend to lose
valence electrons to other species. i.e Metals tend to undergo oxidation during
chemical reactions.
 Non-metals have relatively high electronegativity values and high electron
affinity values.
 Non-metals have a strong tendency to draw valence electrons to themselves in
chemical reactions. i.e Non-metals tend to undergo reduction during chemical
reactions.
 When atoms undergo redox processes, the number of electrons transferred is
determined by the electron configurations of the atoms involved. Electrons are lost or
gained to achieve a stable electron configuration.
Oxidising agents and reducing agents:
 Oxidising agent causes another chemical to be oxidised, the oxidising agent is
itself reduced
 Reducing agent causes another chemical to be reduced. The reducing agent is itself
oxidised.
 The reactivity series of metals ranks metals according to the ease in which
they undergo oxidation
 o The order in which metals and their metal ions appear in the reactivity
series enables you to predict which metals will displace other metals.
o Metals higher up in the activity series can displace those lower down
from solutions of their respective salts. Ie. Metal ion
o Most reactive metals are at the top of the series.

• identify the species oxidised and reduced, and the oxidising agent and reducing agent,
in redox reactions

• understand that oxidation can be modelled as the loss of electrons from a chemical species,
and reduction can be modelled as the gain of electrons by a chemical species; these
processes can be represented using balanced half-equations and redox equations (acidic
conditions only)

• deduce the oxidation state of an atom in an ion or compound and name transitional
metal compounds from a given formula by applying oxidation numbers represented as
roman numerals
Rule 1: The oxidation state of an atom in a free element is zero ie. All elements in elemental
state have oxidation state of zerio.
 The total oxidation number of a neutral molecule is zero.
 Eg. Mg, Na, S8,P4,O2
Rule 2: The oxidation number of a monatomic ion is equal to the charge of the ion.
 Eg. Group 1 metals have a +1 oxidation state in their ions and compounds
 Group 2 metals always have a +2 oxidation state in their ions and compounds
Rule 3: The oxidation state of hydrogen is +1 when hydrogen is bonded to a non-metal
Eg. HCL, HNO3
 When hydrogen is bonded to a metal (metal hydride), the oxidation number is -1.
Eg. NaH
Rule 4: The oxidation state of oxygen is usually -2
 Exceptions:
-
In a period (a species with an O-O linkage) eg. H2O2. Here the oxidation state of
oxygen is -1.
-
In compounds with fluorine, oxygen has a positive oxidation number.
Rule 5: The oxidation state of fluorine is -1 in all its compounds. Eg. HF, OF2.
 For other group 17 halogens, the oxidation state is usually -1, in binary compounds.
Eg. HI, KBr. But in combination with oxygen, the oxidation state is positive. Eg.
HCLO4, chlorine has a +7 oxidation state.
Rule 6: In a neutral molecule, the sum of the oxidation states of all the atoms is zero. Eg.
NH3
 In a polyatomic ion, the sum of the oxidation states of all the atoms equals the
overall charge of the ion.
eg. NH4+
Rule 7: Most electronegative element is assigned the negative oxidation number.
-eg. OF2, SF6
+2-1 +6-1

Calculating oxidation states:

+
 Find the oxidation number for nitrogen in NH4
 We know that hydrogen is +1
+
 NH4 = +1
 x+(4 x 1) = 1
 x = -3
 therefore the oxidation number for nitrogen is -3

• use appropriate representations, including half-equations and oxidation numbers,

to communicate conceptual understanding, solve problems and make predictions.
 An increase in oxidation number indicates oxidation (electrons lost)
 A decrease in oxidation number indicates reduction (electrons gained)
Mg  M2+ +2e-
Fe2+ + 2e- Fe
Interpreting oxidation numbers
 Determine if these half equations are oxidation or reduction
 Fe2+  Fe3+
 Oxidation
-
 MnO4  Mn2+
 Reduction
2-
 Cr2O7  Cr3+
 Reduction
Redox Reactions in Acidic Solutions using half-equations
 The two halves of the reaction are the oxidation half and the reduction half.
 You will typically be given just the oxidising agent and the reducing agent and the
products containing elements other than oxygen and hydrogen.
  Water and hydrogen ions are available to the reaction because the reaction is
occurring in an acidic, aqueous solution, but they are not initially shown.
Step 1: Divide the reaction into an oxidation half and a reduction half by assigning oxidation
states and deciding which species is oxidised and which is reduced.
Eg.
Cr O 2- + C H OH  CO + Cr3+
2 7 2 5 2
Is divided into these two half-reactions:
Cr O 2-  Cr3+
(reduction: Cr changes from2 +67
to +3)  gaining electrons – less
positve
C2H5OH  CO2
(oxidation: C changes from +2 to +4) losing electrons – more positive

Step 2: For each half-reaction, balance by inspection all elements except oxygen and
hydrogen.
Eg. Cr and C both require balancing:

Cr2 O72-  2Cr3+

C2H5OH 
2CO2

Step 3: For each half reaction, balance oxygen by adding water to the side deficient in
oxygen atoms. Water is available because the reaction occurs in aqueous solution.
Eg. In the Cr half, the products side is deficient, In the C half, the reactants side:

Cr2 O72-  2Cr3+ +7H 2O

3H2O + C2H5OH 
2CO2

Step 4: For each half reaction, balance hydrogen by adding hydrogen ions to the side deficient
in hydrogen atoms. Hydrogen ion is available because the reaction occurs in acidic solution.
Eg. In the Cr half, the reactants side is deficient, In the C half, the products side:
14H+ + Cr O 2-
 2Cr + +7H O
2 7 3 2
3H2O + C2H5OH  2CO2 +12H+

Step 5: For each half-reaction, balance the charges by adding electrons to the side with
more positive (or less negative) net charge.
Eg. In the ZCr half, the reactants side has a net charge of +12 and the products side, +6;
In the C half, reactants side has a net charge of 0, the products side, +12:

6e- + 14H+ +Cr2O72-  2Cr3+ +7H2O

3H2O + C2H5OH  2CO2 +12H+ + 12e-

Step 6: Find the lowest common multiple of the number of electrons in the two half-
reactions. Balance the electrons by multiplying each half-reaction by the appropriate factor:
Eg. The lowest common multiple of 6 and 12 is 12:

2(6e- + 14H+ +Cr2O72-  2Cr3+ +7H2O)

12e- + 28H+ +2Cr2O72-  4Cr3+ +14H2O

1(3H2O + C2H5OH  2CO2 +12H+ + 12e-)

3H2O + C2H5OH  2CO2 +12H+ + 12e-
Step 7: add two equations together, cancelling species that are duplicated on both sides of the
reaction.

Eg. 12e- + 28H+ +2Cr2O72-  4Cr3+

+14H2O 3H2O + C2H5OH  2CO2 +12H+
+ 12e-

3H2O + C2H5OH +12e- +28H+ + 2Cr2O72-

 4Cr3+ + 14H2O + 2CO2 +12H+ + 12e-

C2H5OH +16H+ + 2Cr2O72  4Cr3+ + 11H2O + 2CO2

Step 8: Check the equation is balanced
C2H5OH +16H+ + 2Cr2O72  4Cr3+ + 11H2O + 2CO2

Electrochemical cells

• understand that electrochemical cells, including galvanic and electrolytic cells, consist of
oxidation and reduction half-reactions connected via an external circuit that allows
electrons to move from the anode (oxidation reaction) to the cathode (reduction reaction).

 Galvanic (voltaic)
o Converts chemical energy to electrical energy
o Spontaneous process
 Electrolytic
o Converts electrical energy to chemical energy
o Nonspontaneous process
 NOTE:
o Oxidation always takes place at the anode
o Reduction always takes place at the cathode
o AN OX RED CAT

Galvanic cells
• understand that galvanic cells, including fuel cells, generate an electrical potential
difference from a spontaneous redox reaction which can be represented as cell
diagrams including anode and cathode half-equations
 In a galvanic cell:
o Cathode is positive
o Anode is negative
 In an electrolytic cell:
o Cathode is negative
o Anode is positive
  Two half reactions separated into half cells
o Metal/metal-ion electrode
 Electrons flow between them through an external circuit.
 Galvanic cell is a device which converts chemical energy into electrical energy

• recognise that oxidation occurs at the negative electrode (anode) and reduction occurs at
the positive electrode (cathode) and explain how two halfcells can be connected by a salt
bridge to create a voltaic cell (examples of half-cells are Mg, Zn, Fe and Cu and their
solutions of ions)

Salt bridge function:

1. Allows physical separation of the anode and the cathode and the oxidation
and reduction processes
2. Balances charges formed in the 2 half-cell compartments
3. Provides electrical continuity so that the reaction can proceed. Ie. a path for the ions
- Anions move to the anode, cations move to the cathode
- Salt bridge contains a concentrated solution of strong electrolyte
-
• describe, using a diagram, the essential components of a galvanic cell; including the
oxidation and reduction half-cells, the positive and negative electrodes and their solutions of
their ions, the flow of electrons and the movement of ions, and the salt bridge.

Half-Cells:
- If one member of the conjugate pair tina
half-cell is a metal it is usually used at the
electrode
- Some redox pairs do not involve solid
metal. If no metal is present, an insert
electrode, such as platinum or graphite is
used.
- If one of the conjugate pairs is a gas,
a special ‘gas electrode’ is used. Eg.
H+(aq)/H2+ (g)
Standard electrode potential
• determine the relative strength of oxidising and reducing agents by comparing standard
electrode potentials
 A half cell contains a conjugate redox pair
 The reactions that can occur can be written as
reversible reactions depending on whether
the species is being oxidised or reduced
 Strongest oxidising agents have the most
positive reduction potentials
 The strongest reducing agents hve the most
negative reduction potentials.
 The greater the difference between the two, the
greater the voltage of the cell.

Oxidising and Reducing agents:

 Which is the best oxidising agent?
 More likely to be reduced
 Which is the best reducing agent?
 More likely to be oxidised
Electromotive Force (EMF):
 Water only spontaneously flows one way in a
waterfall
 Likewise, electrons only spontaneously flow one
way in a redox reaction, from higher to
lower potential energy,
 A current flows in a galvanic cell because one
half-cell has a greater tendency to push
electrons into the external circuit than the
other half.
 The potential difference between the anode and
cathode in a cell is called the electromotive force (emf) or voltage.
 The maximum voltage that can be delivered by the cell.
 It is also called the cell potential, and is designated Ecell and is measured in volts (V).
Standard Hydrogen Electrode:
 It is impossible to measure the potential difference of an isolated half-cell so their
values are referenced to a standard hydrogen electrode (SHE) which is a
universal reference electrode and a gas electrode
 The reduction potential (E0) for hydrogen is assigned an arbitrary value of 0V
2H+(aq 1M) +2e-  H2(g, 1atm)
• recognise that cell potentials at standard conditions can be calculated from standard
electrode potentials; these values can be used to compare cells constructed from
different materials
 Use the electrochemical series top predict what will happen when 2 specific half-cells
are combined to form a cell.
 A reduction reaction will occur in the half-cell with the higher E0 value whereas an
oxidation reaction will occur in the half-cell with the lower E0 value.
 The positive electrode (cathode) will be in the half-cell with the higher E0 value
(reduction) whereas the negative electrode (anode) will be in the other half-cell
(oxidation
• recognise the limitation associated with standard reduction potentials

 Standard cell potentials given in the electrochemical series are measured under
standard conditions
 When conditions vary from standard conditions, the order of half reactions in the
electrochemical series may also be different and predictions based on the standard
half-cell potentials may not be reliable.
 The electrochemical series gives no information about rate of reaction.

• use appropriate mathematical representation to solve problems and make predictions about
spontaneous reactions, including calculating cell potentials under standard condition.
0 0 0
 E = E (more +ve) – E (less +ve)
 For any redox reaction standard cell potentials allows prediction of
spontaneous reaction
 If the standard cell potential is positive, a redox reaction is spontaneous.
 If the cell potential is negative, a redox reaction is non-spontaneous.

Eg. Galvanic cell:

 For Zn/Cu cell, potential is +1.10V
at 25C and when [Zn2+] and [Cu2+] =
1.0M.
 - a quantitative measure of the tendency
of reactants to proceed to products
when all are in their standard states at
25C
Calculating Cell Voltage:
 Balanced half reactions can be added
together to get overall, balanced
equation.

Electrolytic cells
• understand that electrolytic cells use an external electrical potential difference to provide
the energy to allow a non-spontaneous redox reaction to occur, and appreciate that these can
be used in small-scale and industrial situations, including metal plating and the purification of
copper
 The process by which electrical energy is used to drive a non-
spontaneous chemical reaction.
 It consists of a single container which contains 2
electrodes, an electrolyte and a battery.
 An electrolyte may be molten or aqueous.
• predict and explain the products of the electrolysis of a molten salt and aqueous solutions of
sodium chloride and copper sulfate. Explanations should refer to Eø values, the nature of the
electrolyte and the concentration of the electrolyte

 Molten NaCl:
o Platinum or graphite is used to electrodes because they are inert
(unreactive) and will not react with the contents of the cell.
o No water is present
o Ions are discharged and released as neutral products]
o Ions in electrolyte mixture migrate to oppositely charged electrode
o Anode – Oxidation A-  A + e-
o 2Cl- (l)Cl2(g) +2e-(ox)
o Cathode – Reduction M+ + e-  M
o Na+(l) +e-  Na(l) (red)
 The power supply pushes electrons towards the negative electrode (cathode).
The cations (Na+) are attracted to the cathode where they gain electrons and
become sodium atoms (reduction)
 The anions (Cl-) are attracted to the anode where they lose electrons and become
chlorine atoms. These atoms then form chlorine molecules (Cl2)

Aqueous Electrolytic Cell:

 If electrolyte is aqueous then water can also be oxidised or reduced.
 At cathode  H2O reduced to H2 gas
 At anode  H2O oxidised to O2 gas
 Most energetically favourable reaction will take place. Use the electrochemical series
to predict which of the possible reactions is most likely to occur.
o Reduction: 2H2O + 2e-  H2 + 2OH
o Oxidation: Cl2 + 2e-  2Cl-
o Overall cell equation: 2Cl- + 2H2O  H2 + Cl2 + 2OH
• describe, using a diagram, the essential components of an electrolytic cell; including
source of electric current and conductors, positive and negative electrodes, and the
electrolyte
 In an electrolytic cell, cathode is negative, and anode is positive.


Unit 4: Structure, synthesis, and design

Structure of organic compounds
• recognise that organic molecules have a hydrocarbon skeleton and can contain functional
groups, including alkenes, alcohols, aldehydes, ketones, carboxylic acids, haloalkanes, esters,
nitriles, amines, amides and that structural formulas (condensed and extended) can be used to
show the arrangement of atoms and bonding in organic molecules

 Each carbon has 4 valence electrons meaning it can form 5 covalent bonds with up to
4 other atoms
 Single, double triple bonds can form
o Saturated  only single bonds
o Unsatured  one or more double bonds or triple bonds
Alkanes:
 General formula: CnH2n+2
 Saturated hydocarbons
 Contains only C-H (4112kJ mol-1) and C-C (348kJ mol-1) bonds. These are
strong bonds and therefore will only react in the presence of a strong source of
energy, strong enough to break these bonds.
 Alkanes are stable and can be transported, stored and compressed safely making
them very useful compounds.
 C-C and C-H are non-polar bonds, again, meaning that alkanes are generally very low
in reactivity.
Alkenes:
 General formula: CnH2n
 Alkenes are unsaturated hydrocarbons
 Alkenes are more reactive than alkanes as
the double bond is the site of reactivity
 This bond is relatively easy to break, this creates
two new bonding positions on the carbon atoms.
Alkynes:
 General Formula: CnH2n-2
 Alkynes are unsaturated hydrocarbons
 The rules used for naming branched alkenes also apply for branched alkynes
Haloalkanes:
 A homologous series derived from alkanes where at least one of the hydrogen atoms
is replaced with a halogen
o Contain an atom of fluorine, chlorine, bromine, or iodine
 General formula: Cn H2n+1 X (where X = halogen)
 Unlike the alkanes, haloalkanes possess a polar bond which makes them more
reactive.
 Halogen atom is more electronegative than carbon and so exerts a stronger pull on the
shared electrons in the carbon-halogen bond. Therefore, halogen gains partial negative
charge and carbon gains partial positive charge (ie. electron deficient)
1°, 2° and 3° Haloalkanes:
 This terminology also constitutes the basis for characterising other types of
compounds where the main functional group is attached to a carbon that is either
primary, secondary or tertiary.

Alcohols:
 Naming alcohols:
1. Stem name is that of the largest carbonb chain with -OH in it
2. Number the chain to keep alcohol group in lowest possible number in
chain.
3. Give side chains in alphabetical order as usual. Hydroxyl group
takes priority over alkyl side chains.

Amines:
 The compound is named by replacing the ‘-e’ at the end
of the alkane name with the suffix: ‘-amine’.
 If the nitrogen atom is attached to an end – the carbon
attached to the N is always assigned the number 1. The
amino group takes priority over any alkyl side chains.
  If positional isomers are possible, a number is inserted before the ‘-amine’ to indicate
the carbon to which the amino functional group is attached.
1°, 2° and 3° Amines:
 A primary amine has one carbon atom/group bonded to the nitrogen atom
 A secondary amine has two carbon atoms/group bonded to the nitrogen atom
 A tertiary amine has three carbon atoms/group bonded to the nitrogen atom

 In a secondary or tertiary amine

o The longest alkane chain is numbered.
o Each alkyl group bonded to the N atom is named as a N-alkyl group

Nitriles:
 Are organic chemical compounds that include the functional group C≡N.
 Nitriles are a class of chemical compounds that include a nitrogen atom connected
to a carbon atom by a triple covalent bond.
 Nitriles used to be known as cyanides.
 The root name is based on the longest chain including the carbon of the nitrile group.
 Since the nitrile must be at the end of the chain, it must be C1 and no locant needs
to be specified.
Aldehydes:
 Identify the parent name from the longest carbon
chain containing the carbonyl group.
 In naming aldehydes (alkanals) the carbon atom in the
functional group is assigned the number 1.
 These have one hydrogen atom attached to the C in the
C=O group
 Remove -ane and add -al

Ketones:
 Naming remove ‘e’ and add ‘-one’
 Select longest carbon chain with carbonyl group attached, then number chain so that
C in functional group receives lowest possible number.

Carboxylic Acids:
 Contains carboxyl functional group
 Usual rules of naming apply, but functional group C given number 1.
 Where side chains occur on carboxylic acids, the carbon if the functional (acid)
group is always assigned the number 1.

Esters:
 Esters are polar substances, soluble in H2O. They have pleasant fruity odours, widely
used as natural flavourings.
  Esters are made from the reaction of an alcohol and a carboxylic acid and contain a
carbonyl group attached to an oxygen that is linked to another carbon.

Amides:
 Amides are a class of organic chemical compounds that include a part consisting of a
carbon atom connected to both:
o A nitrogen atom connected to two hydrogen atoms by single covalent bonds
between the nitrogen and each of the hydrogen atoms (that is an -amine group)
o An oxygen atom connected to the carbon atom by a double covalent bond
(that is a carbonyl group)
 Amides are named by changing the -oic acid ending of the corresponding carboxylic
acid to -amide.

• deduce the structural formulas and apply IUPAC rules in the nomenclature of organic
compounds (parent chain up to 10 carbon atoms) with simple branching for alkanes,
alkenes, alkynes, alcohols, aldehydes, ketones, carboxylic acids, haloalkanes, esters, nitriles,
amines and amides

• identify structural isomers as compounds with the same molecular formula but
different arrangement of atoms; deduce the structural formulas and apply IUPAC rules in
the nomenclature for isomers of the non-cyclic alkanes up to C6
 Structural isomers are molecules that have the same molecular formula but
different arrangement of the atoms
 The number of isomers that exist for a molecular formula increases with the size of
the molecule
 Structural isomers can have very different chemical and physical properties.
  2 types  Chain, positional
Chain: Positional:

• identify stereoisomers as compounds with the same structural formula but with different
arrangement of atoms in space; describe and explain geometrical (cis and trans) isomerism
in non-cyclic alkenes.
 Geometric isomers can occur when there is restricted
rotation somewhere in a molecule. Eg. A carbon-carbon
double bond or a ring structure.
 Cis-trans isomers of alkenes occur because the atoms
associated with the carbon double bond are fixed in position.
 They can only occur when each carbon atom in the
double bond is attached to 2 different groups.

Physical properties and trends

• recognise that organic compounds display characteristic physical properties, including
melting point, boiling point and solubility in water and organic solvents that can be
explained in terms of intermolecular forces (dispersion forces, dipole-dipole interactions and
hydrogen bonds), which are influenced by the nature of the functional groups

• predict and explain the trends in melting and boiling point for members of a
homologous series

 Functional groups that are present in organic compounds are responsible for many of
their physical properties
 Organic compounds are made of molecules that are held together by intermolecular
forces. The strength of these intermolecular forces determine physical properties
such as boiling points, melting points, volatility and soluability.
  Boiling occurs when molecules in the liquid state have enough energy to
overcome the intermolecular forces holding them together. Stronger molecular
forces require more energy, and therefore have higher boiling points.

Boiling points:
 Hydrocarbons:
o Only contain weak dispersion forces,
therefore are non-polar.
o Generally lower boiling point than other
organic compounds with similar molecule mass.
o The BP of compounds within a homologous
series increases as chain length increases.
 Effects of branching:
o Straight chain alkanes have greater surface
area and can fit together more closely,
allowing for
more contact between the molecules and therefore forming stronger dispersion
forces.
o Tend to have higher boiling points
 Aldehydes, ketones, esters:
o Held together by dipole-dipole
and dispersion forces.
o All contain a carbonyl group
o Carbonyl group is polar
(because oxygen is more
electronegative
than carbon), which means that these molecules contain a permanent dipole
that can form dipole-dipole interactions with neighbouring molecules.
 Alcohols, carboxylic acids, amines and amides:
o These molecules can form hydrogen bonds
(ie. oxygen nitrogen or fluorine attached to a
hydrogen) there therefore exhibit higher BP.

 Effects of branching:
o Branching decreases dispersion force interactions
o Restricts the molecules ability to form hydrogen
bonds with other molecules
o Branching decreases boiling point
Melting points:
 The melting point within a homologous series generally
increases with increasing carbon chain length; however,
the increase is not as regular as with the BP trend.
 Alkanes -even- numbered carbon chains pack tighter
resulting in stronger intermolecular forces and higher melting
points.
 Alcohols:
o First 3 do not fit the trend
o Melting point determined by the strength of
the IMF (intermolecular forces) and steric
hindrance ie. size and arrangement of
atoms.
o Strength of IMF in alcohols are largely due
to H-bonding. Addition of CH2 does not
significantly increase overall IMF.

• discuss the volatility and solubility in water of alcohols, aldehydes, ketones,

carboxylic acids and halides.
Volatility:
 Refers to an organic compounds ability to form a vapour ie. if they evaporate
easily, they are considered volatile.
 Volatile organic compounds can be detected by their smell and if they contain
weak intermolecular forces.
 High boiling point = less volatile
 Low boiling point = more volatile
 Volatile compounds have higher vapour pressure.
 Hydrocarbons: Only form dispersion forces, volatility depends on chain length
 Haloalkanes, aldehydes and ketones: polar compounds, less volatile than
hydrocarbons.
 Alcohols and carboxylic acids: hydrogen bonding, lower volatility
Solubility:
 Intermolecular forces present in organic compounds effect solubility
 A solute will dissolve in a solvent that has similar intermolecular forces
 Energy is required to break the intermolecular forces in the solute and the solvent.
 Energy is then released when new intermolecular forces form between solute
and solvent.
 A solute will only dissolve if the energy released compensates for energy required.
 Hydrocarbons:
o non-polar nature of hydrocarbons makes them insoluble in water
o they can only form weak dispersion forces with water which are not enough
to compensate for the energy required to break the hydrogen bonds between
water molecules.
o Therefore, they remain immiscible.
o Hydrocarbons will dissolve in non-polar solvents due to their similar
intermolecular forces – miscible.
 Haloalkanes, aldehydes, ketones:
o Haloalkanes are slightly more soluble than hydrocarbons in water due to
their polar carbon-halogen bond.
 o Aldehydes and ketones can form hydrogen bonds between the lone pair
of electrons on the carbonyl group and water molecules.
o But solubility decreases with increasing length of carbon chain because
the hydrocarbon chain cannot
o Becomes more soluble in organic solvents as chain increases.
 Alcohols and carboxylic acids:
o Hydrogen bonds form between polar functional groups and water molecules.
o Small alcohols and carboxylic acids are highly soluble.
o As carbon chain length increases, solubility in water decreases because
of increasing length of hydrocarbon tail, but solubility in non-polar
solvents increases.
o Carboxylic acids are more soluble than alcohols because hydrogen bonds can
form between water and molecular and the carbonyl and hydroxyl groups.

Organic reactions and reaction pathways

• appreciate that each class of organic compound displays characteristic chemical properties
and undergoes specific reactions based on the functional group present; these reactions,
including acid-base and oxidation reactions, can be used to identify the class of the organic
compound

• understand that saturated compounds contain single bonds only and undergo substitution
reactions, and that unsaturated compounds contain double or triple bonds and undergo
addition reactions

 Bromine water is an orange solution of bromine.

 It becomes colourless when it is shaken with an alkene
 Alkenes can decolourise bromine water, but alkanes cannot.

• determine the primary, secondary and tertiary carbon atoms in halogenoalkanes

and alcohols and apply IUPAC rules of nomenclature
 A primary carbon is one that is covalently attached to only one other carbon
 A secondary carbon is one that is attached to two other carbons
 A tertiary carbon is attached to three other carbons
 This terminology also constitutes the basis for characterising other types of
compounds where the main functional group si attached to a carbon that is
either primary, secondary or tertiary.
• describe, using equations: oxidation reactions of alcohols and the complete combustion of
alkanes and alcohols
 Combustion of Alkanes
o Alkanes release a significant amount of energy when they burn – highly
exothermic oxidation-reduction reaction.
o There is a large amount of energy released in forming these double bonds
in carbon dioxide and in water (the products of combustion)
o If the supply of oxygen is plentiful – complete combustion
o Complete combustion of hydrocarbons in the presence of excess oxygen results in
the product of carbon dioxide gas and water vapour
o CH4 + 2O2  CO2 + H2O + energy
 Combustion of Alcohols:
o Like hydrocarbons, alcohols burn in oxygen to produce carbon dioxide
and water, along with the release of significant amounts of energy.
o

substitution reactions of alkanes with halogens

 Substitution: a reactant, such as a halogen, takes the place of a hydrogen atom in

the alkane.

 The UV light is the energy required to break the covalent bond in the chlorine
molecule. This splits the chlorine atom into free radicals.
 The formation of the free radicals initiates a chain reaction that results in the
formation of haloalkane.
Substitution reactions of alkanes:
 Photochemical homolytic fission is the name given to the process that occurs
when in the presence of UV light the bond between the chlorine atoms is broken.
This splits the shared pair of electrons.
  This process produces to free radicals, each with an unpaired electron.
 The unpaired electron makes the free radical very reactive.

substitution reactions of haloalkanes with halogens, sodium hydroxide, ammonia and

potassium cyanide
 In haloalkanes, the large electronegativity difference between halogen and carbon
atoms means that the bond is polar. This bond is weaker than bonds without a dipole.
 The halogen can then be substituted by another halide ion, cyanide ion, ammonia, or
hydroxide ion.
 The new product is either a new haloalkane, nitrile, amine or an alcohol respectively.
 Substitution of haloalkane with ammonia:

 Substitution of haloalkane with cyanide:

o A haloalkane is heated with a solution of potassium cyanide or
sodium cyanide in ethanol.
o This reaction is biologically significant as it results in the lengthening of the
carbon backbone ie. smaller molecules can be made into larger ones.
o Nitrogen is also added meaning the molecule now has a key part of the basic
structure of an amino acid.
o
addition reactions of alkenes with water, halogens and hydrogen halides addition reactions of
alkenes to form poly(alkenes)

• recognise the acid-base properties of amines and explain, using equations, the reaction
with carboxylic acids to form amides

• recognise reduction reactions and explain, using equations, the reaction of Guidance
nitriles to form amines and alkenes to form alkanes
 Alkanes react with hydrogen gas in the presence of a metal catalyst such as nickel
to form alkanes.
 Called a reduction reaction because hydrogen atoms are added.

•Describe using equations: addition reactions of alkenes with water, halogens, and
hydrogen halides (6,7,8)
 Alkenes are generally more reactive than alkanes and involve the addition of a small
molecule to the double bond.
 During addition reactions:
o 2 reactant molecules combine to form 1 product molecule.
o The C=C bond becomes a C-C bond
o The unsaturated compound becomes saturated
o Atoms are added across the double bond
Reaction of alkenes with halogens (6)
 This reaction proceeds at room temperature without a catalyst.
 Bromine is often used as a test for presence of C=C double vonds due to the ease and
speed with which it reacts with alkene.

Reaction of alkenes with water (7)

  Alkenes react with water under specific conditions (eg. Phospohric acid catalyst
and heat) to form corresponding alcohol.

Reaction of alkenes with hydrogen halides (8)

 In this reaction, a hydrogen atom is added to one of the carbon atoms in the C=C and
a halogen to the other.
 The addition reaction can produce 2 isomers.
 The great formation of one isomer can be predicted using Markovnikov’s rule

Markovnikov’s Rule:
 We can predict the correct outcome of any reaction involving the addition of
hydrogen halide to asymmetric alkenes by using Markovnikov’s rule
 STATES: the hydrogen will attach to the carbon that is already bonded to the
greatest number of hydrogens
 “when an unsymmetrical alkene reacts with a hydrogen halide to give a alkyl halide,
the hydrogen adds to the carbon that has the greater number of hydrogen substituents,
and the halogen to the carbon having the fewer number of hydrogen substituents.”

• recognise and explain, using equations, that: elimination reactions can produce unsaturated
molecule and explain, using equations, the reaction of haloalkanes to form alkenes
 When an addition reaction is reversed, it is known as an elimination reaction. The
haloalkane loses 2 atoms (1 hydrogen and 1 halogen) and regains the double bond ie.
an unsaturated molecule is derived from a saturated molecule.
  This reaction requires a strong base and heat to proceed.

•describe, using equations: addition reactions of alkenes to form poly(alkenes)

 The double bond contained within an alkene can easily break and therefore
alkenes can easily join to produce a long chain.
 This process is known as addition polymerisation.

 Monomers- the alkene used in the reaction

 Polymers – represented using repeating units of the momener
 Eg. Ethene is the monomer and this forms polyethene.
Polymers:
 Major product of the organic chemistry industry
 Many useful plastics are polymers of alkenes

•describe, using equations: oxidation reactions of alcohols (1,2,3)

 It is also possible for alcohols to react with strong oxidising agents, such as acidified
potassium permanganate, and selectively oxidise the carbon atom attached to the -OH
group ie. loss of hydrogen and gain of oxygen)
 Alcohols can be oxidised into other important organic compounds.
 The products of the reactions are determined by whether the alcohol is primary,
secondary or tertiary.

Alcohols:
 Primary alchols are oxidised in a two-step reaction, first forming the aldehyde which
is then further oxidised into a carboxylic acid
 To stop the reaction and obtain the aldehyde product, use distillation to remove it
from reaction mixture
 To obtain the carboxylic acid, leave the aldehyde in contact with the oxidising agent
for prolonged time using apparatus for reflux.
 H H H H
I I +[O], heat I o +[O], heat I o
H-C-C-OH H-C-C H-C-C
I I I "-
reflux
I "-ott
H H t H H
ethanol ethanoic acid
primary akohol ethanal
aldehyde
carboxylic acid

+ [O], heat + [O],

ethano] ethanal ethanoic acid
heat
primary alcohol aldehyde carboxylic acid
reflux
H /Cr(VI) Cr(Ill)

Secondary alcohols are oxidized to the ketone by a similar process of oxidation.

H H H H H
I I I I I
H-C-C-C-H +[O], heat
H-C-C-C-H + H20
I I I reflux
I II I
H OH H
H O H
CH3CHOHCH3
(CH3)iCO
propan-2-ol
propanone

+ [O], heat
propan-2-ol propanone
reflux
CH3CHOHCH3 (CH3)iCO

r:IT/C (VI) ---

Cr(III)
Tertiary alcohols are not readily oxidized under comparable conditions. This
would involve breaking the carbon skeleton of the molecule, which requires
significantly more energy. Therefore we will not see a colour change in the potassium
dichromate(VI) oxidizing agent when it is reacted with a tertiary akohol.

H CH3 H
I I I
H-C-C-C-H
I I I
X
+[0], heat
H OH H
2-methylpropan-2-ol

no reaction

+ [O], heat
2-methylpropan-2-ol --- no reaction
H+/ 1 VI) --- ncohange in colour
Reduction of carboxylic acids:
 REMEMBER – oxidation reactions involving alcohols:
 Primary  Alcoholaldehydecarboxylic acid
 Secondary  alcohol  ketone
 These reactions are reversible by using suitable reducing agents:
o Sodium borohydride, NaBH4 in aqueous or alcoholic solution
o Lithium aluminium hydride, LiAlH4, in anhydrous conditions
 H represented the reducing agent
 Dry ether is a solvent
 LiAlH4 is a stronger reducing agent.

• recognise and explain, using equations, that: esters and amides are formed by
condensation reactions.
 Alcohols react with carboxylic acids to form esters in a condensation reaction
o Carboxylic acid + alcohol  ester + water
 Catalysed by concentrated sulphuric acid, H2SO4
 The ester, which has a distinct smell, has the lowest boiling point of the
components of the reaction mixture and so can be separated by distillation.
Ester formation:
• recall the acid-base properties of carboxylic acids and explain, using equations, that
esterification is a reversible reaction between an alcohol and a carboxylic acid
 The condensation reaction between carboxylic acids and alcohols is a
reversible reaction. (Hydrolysis reaction)
 The esters react with water to form carboxylic acid and alcohol.
 This reaction is catalysed by an alkali or dilute acid and requires heat.

• recognise and explain, using equations, that: easters and amides are formed by condensation
reactions
 Another key condensation reaction of carboxylic acids is the formation of amids by
reacting a carboxylic acid with ammonia or an amine.
 Primary amides – carboxylic acid + ammonia
o General formula RCONH2
 Secondary amides – carboxylic acid + amine
o General formula RCONHR’
Amide formation:

• understand that organic reactions can be identified using characteristic observations

and recall tests to distinguish between: alkanes and alkenes using bromine water
primary, secondary and tertiary alcohols using acidified potassium dichromate (VI) and
potassium manganate (VII)
• recognise reaction reactions and explain, using equations, the reaction of nitriles to
form amines
 Nitriles contain the cyano functional group (C≡N)
 The reduction of nitriles involves the addition of hydrogen atoms at the position of the
triple bond.
 This results in a C-N single bond and a terminal amino group (-NH2)
 The reaction requires increased temperature and a metal catalyst.

•understand that the synthesis of organic compounds often involves constructing

reaction pathways that may include more than one chemical reaction
 Simpler molecules, such as alkanes, alkenes and alcohols may be used as
starting materials to make other molecules.
 They are pre-cursors of target molecules.
 The individual reactions are a series of steps that make up a reaction pathway that
can be used to create a desired product.

• deduce reaction pathways, including reagents, condition and chemical equations, given
the starting materials and the product.
Organic materials: structure and function

• appreciate that organic materials including proteins, carbohydrates, lipids and synthetic
polymers display properties including strength, density and biodegradability that can be
explained by considering the primary, secondary and tertiary structures of the materials

The amino acids used to produce proteins in the human body have the general formula H2N-
CH(R)-COOH
 2-amino acid because the amino group is bonded to
the 2 carbon (also known as α-amino acid)
nd

 Amino acids are commonly given three

letter abbreviations
 The major difference between one amino acid and
another is the group of atoms that make up the R
group.
The side chain may be:
 Non-polar or polar
 Have functional groups that can behave as:
o Proton donors
o Proton acceptors

Acid base properties of amino acids:

 Amino acids are difunctional ie. they contain 2 functional groups – amino and
carboxylic acid. Therefore, amino acids are amphoteric.
 The nature of the side chain can also affect the acid-base properties.
 In solution amino acids may be in the form of zwitter ions:
o General formula +H3N-CH(R)-COO-
+
o NH2 can act as a base accepting protons to become NH3
o COOH can act as an acid donating a proton to become COO-
 Different chemical forms of an amino acid can be in equilibrium in a solution.
 The predominant form will depend on the pH of the solution and the type of amino
acid.
 Intermediate pH (5-7) zwitterion is most abundant
  Low pH cation is most abundant
 +H3N-CH(R)-COO- (aq) + H3O+(aq) +H3N-CH(R)-COOH(aq)+H2O(l)
 High pH the anion is most abundant
 +H3N-CH(R)-COO- (aq) + OH-(aq) +H2N-CH(R)-COO- (aq) +H2O(l)

•describe the condensation reaction of 2-amino acids to form polypeptides (involving up to

three amino acids), and understand that polypeptides (proteins) are formed when amino
acids monomers are joined by peptide bonds
 Formed by condensation polymerisation reactions.
 The functional groups react together to form a new functional group (amide
group) which links the monomers. Water is also produced.

Naming polypeptides:
 The amino acid sequence is described using three letter abbreviations
 The structure is drawn so that the free amino group is on the left (N-Terminal) and the
free carboxyl group is on the right (C-Terminal)
  A polypeptide constructed from more than 50 amino acids is a protein.

• describe and explain the primary, secondary (α-helix and β-pleated sheets), tertiary
and quaternary structure of proteins
 Primary structure:
o The number, type and sequence of the amino acids units are known as
the primary structure.
o Represented by the three-letter abbreviations for the amino acids.
o Name starting at the N-terminal amino acid and ending with the C-terminal
amino acid.

 Secondary structure:
o Folding of sections of a protein molecule produce a secondary level structure.
α-helix:
 H-bonds form between the polar -NH group in one peptide link and the polar C=O
group in another peptide link at regular intervals.
 The H-bonds make the molecule coil into the shape of an α-helix.
β-pleated sheets:
 H-bonds also form between peptiude links on neighbouring polypeptide chains
 This stabilises the protein structure

 Tertiary structure:
o Produced by the 3d folding of proteins secondary structures.
o The side chains (R-groups) of the ammino acid units influence the overall 3d
shape of the protein molecule.
o 5 types of attractions are involved in chain folding:

 Quaternary structure:
o Some proteins are composed of 2 or more polypeptide chains, and may even
interact with non-protein molecules to produce a larger, more complex
function unit ie. quaternary structure.
o Eg. Haemoglobin – the oxygen transporting protein
o Each red blood cell contain approx. 250 million molecules of haemoglobin.

• recognise that enzymes are proteins and describe the characteristics of biological catalysts
(enzymes) including that activity depends on the structure and the specificity of the
enzyme action
 Enzymes are biological catalysts that accelerate
the rate of chemical reactions in cells.
o They are needed in small amounts and
are not used up or changed during the
reaction
o They do not alter the position of
equilibrium
o They provide an alternative
reaction pathway that lowers the
activation energy.
Inorganic catalysts vs enzymes:
 Enzymes generally only catalyse one specific reaction, or a reaction that involves
a particular chemical bond or functional group – enzyme specificity
 Whereas inorganic catalysts, such as metallic platinum, can be used to catalyse many
different reactions that use a variety of reactants.
 Enzymes are more sensitive than inorganic catalysts to changes in reaction conditions
eg. Temperature and pH.
 The 3D shape of enzymes is affected by temperature and pH, and a change in pH
and/or temperature disrupts the attractions in the protein that determines its
tertiary shape.
 Catalytic activity is highly specific and depends on tis overall 3D structure
 The active site is the specific part of the enzyme molecule which interacts with a
reactant (substrate)
 The types of intermolecular for bonds formed between an enzyme and a substrate are
the same as those that dictate the tertiary structure and can include H-bonds, ionic
interactions, dipole-dipole attractions, and dispersion forces.

Lock and key model:

 The substrate molecule fits into the enzyme like a key into
a lock, forming an enzyme-substrate complex.
 The enzyme is specific for a particular substate

Induced fit model:
 Chemists have also realised that enzymes have flexible
structures ie. the shape of the active site can be modified by
the binding of a substrate.
Enantiomers:
 Another type of stereoisomer which occurs when
4 different substituents are bonded to a central
carbon atom (chiral carbon atom)
 They form a mirror image but cannot
be superimposed onto each other
 Enzymes can determine between the
enantiomers of a chiral substrate because their
shape and active site will not match up.
 All amino acids except glycine are
enantiomers, which means enzymes also have
this type of stereoisomerism.
 Only one enantiomer might fit the active site
and participate in the reaction.
• recognise that monosaccharides contain either an aldehyde group (aldose) or a ketone
group (ketose) and several -OH groups, and have the empirical formula CH2O
 The smallest carbohydrates are monosaccharides.
 They are white, sweet-tasting solids that are highly soluble in water due to polar
hydroxyl groups which form hydrogen bonds with water.
 The most common monosaccharides are glucose, galactose, and fructose. They have
the same molecular formula and are isomers of each other.

Straight chain form:

 Aldoses:
o Straight chain glucose has an aldehyde functional group

 Ketoses:
o Straight chain fructose has a ketone functional group

• distinguish between α-glucose and β-glucose, and compare and explain the
structural properties of starch (amylose and amylopectin) and cellulose
 Two different forms of glucose can be found in many different organisms
 B-glucose can be converted to a-glucose via straight chain form. When the
straight chain closes to form a ring, the hydroxyl group can either be above
of below the ring.
 

• The straight chain and α-ring forms of glucose and fructose are given in the Chemistry
data booklet.

• The common names, symbol, structural formula and pH of isoelectric point for amino
acids are given in the Chemistry data booklet.

• recognise that triglycerides (lipids) are esters and describe the difference in
structure between saturated and unsaturated fatty acids
 Fats and oils belong to the class of biological molecules called triglycerides (lipids).
o Fats are solid at room temperature
o Oils are liquid at room temperature
 Triglycerides are made by condensation reactions between a glycerol molecule and 3
fatty acid molecules.
o A condensation reaction occurs between the carboxyl group (COOH) and
the hydroxyl group (-OH), forming an ester functional group (-COO-).
Water is released.

Saturated fatty acids:

 Have hydrocarbon chains only containing single C-C bonds
o General formula CnH2n+1COOH
Unsaturated fatty acids:
 Monounsaturated fatty acids contain 1C=C double bond in hydrocarbon chain.
o General formula CnH2n-1COOH
 Polyunsaturated fatty acids contain more than 1 C=C double bond.
Omega-3 vs Omega-6
 Unsaturated fatty acids are classified according to the position of the first double bond
from the end of the hydrocarbon chain.
 The omega carbon is the carbon in the methyl group at the end of the hydrocarbon
chain.
 Omega-3 has C=C on the 3rd carbon from the omega carbon.

• describe, using equations, the base hydrolysis (saponification) of fats (triglycerides)

to produce glycerol and its long chain fatty acid salt (soap)
The reaction to make soap is the reverse of the condensation reaction
 Traditionally, soap was made by heating animal fat or vegetable with a strong alkali
(NaOH).
 When the triglyceride molecules are heated with NaOH, the 3 ester links are
hydrolysed. This is known as base hydrolysis or saponification when it refers
specifically with esters.
 The products of the hydrolysis are glycerol and sodium salts of three fatty acids.
These sodium salts are the main components of soap.
 The metal hydroxide used can affect the soap produced. Eg. Fatty acid sodium salts
produce a solid soap whereas fatty acid potassium salts produce a liquid soap.

Hydrolysis of triglycerides in the body:

 Triglycerides undergo enzyme-catalysed hydrolysis during digestion.
  They are insoluble in water which means their molecules remain intact as they
pass through the digestive system until they reach the small intestine.
 In the small intestine, bile emulsifies the fats, breaking them down into smaller
particles. This increases the surface area of the fats, which means that lipase, a water-
soluble enzyme, can access more triglyceride molecules, increasing the rate of
hydrolysis.

 Lipase enters the small intestine from the pancreas and catalyses the hydrolysis of the
3 ester bonds.

•explain how their cleaning action and solubility in hard water is related to their chemical
structure
 The most common stain that needs to be removed from laundry is body oil.
 Oils are non-polar, but water is a polar solvent.
 We know that substances with similar types of intermolecular forces will dissolve in
each other; however, if they are different, they will not.
 Cleaning presents a dilemma, but soaps and detergents provide solution.
Chemical structure of soaps:
 The long fatty acid ions in soap have a non-polar hydrocarbon chain and a
negatively charged carboxylate functional group. These ions are able to form a link
between oil and water.
 Water is polar and bonds with the charged carboxylate group – ‘hydrophillic’ end.
  The non-polar hydrocarbon chain mixes with the non-polar oil and is ‘hydrophobic’

 In water, soap particles clump together to form micelles. They are a spherical
shape with hydrophobic tails in the middle and hydrophilic ends are on outside.
 During washing clothes, vigorous agitation breaks up micelles formed by soap.
 As agitation continues, water forms ion-dipole bonds with the negatively
charged carboxylate group, and the oil is lifted from the fabric.
 Once the oil lifts from the fabric, the non-polar tails surround the oil in a stable
arrangement.

Cleaning in hard water:

 Hard water contains high levels of metal ions such as calcium, magnesium, and iron
(II) and this can limit the effectiveness of the soap.
 Fatty acid ions in soap react with the metal ions forming insoluble metal salts.
 This results in:
o Poorly washed clothes
o Blocked drains from soap scum
o Soap scum (grey precipitate) in wash tubs and around basins and taps.
o When washing with soap in hard water, either extra soap needs to be used or
the metal ions need to be removed using carbonate ions.
• explain how the properties of polymers depends on their structural features including; the
degree of branching in polyethene (LDPE and HDPE), the position of the methyl group in
polypropene (syntactic, isotactic and atactic) and polytetrafluorethene.

• describe the condensation reaction of monosaccharides to form disaccharides

(lactose, maltose, and sucrose) and polysaccharides (starch, glycogen and cellulose)
 Disaccharides are formed from a condensation reaction between 2 monosaccharides.
 2 glucose molecules combine to form maltose and a water molecule is formed.
• understand that polysaccharides are formed when monosaccharide monomers are joined
by glycosidic bonds.
 Three most important polysaccharides are starch cellulose and glycogen.
 Each of these have different properties even though they are polymers of the same
monomer (glucose).
 Starch:
o Plants can produce and polymerise a-glucose molecules to form starch. Plants
store starch so that it can later be metabolised to produce energy via cellular
respiration.
 Amylose – linear
 Amylopectin – branched
 Both forms have different solubilities. Occasional branching restricts the
coiling of the polymer leaving many -OH groups exposed and increasing
solubility of amylopectin.

 Cellulose:
o the main structural material in plants found in cell walls in plant cells.
o Formed from polymerisation of B-glucose
 Glycogen:
o Polymer of a-glucose but it is highly branched.
 o It is formed from excess glucose and stored in the liver or muscle to be
used when glucose levels are low.
• distinguish between a-glucose and b-glucose and compare and explain the
structure properties of starch (amylose and amylopectin) and cellulose

Topic 2: Chemical synthesis and design

Chemical synthesis
• appreciate that chemical synthesis involves the selection of particular reagents to form
a product with specific properties
 Organic chemists develop compounds such as pharmaceuticals, polymers
and nanomaterials, with specific properties for a purpose.
 Once the desired compound has been identified, they then derive an efficient way
to make it using readily available starting
materials.
 Chemists find it easier to start with
target molecule and work backwards to
simpler molecules – this is known as
retrosynthesis
Modifying Chemical Properties:
 Once an active compound has been identified, it is important to synthesise a
number of derivatives with more desirable properties to create the most effective
product.
o Eg. Aspirin – salicylic acid was one of the first a analgesics developed, buyt it
caused internal bleeding due to its acidic nature. A number of derivatives
were synthesised which had similar chemical structure and therapeutic
properties but without the detrimental side effects
o Aspirin is a prodrug – a biologically inactive derivative of a compound that is
metabolised through chemical reactions or enzymes into the active form of the
drug. Prodrugs reduce side effects and toxicity and improve chemical
stability.
Altering solubility:
 The bioavailability of a drug inside the body is related to how fast the chemical can
be absorbed, which is related to its solubility.
  Solubility is one of the main parameters to formulating a drug, that produces the
desired pharmacological response without exceeding the TD50 (toxic response is
<50% pop.)
 The solubility of a tablet or capsule depends on:
o The pH and temperature inside the body
o The structure of the capsule or tablet
o The nature of the packing ingredients in the capsule or tablet.
o Eg. Aspirin -to increase its solubility in water, the sodium salt is made.
Aspirin:
 Salicylic acid contains an OH group attached to a
benzene ring. Aspirin does not contain this, but has an
acetyl group attached.
 Aspirin is then hydrolysed slowly by water to form
salicylic acid in the alkaline conditions of the small
intestine where it is absorbed into the blood.
 When aspirin reaches the alkaline conditions of the
small intestine, the H3O+ ions are removed, so the
equilibrium will shift to the right and the aspirin will
dissolve.
 The sodium salt is created because it is ionic and dissolves completely in
water making it easier for patients to digest.

• understand that reagents and reaction conditions are chosen to optimise the yield and rate
for chemical synthesis processes, including the production of ammonia (Haber process),
sulfuric acid (contact process) and biodiesel (base-catalysed and lipase-catalysed methods)

 The Haber process made the production of high nitrogen content fertilisers
feasible which led to better crop yields in agriculture.
o N2 + 3H2 2NH3
 It is also used in the manufacture of plastics, explosives, textiles pesticides and dyes.
 In industry it is essential to balance the reaction conditions for high equilibrium yield
and reaction rate for the best economic outcome.
Effect of changing temp and pressure:
 There are 4 gaseous molecules on the reactant side and 2 gaseous molecules on the
product side.
 By increasing the pressure of the reactor, the reaction will shift to the right favouring
the side with the fewer moles of gas and increasing the yield of the product at
equilibrium.
 The habor process is exothermic H=-92kJ/mol, therefore, a decrease in temperature
will cause the system to favour the products and increase equilibrium yield.
Effect of catalyst:
 The most common catalyst is finel ground magnetite (Fe3O4)
 The use of a catalyst increases the reaction rate but does not directly affect
the equilibrium yield.
 The reaction can proceed at a viable rate at a lower temperature than it would without
a catalyst.
 The contact process is the industrial manufacture of sulphuric acid and sulphur from
iron sulphide.
 Completed in a 3 step process:
o Production of sulphur dioxide
o Conversion of sulphur dioxide into sulphur trioxide
o The conversion of sulphur trioxide into sulphuric acid

 Only the conversion from sulphur dioxide to sulphur trioxide is reversible; all
other steps are irreversible.
1.
Sulphur is burned in excess in the air in the reaction : S + O2 SO2
2.
Sulphur trioxide is produced 2SO2 + O2  2SO3
3.
Sulphur trioxide is converted to sulphuric acid: SO3 + H2SO4 H2S2O7
4.
The oleum can then be reacted safely with water to produced concentrated
sulphuric acid: H2S2O7 + H2O  2H2SO4
 Biocatalyst:
o term for biologically produced industrial catalyst, which includes, but is not
limited to enzymes.
o The use of enzymes allow manufacturers to produce the same, or higher,
quality products, with less raw materials, energy consumption and
waste.
o Benefits of biocatalysts include:
 Fewer by-product use
 Reduced energy use
 Reduced environmental pollution
 Reduced toxicity when biocatalyst reaches environment.
 Lipase-catalysed production of biodiesel:
o The reduced availability of fossil fuels and associated environmental
issues has increased the need to find alternate fuel sources.
o Biodiesel is produced from lipid feedstock and alcohol
o Is produced by transesterification of vegetable oil and animal fats using
NaOH (alkali catalyst) and sulphuric acid at high temperatures.
o An alternative approach is the enzymatic hydrolysis using lipase to catalyse
the transesterification.
 Advantages and limitations of using lipase:
Advantages Limitations
 No soap formation  Longer reaction time
 Esterification of both fatty acids  Higher catalyst concentration
and trigylcerides in a single step. required
  Higher quality glycerol produced  Higher production cost
 Milder conditions, therefore,  Reduction in effectiveness after
lower energy consumption 100 days application

• understand that fuels, including biodiesel, ethanol and hydrogen, can be synthesised from
a range of chemical reactions including, addition, oxidation and esterification
 Biodiesel is a fuel derived from vegetable oils and fats with similar
combustion properties to regular petroleum diesel fuel.
 It can be produced from oil-yielding crops, such as soybean, canola, corn or
sunflower via a process known as transesterification
 Ethanol is produced by the addition reaction of steam and ethene using a strong acid
catalyst.

• understand that enzymes can be used on an industrial scale for chemical synthesis to
achieve an economically viable rate, including fermentation to produce ethanol and lipase-
catalysed transesterification to produce biodiesel
Advantages of lipase in biodiesel production Limitations of lipase in biodiesel production
 Lipase works in both hydrophilic  Significant cost
and hydrophobic solvents  Reduction in activity if glycerol
 Can be produced in bulk covers lipase, reducing contact with
 Show considerable catalytic ability substrate
ie. long and branched alcohols.  Reduced activity due to volume of
 Can be re-used after removal oil molecule.
 Higher thermostability

• describe, using equations, the production of ethanol from fermentation and the hydration
of ethene
 It is possible to form ethanol by either substitution or addition reactions; however,
industrially, it is produced by the addition reaction of steam and ethene using a strong
acid catalyst.

• describe, using equations, the transesterification of triglycerides to produce biodiesel

 Fats and oils are triglycerides; their structure consisting of 3 hydrocarbon
chains attached by ester functional groups.
  In the transesterification process, the triglyceride is
reacted with short-chain alcohols to produce a
different ester.
 Reaction carried out at low temperature and pressure
using a base as a catalyst.

•
• discuss, using diagrams and relevant half-equations, the operation of a hydrogen fuel
cell under acidic and alkaline conditions.
 A fuel cell is a type of galvanic cell that
generates electricity from redox reactions
quietly and efficiently and with almost no
pollution.
 Reactants are not stored in fuel cells and need
to be continuously supplied.
Alkaline conditions:
 Alkaline fuel cells operate using a base as
the electrolyte eg. KOH
 At the anode (-), hydrogen gas is oxidised by
reacting with hydroxide ions from the
electrolyte.
o There is a catalyst (platinum metal)
incorporated into the anode to increase the rate of oxidation.
o H2(g) + 2OH- 2H2O(l)+e-
(aq)
 At the cathode (+), oxygen gas is reduced
o A catalyst such as nickel powder or a nanomaterial can be used.
o O2(g) + 2H2O(l) +4e- --Catalyst4OH-(aq)
Acidic conditions:
 The hydrogen enters the fuel cell and the atoms are ionised to form H+ at the anode.
 The oxygen enters the cathode and is reduced by gaining electrons and combings with
H+ to form water.
 At the anode (-) hydrogen gas is oxidised
o 2H2(g)  4H+(aq) +4e-
 At the cathode (+), oxygen gas is reduced
 o O2(g) + 4H+(aq) + 4e- 2H2O(l)
 The overall equation for the reaction in both alkaline and acidic conditions is:
o 2H2(g) + O2(g)  2H2O(l)
Hydrogen fuel cell efficiency:
 Generally quoted as being 40-60% efficient compared with thermal power stations
(30-40%) and car engines (25-30%).
 More efficient due to being able to transform chemical energy directly into
electrical energy rather than having a series of different energy conversions.
 Waste heat can also be used to produce steam, which can then be used to operate a
turbine or produced more heat, increasing the efficiency to 85%.
 A fuel cell using hydrogen can be described as ‘zero-emissions’ because water, heat
and electricity are the only products, however, hydrogen needs to be produced using
renewable energy.
Hydrogen Production:
 95% of hydrogen is produced from fossil fuels through process of steam reforming.
 The hydrogen produced in this way has a slower energy content as some of the
chemical energy is lost as waste during heat production.
 It is argued that this is still cleaner than just using fossil fuels as the CO2 can be
captured at the site preventing release into the atmosphere.

• calculate the yield of chemical synthesis reactions by comparing stoichiometric quantities

with actual quantities and by determining limiting reagents.

Green chemistry

• appreciate that green chemistry principles include the design of chemical synthesis
processes that use renewable raw materials, limit the use of potentially harmful solvents and
minimise the amount of unwanted products

• outline the principles of green chemistry and recognise that the higher the atom economy,
the ‘greener’ the process

• calculate atom economy and draw conclusions about the economic and
environmental impact of chemical synthesis processes.