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First Law of
Energy cannot be created or destroyed. It can only change its form.
Thermodynamics
The enthalpy change for a reaction depends only on the initial and final
Hess’s Law states and is independent of the route taken from reactants to products.
(This is the First Law of Thermodynamics applied to chemical systems.)
Enthalpy change This is the change in heat content of a chemical system at constant
∆H pressure
Exothermic A change which gives out heat to the surroundings (∆H is –ve)
Endothermic A change which takes heat in from the surroundings (∆H is +ve)
Changes measured under standard conditions are for 100 kPa pressure
Standard conditions and a specified temperature (often 25OC / 298K). The symbol Ө is used
for this.
The normal state (solid, liquid or gas) of a substance under standard
Standard state conditions. (Water can be either pure liquid or water vapour at room
temperature and pressure, so the state symbol should always be used.)
Standard enthalpy The enthalpy change when 1 mole of a compound is formed from its
of Formation elements under standard conditions, with all substances in their standard
∆HfӨ states. By definition, ∆HfӨ for any element is zero.
Standard enthalpy The enthalpy change when 1 mole of a substance is burned completely
of Combustion in pure oxygen under standard conditions, with all substances in their
∆HcӨ standard states. (Water is usually taken to be liquid here.)
This is the enthalpy change when 1 mole of a specific bond is broken
Bond Dissociation
(all molecules and atoms are in the gas phase).
Enthalpy ∆HD
Remember that bond breaking is an endothermic process.
This is the average enthalpy change when 1 mole of a particular type of
Mean Bond bond is broken (all species in the gas phase). The values are
Enthalpy approximate because an average is taken of all the compounds
containing that particular bond (e.g., a C-H bond).
This is the minimum energy required by particles when they collide to
Activation Energy
enable reaction to occur. It is a fixed value for any reaction.
This is a substance which speeds up a chemical reaction, but which is
Catalyst (nature) not used up and can be recovered chemically unchanged at the end of
the reaction.
The catalyst provides an alternative route for the reaction with a lower
Catalyst (action)
activation energy.
A state of dynamic equilibrium is reached for reversible reactions when
Dynamic the rates of the forward and reverse reactions are equal. Both reactions
equilibrium continue, but the concentrations of all products and reactants in the
mixture remain unchanged.
Le Chatelier’s A system at equilibrium will respond in such a way as to oppose any
Principle change made to it.
This is the loss of electrons.
Oxidation
Oxidation number of an element increases (gets more positive)
Oxidising Agent A species which accepts electrons.
This is the loss of oxygen or the gain of electrons.
Reduction
Oxidation number of an element decreases (gets less positive)
Reducing Agent A species which donates electrons.
Redox Reaction Reduction and oxidation always happen together
A redox reaction where one element is simultaneously oxidised and
Disproportionation
reduced, e.g., chlorine in water (0 to +1 and 0 to –1)
Compounds with the same molecular formula and the same structural
Stereoisomers formula, but the atoms or groups are arranged differently in 3-D space.
There are two types of stereoisomerism: geometric and optical (A2).
Compounds with the same molecular formula and structural formula,
Geometric (or E-Z) but atoms or groups are fixed either on the same side (Z-isomer) or on
isomers opposite sides (E-isomer) of a bond which cannot rotate freely, e.g., a
C=C double bond.
Homolysis (or The equal splitting of a covalent bond where each atom in the bond
homolytic fission) receives one electron. This leads to the formation of free radicals.
Heterolysis (or The unequal splitting of a covalent bond where one atom in the bond
heterolytic fission) takes both electrons. This leads to the formation of ions.
Free radical A species (atom, molecule or ion) with an unpaired electron.
A species which can accept a lone pair of electrons (attracted to
Electrophile
electron-rich centres). [A Lewis Acid – see A2 Modules 4 & 5)
A species which has a lone pair of electrons which can be donated
Nucleophile
(attracted to electron deficient centres). [A Lewis Base – see A2]
This term refers to an activity that has no net annual carbon (greenhouse
Carbon neutral
gas) emissions to the atmosphere.
A2 CHEMISTRY MODULE 4 DEFINITIONS (AQA)
Homogeneous A chemical system where all components in the mixture are in the same
system phase, e.g., all liquids or all gases
Heterogeneous A chemical system where components in the mixture are in different
system phases.
This is the ratio of the product concentrations raised to the powers of
their respective stoichiometric coefficients to the reactant concentrations
Equilibrium raised to the powers of their respective stoichiometric coefficients.
Constant, KC Stoichiometric coefficients are the balancing numbers in the chemical
equation. Concentrations must be in units of mol.dm-3
The numerical value of KC changes only with temperature.
This is similar to KC, except that partial pressures are used instead of
Equilibrium concentrations. This applies only for gases (since vapour pressures of
Constant, KP solids and liquids are negligible compared to gases).
The numerical value of KP changes only with temperature.
The sum of the individual partial pressures of gaseous components in a
mixture of gases equals the total pressure. Each gas exerts the same
Partial Pressure pressure as it would if it occupied the whole volume by itself. If the
total pressure is known, the partial pressure of a component is the total
pressure multiplied by its mole fraction: pA = PT × xA
This is the number of moles of a component divided by the total number
Mole fraction
of moles in the mixture, e.g., xA = nA / ntotal
Molecules with the same molecular formula, but which have atoms
Isomers arranged differently in some way. There are two kinds, structural and
stereo.
Molecules with the same molecular formula, but with the atoms joined
up in different ways to different atoms. There are three types:
Structural Isomers • chain – the carbon skeleton is different
• positional – the functional group is in a different place in the chain
• functional group – the functional group is different
Here the molecular formula and the structural formula are the same, but
the atoms are arranged differently in space. There are two kinds:-
• geometric – atoms or groups are fixed on either the same or opposite
sides of a bond that cannot rotate freely, e.g., a double bond in
alkenes. The two forms are called cis- and trans- respectively
Stereoisomers
• optical – when a C atom in a molecule is asymmetrical, i.e., has 4
different atoms or groups attached, so that mirror images are
possible. The substance rotates the plane of polarised light, one
enantiomer rotates the light clockwise (+) and the other rotates it
anti-clockwise (-)
A2 CHEMISTRY MODULE 5 DEFINITIONS (AQA)
Definitions of thermodynamic quantities from AS Module 2 are also required in this module and
are repeated here for completeness.
Enthalpy change This is the change in heat content of a chemical system at constant
∆H pressure
Changes measured under standard conditions are for 1 atmosphere
Standard conditions pressure (100 kPa) and 25OC (298K) and a concentration of 1M for
solutions. The symbol o is used for this.
The normal state (solid, liquid or gas) of a substance under standard
Standard state conditions. (Water can be either pure liquid or water vapour at room
temperature and pressure, so the state symbol should always be used.)
Standard enthalpy The enthalpy change when 1 mole of a compound is formed from its
of Formation elements under standard conditions, with all substances in their standard
∆Hfo states. By definition, ∆Hfo for any element is zero.
Standard enthalpy The enthalpy change when 1 mole of a substance is burned completely
of Combustion in pure oxygen under standard conditions, with all substances in their
∆Hco standard states. (Water is usually taken to be liquid here.)
This is the enthalpy change when 1 mole of a specific bond is broken
Bond Dissociation
(all molecules and atoms are in the gas phase).
Enthalpy ∆HD
Remember that bond breaking is an endothermic process.
This is the average enthalpy change when 1 mole of a particular type of
Mean Bond bond is broken (all species in the gas phase). The values are
Enthalpy approximate because an average is taken of all the compounds
containing that particular bond (e.g., a C-H bond).
Standard enthalpy This is the enthalpy change for the production of 1 mole of gaseous
of Atomisation atoms (= ½ ∆HD for a diatomic molecule or ∆Hsub for the sublimation of
∆Hato an atomic solid like sodium or graphite)
The enthalpy change for the removal of one mole of electrons from 1
Standard enthalpy
mole of species in the gas phase, forming 1 mole of positive ions
of Ionisation
• 1st IE is for X(g) → X+ (g) + e-
∆Hio
• 2nd IE is for X+(g) → X2+ (g) + e-
The enthalpy change for the addition of one mole of electrons to 1 mole
Standard Electron
of species in the gas phase, forming 1 mole of negative ions
Affinity
• 1st EA is for X(g) + e- → X- (g)
∆Heao
• 2nd EA is for X-(g) + e- → X2- (g)
This is for ionic compounds and can be defined in two ways:-
• dissociation = separating the lattice into gaseous ions (endothermic)
Lattice enthalpy
e.g., NaCl(s) → Na+ (g) + Cl – (g)
∆HLo
• formation = forming the lattice from gaseous ions (exothermic)
e.g., Na+ (g) + Cl – (g) → NaCl(s)
This is the enthalpy change when 1 mole of gaseous ions is dissolved in
Hydration enthalpy
water to form 1 mole of hydrated ions in solution, e.g.,
∆Hhydo
Na+ (g) → Na+ (aq) or Cl – (g) → Cl – (aq)
This is the enthalpy change when 1 mole of an ionic solid is dissolved in
Solution enthalpy
enough water to ensure that the dissolved ions are well separated and do
∆Hsolo
not interact with each other
Spontaneous This is a change which has a natural tendency to occur without being
change driven by external influences. It can occur in one particular direction,
but not the reverse unless conditions, e.g., temperature, are changed.
Entropy can be thought of as the degree of disorder in a substance.
Entropy, S (This is not technically correct. It is really related to the number of
ways of distributing energy amongst the particles in a substance.)
Entropy decreases as temperature decreases, so it is reasonable to
assume that at 0 K all substances will be perfectly ordered and have zero
Absolute Standard
entropy. It is possible, therefore, to define an absolute entropy for a
Entropy, So
substance at other temperatures. This is not possible for enthalpy,
where we can only consider enthalpy changes.
∆Go = ∆Ho - T∆So
The FREE energy change is effectively the energy which is available for
Gibbs Free Energy
useful work, after removal of that part of the total heat change which
change, ∆Go
goes into disorder of the system. ∆G o = 0 at equilibrium and must be
negative for any spontaneous change (feasible reaction).
These are measured for any redox system relative to the standard
hydrogen electrode. They are expressed as reduction reactions (the right
Standard Electrode
hand electrode, with the standard H2 electrode as the left hand
Potential, Eo
electrode). A more positive Eo means the system prefers to be in the
reduced form (i.e., behaves as an oxidising agent) and vice versa.
The cell potential is the potential difference between two electrodes
coupled together. This is often referred to as the electromotive force (or
e.m.f.) if the cell. Experimentally, this is measured using a high
Standard Cell
resistance voltmeter (so that virtually no current is drawn). To calculate
Potential, Ecello
the value of the e.m.f. of the cell, the two Eo values are combined and
the value must be positive for a spontaneous (feasible) reaction:-
Ecello = EoRHS - EoLHS