Thermodynamics

Key notes and ideas for revision!

Key definitions
Lattice formation of enthalpy: the enthalpy change when one mole of ionic solid is formed from its gaseous ions under standard conditions.

Lattice disassociation enthalpy: the enthalpy change when one mole of ionic solid disassociates to form its gaseous ions under standard conditions.
Enthalpy of formation the enthalpy change when one mole of a compound is formed from its elements in their standard states under standard conditions. Enthalpy of atomisation of an element the enthalpy change when 1 mole of gaseous atoms is formed from its elements in their standard states. Enthalpy of atomisation of a compound the enthalpy change when 1 mole of compound in its standard state is converted into gaseous atoms Bond disassociation enthalpy the enthalpy change when all bonds of the same type break in 1 mole of gaseous molecules.

First ionisation enthalpy the enthalpy change when 1 mole of 1+ ions are formed from 1 mole of gaseous atoms Second ionisation enthalpy the enthalpy change when 1 mole of 2+ ions are formed from 1 mole of 1+ ions.

First electron affinity the enthalpy change when 1 mole of 1- ions are formed from 1 mole of gaseous atoms. Second electron affinity the enthalpy change when 1 mole of 2- ions is formed from 1 mole of 1- ions.
Enthalpy of hydration the enthalpy change when 1 mole of aqueous ions is produced from gaseous ions Enthalpy of solution the enthalpy change when 1 mole of ionic solid dissolves in an excess of water.

Calculating enthalpy changes

The enthalpy change is the energy required to break bonds in the reactants and the energy released from the bonds formed in the product. H = products reactants Born Haber Cycles show the enthalpy changes of a reaction directly and indirectly. The enthalpy change will remain the same

Theoretical lattice enthalpies are often different to experimental values You can work out a theoretical lattice enthalpy by doing
calculations based on the purely ionic model of a lattice The purely ionic model assumes that all the ions are spherical in the lattice and charge is evenly distributed around them. The experimental lattice enthalpy is normally different as it has been found that the ions have some covalent character and ions arent exactly spherical. Positive ions polarise negative ions to an extent that the shape is distorted to different extents. The more polarisation there is, the more covalent the bonding is. If experimental values exceed the theoretical, this suggests that the bonding is stronger than what the purely ionic model suggests and bonds are more polarised with a lot of covalent character. If values are quite close, then its assumed that it fits the

Enthalpies of solution
Dissolving involves enthalpy changes. When an ionic solid dissolves in water; 2 things happen:
Bonds between ions break this is ENDOTHERMIC! This is the enthalpy of disassociation. (the enthalpy change when an ionic solid disassociates to form its gaseous ions under standard conditions) Bonds between ions and water are made this is EXOTHERMIC. This is the enthalpy of hydration (the enthalpy change when 1 mole of aqueous ions are formed from gaseous ions)

Dissolving ionic compounds

Ions are strongly attracted to water as water is a polar molecule. Oxygen is more electronegative than hydrogen and creates a dipole within the molecule. Enthalpy of solution is the enthalpy change when 1 mole of ionic solid dissolves in an excess of water. The more exothermic soln the more likely the solution is to dissolve.

Enthalpy change can be calculated using Hess law!

Put the ionic lattice first and then the dissolved ions on the top. Connect them with an arrow of enthalpy of solution DIRECT ROUTE Connect the ionic lattice to the gaseous ions through lattice disassociation enthalpy (this will be a positive value) (negative value will the lattice enthalpy of formation) Connect the gaseous ions to the dissolved ions through enthalpy of hydration if each ion. This completes the indirect route. Values are negative. The enthalpy change of solution is endothermic but is compensated for by a small increase in entropy.

Calculating enthalpy of soln

Hsoln = Hhydration Hlattice formation Hsoln = Hhydration disassociation + Hlattice

The greater the lattice energy, the harder it is to separate the ions and lower the solubility. The greater the hydration energy, the greater the energy released and when dissolving in water it will be very soluble.

Mean bond enthalpies

Averages of bond enthalpies WILL NEVER BE ACCURATE

Types of bonds and strength will vary in strength depending on its environment.
Bond enthalpies used are averages. They may be different to the ones in the actual compound.

Entropy tells you how much disorder there is

Entropy is the measure of how many ways particles can be arranged and the number of ways that energy can be shared out between the particles. Substances like disorder so particles try to move to increase the entropy. Things that affect entropy includes:
PHYSICAL STATE solid particles wobble about a fixed point (which increases with heat) and it has the lowest entropy as theres hardly any randomness. When solid is melted to liquid, there is an increase in disorder as particles are no longer in a fixed position, but there is a state of order still but theres increased entropy. When this is vaporized gas particles are formed and they whizz around wherever they like. They have the most random arrangements of particles and therefore the highest entropy values.

Dissolving affects entropy

Dissolving a solid increases the entropy. Dissolved particles move freely as they are no longer in a fixed position. MORE PARTICLES = MORE ENTROPY
The more particles there are, the more ways their energy can be arranged as the number of moles increases.

Entropy increase may explain spontaneous endothermic reactions

A spontaneous reaction will JUST HAPPEN BY ITSELF!! No energy input is required there must be other factors other than enthalpy that contributes towards spontaneity.

Endothermic reactions are also spontaneous despite putting energy in. in some endothermic reactions, energy doesnt need to be supplied it just happens.
E.g. water evapourates at room temperature the change to break bonds is endothermic but no energy is supplied. It changes state and entropy increases. Reaction with sodium hydrogencarbonate and HCl is a spontaneous endothermic reaction and also results in an increase in entropy.

Calculating entropy change:

S = Jmol-1 Reactions wont happen unless the total S value is positive. System refers to the entropy change between reactants and products

Stotal = Ssystem +Ssurroundings

Ssystem = products reactants Ssurroundings = H
T (in K)

Free energy change

Free energy change G is a measure used to predict. G is negative or equal to zero then the reaction may happen by itself. G takes into account changes in enthalpy and entropy in the system G (Jmol-1) = H(Jmol-1) TS

H has to be x103
T is in K S is in JK-1mol-1

The feasibility of some reactions depends on temperature.

If the reaction is exothermic (negative H) and has a positive S and then G is always negative. Reaction is feasible at any temperature.

If reaction is endothermic (positive H) and has a negative S - G is always positive and reaction isnt feasible at any temperature.
S is positive and H is positive reactions only feasible at very high temperatures. S and H is negative, reaction will only be feasible under certain temperatures but not at high temperatures. E.g. the freezing of water is an exothermic process but wont work at high temperatures.

Calculating the temperature a reaction becomes feasible

When G is zero a reaction becomes feasible. Calculating temperature by: T = H S
T=K H = Jmol-1 (x103) S = JK-1mol-1