Thermochemistry

The basics
• 1st Law – Energy cannot be created or destroyed,
it can only be converted from one form to
another e.g in chemical reactions
• 2nd Law – a process can only be spontaneous in
one direction and the spontaneous process will
lead to an increase in entropy (disorder)

Laws of Thermodynmaics
• Enthalpy change (ΔH)
• Entropy change (ΔS)
• Free-energy change (ΔG)
• These are all state functions, meaning it doesn’t matter
how they get from start to end, the energy or entropy
change will be the same.

The terms
• Values given are normally under standard state
conditions, which is indicated by a superscript circle e.g.
ΔH°
• Gases are at 1 atm pressure
• All liquids and solids are pure
• All solutions at 1 M concentration
• Temperature is 25°C or 298 K
• Energy of formation of an element in its normal state is 0

Standard State Conditions

• Enthalpy change is a measure of the energy absorbed or
released during a reaction
• When bonds are formed, energy is released
• When bonds are broken, energy is absorbed
• Exothermic: ΔH<0, products have stronger bonds than
reactants
• Endothermic: ΔH>0, reactants have stronger bonds than
products

Enthalpy
• The energy change when one mole of a compound is
formed from its component elements under standard state
conditions
• ΔH° = ΣΔHf° products - ΣΔHf° reactants
• E.g. 2CH3OH(g) + 3O2(g)  2CO2(g) + 4H2O(g)

ΔH° = [2(ΔHf°CO2) + 4(ΔHf°H2O)] – [2(ΔHf°CH3OH)+ 3(ΔHf°O2)]

Remember (ΔHf°O2) = 0

Heat of Formation (ΔHf°)

• Heat capacity is a measure of how much the temperature
of an object is raised when it absorbs heat
• A substance with al arge heat capacity can absorb a lot of
heat with the temperature changing only a small amount
e.g. water
• Cp = ΔH/ΔT (ΔH – heat added, ΔT – temperature
change)

Heat Capacity (Cp)

• Is the amount of heat required to raise the
temperature of 1 gram of substance by one
degree Celsius (or Kelvin)
• Q = mcΔT m – mass of substance (g or kg)
c – specific heat
ΔT – temperature change (K or ˚C)
• Water has a heat capacity of 4.18 J/g˚C

Specific heat
• ΔG = ΔG˚ + RT ln Q
• R – gas constant (8.31), T - absolute temperature, Q –
reaction quotient (a constant)
• At equilibrium ΔG = 0 and Q = K so
ΔG˚ = -RT ln K or ΔG˚ = -2.303RT log K
• If ΔG˚< 0, K> 1 so products favored
• If ΔG˚> 0, K< 1 so reactants favoured

ΔG and equilibrium
Energy diagrams
Energy diagram - catalyst