4 Energy of chemical reactions

a) 1st law of thermodynamics

b) Enthalpy
c) Hess‘s law
d) Enthalpy of formation
4 Energy: a) 1st law of thermodynamics
• Generally energy conservation is valid
• Also true for chemical reactions:

exothermic: Energy is released

endothermic: support of energy needed
4 Energy: a) 1st law of thermodynamics
• internal energy U: energy content of chemical compounds

chemical reactions: DU = U(product) – U(reactand)

• 1st law of thermodynamics:

DU = DQ + DW (Q: heat, W: work)

4 Energy: a) 1st law of thermodynamics
• 1st law of thermodynamics:

DU = DQ + DW (Q: heat, W: work)

Q > 0 endothermic
Q < 0 exothermic

W > 0 ‚work on the system ‘, e. g. Compression

• W = - ∫pdV with pressure p, volume V

4 Energy: b) Enthalpy
• gr: enthalpein – to heat up
• Enthalpy H very useful for chemical reactions:

H = U + pV => dH = dQp (heat at constant pressure)

• importance: H is a state function!
• DH = H(products) – H(reactants)
e. g. 2 H₂ (g) + O₂ (g) → 2 H₂O (g) DH = -483,6 kJ

• Measurement of reaction enthalpies: calorimeter

4 Energy: b) Enthalpy
4 Energy: b) Enthalpy
• Function of bomb calorimeter:
– combustion (exothermic): heat released to the water
– DQ = n * Cm * DT = m * Cs * DT
– C: molar (m) or specific (s) heat capacity (of water)

• also in use: heat of combustion: DH = C‘(calorimeter) * DT

• for analysis of unknown substances:
mass related combustion enthalpy DH/m, unit: kJ/g => tabulated values
4 Energy: c) Hess‘s law
• for the determination of any reaction enthalpies
• State function: only start and endpoint needed
(in this case: reactant + product)
• reaction can be ‘set together‘ from other (arbitrary) reaction steps
e. g. combustion of methane (see next page)
• ‚replacement reactions‘ don‘t need to be possible in practice
• Important reactions & enthalpies:
C(s) + O₂ (g) → CO₂ (g) DH = -393,5 kJ/mol(CO₂)
H₂ (g) + 0,5 O₂ (g) → H₂O (l) DH = -285,8 kJ/mol(H₂O)
4 Energy: c) Hess‘s law
4 Energy: d) enthalpy of formation
• Formation from the elements (tabulated!)
• Standard conditions: 1 bar, 298 K, aggregate state at these conditions
z. B. H₂O (l), O₂ (g), C (s) (graphite)

• C₃H₈ (g) + 5 O₂ (g) → 3 CO₂ (g) + 4 H₂O (l) (see next page)

• Can also be calculated at different temperatures, not discussed here

4 Energy: d) enthalpy of formation
4 Energy: d) enthalpy of formation
Application for different areas, examples:
• food:
• sugar: C₆H₁₂O₆ (s) + 6 O₂ (g) → 6 CO₂ (g) + 6 H₂O (l)
DH = - 2803 kJ/mol(glucose)
• fat: 2 C₅₇H₁₁₀O₆ (s) + 163 O₂ (g) → 114 CO₂ (g) + 110 H₂O (l)
DH = -75,52 MJ/(2 mol tristearin)
• fuel:
• 2 CH₃OH (l) + 3 O₂ (g) → 2 CO₂ (g) + 4 H₂O (l) DH = -726 kJ/mol (methanol)
• CH₄ (g) + 2 O₂ (g) → CO₂ (g) + 2 H₂O (l) DH = -890,3 kJ/mol (methane)