Enthalpy and Thermochemistry
Enthalpy and Thermochemistry
Enthalpy and Thermochemistry
Energies changes at constant pressure are called the enthalpy, given the symbol H.
Heat changes during reactions are important from mechanistic, process and safety
considerations.
H = U + pV
Hess’ Law:
13
The total enthalpy change for a reaction is independent of the path by which the reaction
occurs.
An easy example:
(1) CO(g) + ½ O2(g) → CO2(g) ΔH1 = - 283.0 kJ mol-1
Alternatively,
(2) C(graph.) + ½ O2(g) → CO(g) ΔH2 = - 110.5 kJ mol-1
(3) C(graph.) + O2(g) → CO2(g) ΔH3 = - 393.5 kJ mol-1
Hess’ Law allows us to treat the chemical equations and the enthalpy changes in the same
way as algebraic equations.
Subtracting (2) from (3) gives the equivalent of (1) and leads to the same result for ΔH.
{C(graph.) + O2(g) } - {C(graph.) + ½ O2(g) } → {CO2(g) } - {CO(g) }
CO(g) + ½ O2(g) → CO2(g)
14
An alternative method:
C ( gr a p h ) + O 2
Δ H 2,
-1 1 0 .5
CO + ½ O2
ΔH3
- 3 9 3 .5
ΔH1
- 283
CO2
This method has a number of important applications
More important use: calculation of ΔH for reactions which would are difficult or impossible to
carry out in practice.
Ethene and ethane are by-products from the cracking of oil. The enthalpy change at 25 °C for the reaction
of graphite and hydrogen gas to form each is +52.26 kJ mol-1 and -84.68 kJ mol-1 respectively. Calculate
the ΔH for the hydrogenation of ethene to give ethane.
_________________________________________________________
From the data given
Note: these are for thermodynamic data NOT to be confused with ‘STP’ for gases, 1atm, 0
°C.
2
Therefore, we define a standard enthalpy of reaction as the enthalpy change at 1 bar and 25
°C for a reaction with all components in their standard states - ΔH°298.
The superscript ° indicates that the components are in their standard states at standard
pressure and the subscript indicates the temperature.
Thermochemical equations:
“when 1 mol of nitrogen reacts with three moles hydrogen to form 2 moles of ammonia at 25
°C and 1 bar pressure, -92.2 kJ is evolved”
Or
½ N2(g) + 1½ H2(g) → NH3(g) ΔH°298 = - 46.1 kJ mol-1
3
ΔH°f is the enthalpy change when 1 mole of a compound is formed under standard conditions
from its constituent elements in their standard states.
Values are quoted at the standard temperature of 25 °C or 298.15 K. Tables of ΔH°f,298 are
available – Atkins Appendix 1.
Br and I often react in the vapour but the standard states are the liquid and solid respectively.
Examples
In each of the three reactions, the enthalpy of the reactants is zero so that the enthalpy change
for the reaction represents the enthalpy of formation of the products.
Calculate the enthalpy change for the gas phase reaction between hydrogen and iodine vapour at 25 °C.
_________________________________________________________
However, the standard state for iodine is the solid so that ΔH°f,298 for I2(g) ≠ 0. ΔH°f,298 for HI(g) is 26.48 kJ
mol-1.
ΔH°f,298 ( I2(g)) = ΔH°f,298 ( I2(s)) + ΔH° ( I2(s)→ I2(g)) = 0 + 62.44 kJ mol-1
5
Applications of enthalpies of formation
We can use Hess’ Law to write this reaction as if it has an intermediate stage:
ΔH oa
[ ] ΔH ob
3 C2 H 2( g) ⎯ ⎯⎯→ 6 C(graph) + 3 H 2( g) ⎯ ⎯⎯→ C6 H 6( g)
6
o
or ΔH 298 (reaction) = ∑ o
νi ΔH f ,298 ( products) − ∑ νi ΔH of ,298 ( reactants)
νi represents the stoichiometric coefficient.
This method can be used to calculate ΔH for any reaction where we have ΔH°f,298 data for the
components.
ΔHo298 (reaction) = ∑ν ΔH
i
o
f ,298 ( products) − ∑ν ΔH
i
o
f ,298 ( reactants)
7
= [- 2455.2] - [ -2564.8]
= 109.6 kJ mol-1.
Note: For clarity, the units have been omitted from the intermediate stages of the calculation. All enthalpy values are in
kJ mol-1.