Thermochemistry
Thermochemistry:
The study of heat produced from or required by chemical reactions
2.7 Standard enthalpy changes
The standard state of a substance at a specified temperature is its
pure form at 1 bar.
∆vapHΘ
H2O(ℓ) → H2O(g)
∆vapHΘ (373K) = 40.66 kJ/mol
T = 25℃ (298.15K) conventional Temp.
Enthalpies of Physical Changes 1
standard enthalpy of transition, ∆trsHo, the standard
enthalpy change that accompanies a change of physical state.
standard enthalpy of vaporization, ∆vapHo, the standard
enthalpy change accompanying the conversion of a solid or
liquid to a vapour.
standard enthalpy of fusion, ∆fusHo, the standard enthalpy
change accompanying the conversion of a solid to a liquid.
addition of enthalpy changes, as in ∆subHo = ∆fusHo + ∆vapHo
(at the same temperature).
Enthalpies of Physical Changes 2
(a) Enthalpies of physical change
H2O(s) → H2O(ℓ) ∆fusHΘ(273K) = 6.01kJ/mol
Θ
H2O(s) → H2O(g) ∆subH
Θ
H2O(ℓ) → H2O(g) ∆vapH
Θ Θ
H2O(s) → H2O(g) ∆fusH + ∆vapH
overall, ∆subHΘ = ∆fusHΘ + ∆vapHΘ
Enthalpies of Transition
Enthalpies of Changes
Enthalpies of Chemical Changes 1
(b) Enthalpies of chemical change
Standard reaction enthalpy
CH4(g) + 2O2(g) → CO2(g) + 2H2O(ℓ)
Θ
∆rH = − 890kJ/mol
2A + B → 3C + D
Θ Θ Θ Θ Θ
∆rH = {3 H m (C) + H m(D)} − {2 H m(A) + H m(B) }
Θ
Hm (J) = standard molar enthalpy of species J
Θ Θ Θ
∆rH = ∑ νHm − ∑ νHm
product reactant
Hess’s Law
(c) Hess’s law
The standard enthalpy of an overall reaction is the sum of the
standard enthalpies of the individual reactions into which a
reaction may be divided.
Example 2.5
① hydrogenation of propene
CH2=CHCH3(g) + H2(g)→ CH3CH2CH3(g) −124 kJ/mol
② Propane Combustion
CH3CH2CH3(g) + 5O2(g) → 3CO2 (g) + 4H2O (ℓ) −2220 kJ/mol
Calculate the standard enthalpy of combustion of propene
C3H6(g) + 9/2 O2(g) → 3CO2(g) + 3H2O(ℓ)
∆rHΘ (kJ/mol)
C3H6(g) + H2(g) → C3H8(g) −124
C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(ℓ) −2220
H2O(ℓ) → H2(g) + ½ O2(g) +286
C3H6(g) + 9/2 O2(g) → 3CO2(g) + 3H2O(ℓ) −2058
2.8 Standard H of Formation
2.8 Standard enthalpies of formation
standard enthalpy of formation,∆fHo, the standard
reaction enthalpy for the formation of the compound from
its elements in their reference states.
reference state, the most stable state of an element at the
specified temperature and 1 bar.
ex. Standard enthalpy of formation of liquid benzene.
6C (s, graphite) + 3H2(g) → C6H6 (ℓ)
∆fH (H6C6,ℓ) = 49.0 KJ/mol
Reaction Enthalpy
* Standard enthalpy of formation in its reference state: ZERO
Θ
N2 (g) → N2 (g) , ∆ f N2 (N2 , g) = 0
∆ f H Θ ( H + , aq ) = 0
* Reaction enthalpy in terms of
enthalpies of formation
∆ r H Θ = ∑Pr oductsν∆ f H Θ
− ∑Re ac tan tsν∆ f H Θ
Example A
Example B
Molecular Modeling
(b) Group contribution: molecular modeling
Θ
∆Hf (C6H14,ℓ) = ? C(H)3C ; two
C(H)2C2 ; four
∆HfΘ(C6H14,g)
=2(−42.17 kJ/mol)+4(− 20.7 kJ/mol)
= − 167.1 kJ/mol
C6H14 standard enthalpy of vaporization =
33.1 kJ/mol
∆HfΘ(C6H14,ℓ)
= (− 167.1 kJ/mol) – (33.1 kJ/mol)
= − 200.2 kJ/mol
cf) Measured value: − 198.7 kJ/mol
2.9 Temperature Dependence
dH = CP dT (at constant pressure)
T2
H (T2 ) = H (T1 ) + ∫ C p dT
T1
* Standard reaction enthalpy:
Kirchhoff’s law
T2
∆ r H o (T2 ) = ∆ r H o (T1 ) + ∫ ∆ r C po dT
T1
∆ r C P = ∑Pr oductsν∆ f C P ,m
Θ Θ
− ∑Re ac tan tsν∆ f C P ,m
Θ
State and Path Functions
* State functions: U, H, …….
* Path functions: w, q, ……
* Path 1: Adiabatic expansion
q=0
* Path 2: non-adiabatic expansion
q` enters the system
q` ≠ 0
2.10 Exact and inexact differentials
¨ exact differential, an infinitesimal quantity which, when
integrated, gives a result that is independent of the path
between the initial and final states.
f
∆U = ∫ dU = U f − U i
i
¨ inexact differential, an infinitesimal quantity that, when
integrated, gives a result that depends on the path between
the initial and fin al states.
f
q=∫ dq
i , path
Example 2.7
Consider a perfect gas inside a cylinder fitted with a piston. Let the initial state be
T, Vi and the final state be T, Vf. The change of state can be brought about in
many ways, of which the two simplest are the following: Path 1, in which there is
free expansion against zero external pressure; Path 2, in which there is reversible,
isothermal expansion. Calculate w, q, and ∆U for each process.
