Thermochemistry

Put the physics to work:

Atomic and molecular change.

 Standard Heat of Formation- DHof
Enthalpy required to form ONE mole of
substance FROM ITS ELEMENTS at 25oC and 1
bar

Note: if an element exists in more than one form under standard

conditions then the most stable form is used, (eg O2 is used
not O or O3.)
By definition DHof is zero for the most stable form of any element
– because no reaction is needed to convert it.
 Thermochemistry - example

Standard Heat of reaction

DHo
r
Change in enthalpy
associated with various
physical and chemical
processes
e.g. Heat of ionization

This energy is supplied to the system

 Hess Law
If a reaction may be carried out in a series of
steps, DH for the overall reaction will equal the
sum of enthalpy changes for the individual
steps.
Hess Law

Many textbook examples…

Units kJ/mol
 Thermochemistry - Examples

• What is the standard reaction enthalpy DHr for

the following reactions ?

1. NH3 (g) + HCl (g) ¾® NH4Cl (s)

2. CH3COOC2H5 + H2O ¾® CH3COOH + C2H5OH

 DHr for: NH3(g) + HCl(g) ® NH4Cl(s)
Using Heats of formation (in kJ mol-1):

½ N2 (g)+ ½ Cl2 (g) + 2H2 (g) ® NH4Cl (s) DHof = -314.43 (1)

½ H2 (g) + ½ Cl2 (g) ® HCl (g) DHof = -92.31 (2)

½ N2 (g) + 1 ½ H2 (g) ® NH3 (g) DHof = -46.11 (3)

 Short cuts with Hess Law
• Remember - Hess Law is general and can be
applied to ANY combination of eqns. With
known enthalpies

• However, using standard tables the following

short cuts are possible:

• (see back of Atkins or online NIST Webbook)

 Short cuts with Hess Law #2

• Heats of Reaction:
• Using Heat of Formation from Tables:

N2O5 (s) ® 2 NO2 (g) + ½ O2 (g)

ΔHfº N2O5 = -43.1 kJmol-1 ΔHfº NO2= 33.18 kJmol-1 ΔHfº O2= 0
Heat Capacity

This first step is (assumed to be) a reversible, adiabatic expansion

Relationship between Cp & Cv

For an Ideal Gas

Cp - Cv = R
 Reversible Adiabatic Expansion
• Definition:

Expansion where there is no heat exchange

between system and surrounding during the
process
Heat Capacity Exp 4
Summary

For adiabatic change

PVg = constant

g = Cp /Cv
Experiment measures g
 Heat Capacity Exp 4

At constant Volume q = DU /DT = Cv

The larger Cv is, the more heat must be added

to raise the temperature by DT

How is this increase in energy stored in the

molecular system ??
 Heat Capacity Exp 4
U – the internal energy of a system is the SUM of all
modes (degrees of freedom) of energy

U = trans + rot + vib + electronic + nuclear + ……

 Degrees of freedom
• Translation of the molecule as a whole (3 DOF)

213 Trevitt 20
 Rotational DOF (NROT)
• 2 axes (NROT=2) for a linear molecule

rotation about
the molecular
axis does not
change the
nuclear
coordinates

• 3 axes (NROT=3) for a non-linear

molecule

213 Trevitt 21
 Vibrational modes of a molecule
• 3N-5 normal vib. modes for a linear molecule

• eg HCl N = 2 \ 1 normal vibrational mode

• diacetylene N = 6 \ ___ normal vibrational modes

• 3N-6 normal vib. modes for a non-linear molecule

• H2O N = 3 \ ___ normal vibrational modes

symmetric stretch asymmetric stretch bending

213 Trevitt 22
 How many modes?

An N-atom molecule has 3 N degrees of freedom

distributed as :

________________________________________________________
linear non-linear
________________________________________________________
translation 3 3
rotation 2 3
vibration 3N-5 3N-6
________________________________________________________
 Equipartition of Energy Principle
This states that on average there is:
½ RT (J mol )
-1

for each rotational & translational modes

AND
RT (J mol-1)
for each vibrational mode
This is a classical theory
 g – comparison expt and theory
Monatomic gas Ar

Therefore g = 5/2 R / 3/2 R = 5/3 = 1.66

(expt : g » 1.65)
 g – comparison expt and theory
• CO2

Therefore g = (R*15/2) / (R*13/2) = 1.15

(expt : g » 1.29)
N2

You try?
 g- comparison
• Expt. Value for CO2 is equivalent to only 1 of the 4
vibrational modes contributing (most of the heat in
the in trans and rots DOFs)

• Gamma for CO2 is temperature dependent

Quantum principles underpin this…

(see Einstein Temp etc.. For further reading)
 Summary
• Heat Capacity measurement provides insight
into how energy is stored within molecules

• Translational and rotational energy levels are

spaced close together cf RT

• But vibrational energy levels are more widely

spaced so at low/moderate temperatures they
participate weakly… but this changes at higher
temps Will develop these concepts throughout CHEM213
 Final thought
• In small molecules, e.g N2 and O2, there is very
little energy in the vibrational mode … so vibs
contribute little to the overall heat capacity at
room temperature

• But what about?