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INTRODUCTION TO CHEMISTRY
II
U q w
Recap
1. State function: value depends only on current state of the system and is
independent of how that state has been prepared (e.g U, H)
w Pext V 0
U UB UA qV
Recap
• Processes at Constant Pressure
• Irreversible Expansion: where external pressure is constant throughout the
expansion
w PV Pext V
Vf
𝑤𝑟𝑒𝑣 = −nRT ln
Vi
• Wrev > Wirrev
Thermochemistry
• Definition
The study of heat produced or absorbed by chemical reaction(s).
• 𝑈𝐵 − 𝑈𝐴 = 𝑞𝑝 − 𝑃∆𝑉
U B U A q p PVB V A
q P U B U A PVB V A
q P U B PV B U A PV A
q P U B PV B U A PV A
Thermochemistry
• The quantity (U +PV) is called heat content (also called enthalpy, H)
q P U B PV B U A PV A
q P H B H A H
◦ e.g. heat absorbed in the system from the surroundings is equal to the
increase in heat content of the system
Thermochemistry
Heat of Reactions
• The study of thermochemistry of reactions is normally divided into
different types of reactions for convenience.
θ °
Standard state of the enthalpy (298 K, 1 bar) is denoted as ∆𝐻298𝐾 𝑜𝑟 ∆𝐻298𝐾
C( graphite) 2 H 2 ( g )
CH 4 ( g )
e.g. Standard enthalpy of fusion fus H
• standard enthalpy change arising
from conversion of solid to liquid
sub H vap H
Thermochemistry
• Enthalpy is a state function
H 0f , 298 K
• NOTE: The standard enthalpy of formation for the most stable form of any
element is 0 kJ mol-1
• since O2 is the elemental state of oxygen
H 0f O2 ( g ) 0
Thermochemistry
C2 H2 (g)
2C (graphite) H2 (g) H 226.7 kJ mol 1
H2O2 (l)
H2 (g) O2 (g) H + 187.8 kJ mol 1
Generalisation
Hrxn
0
Hf0 (products) H 0
f (reac tan ts)
Example
Given the following thermodynamic data,
Hrxn
0
Hf0 (products) H 0
f (reac tan ts)
Example
CH4 (g) + 3Cl2 (g) CHCl3 (l) + 3HCl (g)
Hrxn
0
Hf0 (products) H 0
f (reac tan ts)
ΔH rxn
0
= Δf H ° (CHCl3 + 3 Δf H ° (HCl - Δf H ° (CH 4 + 3 Δf H ° (Cl2
= [(-135.1 kJ mol-1 ) (3 x - 92.31 kJ mol-1 )] - [(-74.81 kJ mol-1 ) + (3 x 0 kJ mol-1 )]
= - 337.43 kJ mol-1
Thermochemistry
Enthalpy of Combustion ΔcH°
• Standard enthalpy change when a substance (typically an organic
compound) undergoes complete combustion with oxygen under standard
conditions
U UB UA qV
Re: H = U + PV
For gases, treated as perfect, pV = nRT
H = U + PV
H = U + nRT
ΔH = ΔU + nRT