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CHEM 1067

INTRODUCTION TO CHEMISTRY
II

Dr. Nigel John


Office: Rm 304, C1 BLDG
Email: Nigel.John@sta.uwi.edu
Recap
• First Law of Thermodynamics: The internal energy of an isolated system is
constant

In an isolated system, q = 0 and w = 0 therefore ΔU = 0

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)

Is work a State Function??


NO, it is path dependent

2. Extensive property: dependent on size / amount of substance in the


system e.g. U, V, mass

3. Intensive property: physical property independent of size of the sample


e.g. temperature, melting point, boiling point, molecular weight, and
density
Recap
• Processes at Constant Volume
ΔV= 0

w   Pext V  0

U  UB  UA  qV
Recap
• Processes at Constant Pressure
• Irreversible Expansion: where external pressure is constant throughout the
expansion
w  PV  Pext V

• Isothermal Reversible Expansion: where Pext = P at each stage of the expansion

Vf
𝑤𝑟𝑒𝑣 = −nRT ln
Vi
• Wrev > Wirrev
Thermochemistry
• Definition
The study of heat produced or absorbed by chemical reaction(s).

- In the laboratory most reactions are carried out at constant pressure,


therefore the heat changes at constant pressure (enthalpy) is more
important than heat changes at constant volume (internal energy).

Chemistry3, second edition, Chapter 13, Energy and Thermochemistry


Thermochemistry
• From 1st law of Thermodynamics, ∆𝑼 = 𝒒 + 𝒘
U  U B  U A  q  w

• 𝑈𝐵 − 𝑈𝐴 = 𝑞𝑝 − 𝑃∆𝑉
U B  U A  q p  PVB  V A 

• Where heat at constant pressure is denoted qp


• Rearrange the equation

q P  U B  U A  PVB  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

For constant pressure process, heat transferred is equal to the change


in heat content of the system, 𝑞𝑝 = ∆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.

E.g. Combustion, hydrogenation, formation reactions


Thermochemistry

• Standard State of Reactions


• ∆H and ∆U are state properties therefore their values depend on the
conditions of their initial and final state.

• For comparison of enthalpies of different reactions, standard conditions


must be set for the initial and final state. This is called standard state
conditions.

• Standard state of reactions provides a constant baseline from which


other measurements can be made
Thermochemistry
• Standard state of a substance at a specified temperature (usually 298 K) is its pure
form at 1 bar pressure (not 1 atm)
i.e. Standard state = 298 K, 1 bar

θ °
Standard state of the enthalpy (298 K, 1 bar) is denoted as ∆𝐻298𝐾 𝑜𝑟 ∆𝐻298𝐾

• Each substance will have its own standard state

C( graphite)  2 H 2 ( g ) 
CH 4 ( g )

- All elements in their standard states have arbitrarily zero enthalpy


Thermochemistry
Enthalpies of physical change
Standard enthalpy of transition,  trs H 
• standard enthalpy change arising from
a change in physical state


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

For processes occurring at


the same temperature
Thermochemistry

• The standard enthalpy changes of a


forward process and its reverse must
differ only in sign

E.g. ΔcondH° (H2O, g) = - 44 kJ mol-1


ΔvapH° (H2O, l) = + 44 kJ mol-1
Thermochemistry
Heat of Formation (or Enthalpy of Formation)
• Heat content when one mole of compound in its standard state is formed from its
elements in their standard states.

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

C 2 H 2 ( g ) H 0f  226.7 kJ mol 1 H 2 O2 (l ) H 0f   187.8 kJ mol 1

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

H   ve unstable compound with respect to elements


H   ve stable compound with respect to elements
Thermochemistry
• Enthalpy of Reaction in terms of Hf0

• the standard enthalpy change Hrxn


0
of a process is the difference
between the products in their standard states and the reactants in their
standard states, all at a specified temperature

Hrxn
0
   Hf0 (products)    H 0
f (reac tan ts)
Example
Given the following thermodynamic data,

Compound ΔfHɵ (kJ mol-1)


CH4 (g) -74.81
Cl2 (g) 0
CHCl3 (l) -135.1
HCl (g) -92.31

Calculate the standard reaction enthalpy for the halogenation


of CH4 is at 25°C
CH4 (g) + 3Cl2 (g) CHCl3 (l) + 3HCl (g)

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

• The standard enthalpy of combustion, ΔcH° is the standard reaction


enthalpy for the complete oxidation of an organic compound to CO2 (g)
and H2O (l) if the compound contains C, H, O, and to N2 (g) if N is also
present.

Eg. Combustion of glucose

ΔcH° = - 2808 kJ mol-1


Thermochemistry

• ΔcH° measured by using a bomb calorimeter

U  UB  UA  qV
Re: H = U + PV
For gases, treated as perfect, pV = nRT

H = U + PV
H = U + nRT
ΔH = ΔU + nRT

→ Enthalpy combustion, ΔcH:


ΔcH = ΔcU + ΔngRT