c



 
c


 

 

‡ Chemical thermodynamics allows us
to predict both the direction and the
extent of spontaneous chemical and
physical change under particular
conditions using a property called the
Gibbs free energy, O
c    
‡ Chemical reactions and physical
changes almost always either absorb
or release energy as heat

‡ Energy may be distributed throughout

a chemical system in a large number
of different ways, some of which have
significantly higher probabilities than
others
c    
O3J±

‡ Jenthalpy of the system
± Function related to the heat absorbed or
evolved by a chemical system

‡
entropy of the system

± Measure of number of ways energy is
distributed throughout a chemical system

‡ temperature in kelvin
c    
ǻO 3 ǻJ ± ǻ

‡ ǻOallows us to determine whether a
particular chemical reaction or physical
change is spontaneous
‡ If ǻO  0, the process is spontaneous
‡ If ǻO G 0, the process is
nonspontaneous
‡ If ǻO 3 0, the system is at equilibrium
 c


‡ System refers to the particular
chemical species being studied
‡ Surroundings are everything else
 c


‡ Universe refers to the system and the
surroundings
‡ Boundary defined as region across
which heat flows
c    
‡ Open systems
± Can gain or lose mass and energy
across their boundaries
‡ Closed systems
± Can absorb or release energy, but not
mass, across the boundary
‡ Isolated systems
± Can not exchange matter or energy with
their surroundings
c    
‡ SI unit of energy
± Joule
± 1 J 3 1 kg m2 s-2
± 1 kJ 3 103 J

‡ Thermodynamic equations require the

temperature in kelvin
± Temperature difference (ǻ  of 1 K is
numerically equal to ǻ of 1 °C
 c 
‡ Internal energy (u
± The sum of energies for all of the
individual particles in a sample of matter

± Interested in the CHANGE in internal

energy that accompanies a process

ǻuufinal uinitial
ǻuuproducts ureactants
 c 
‡ Internal energy
± Chemical system can exchange energy
with its surroundings in two ways
± Either absorbing heat from or emitting
heat to the surroundings
± Doing work on the surroundings of
having the surroundings do work on it
± Work may be defined simply as motion
against an opposing force
 c

‡ Internal energy
± Type of work most
often encountered in
chemical systems is
the compression or
expansion of gas
± Often called pressure-
volume or R work
±
 Rǻ
 c 
‡ First law of thermodynamic
ǻu

±  - heat
±
- work
± Energy can be transferred between
systems as either heat or work
± It can never be created or destroyed
± Law of conservation of energy
 c 
‡ State functions
± Value is dependent only on the current
state of the system
± ǻÚÚ
 Ú



± Independence from the method or
mechanism by which a change occurs is
the important feature of all state
functions
 c

‡ State functions
±  and
are NOT state functions
± The values of 
and
are
dependent on
the path
of change
 c 
‡ Heat Capacity
± Heat and temperature are not the same
thing
± Heat is a transfer of energy due to a
temperature difference
 3 ǻ
±  - heat (J
±  - heat capacity (J K-1
 c 
‡ Heat Capacity
± Heat capacity depends on the size of the
sample
± A property with a value that depends on
the size of the sample is an extensive
property
± A property with a value independent of
the size of the sample is an intensive
property
 c 
‡ Heat Capacity
± Divide heat capacity (extensive property
by the mass of the sample to form
specific heat capacity (intensive
property


Y `

± Y - specific heat capacity (J g-1 K-1

± Divide by amount instead of mass to
form molar heat capacity (J mol-1 K-1
 c 
‡ Heat Capacity
Y ǻ
If a gold ring with a mass of 550 g changes
in temperature from 250 to 280 °C, how
much heat has it absorbed?
 3 550 g Y 3 0129 J g±1 K±1 ǻ 3 3 K
 Yǻ
(0129 J g-1 K-1 × (550 g × (3 K
3 21 J
 c

‡ The determination of heat
± Calorimeter
‡ Apparatus designed to
minimise heat loss
between the system
and surroundings
± Bomb calorimeter
‡ System remains at
constant volume
‡ ǻu 3 

‡ ǻu 3 
 c

‡ Enthalpy: the heat of reaction at
constant pressure
ǻu

ǻuR Rǻ
± Inconvenient as need
to know ǻ
± Define a new thermodynamic
property called enthalpy (J
ǻJR
 c 
‡ Enthalpy: the heat of reaction at
constant pressure
JuR
ǻJǻuRǻ

± Substituting ǻuR Rǻ 


ǻJR Rǻ Rǻ
ǻJR
 c 
‡ Enthalpy: the heat of reaction at
constant pressure
± The heat of reaction at constant pressure
is equal to ǻJ
± The heat of reaction at constant volume
is equal to ǻu
± ǻJ G 0 reaction is endothermic
± ǻJ  0 reaction is exothermic
± The difference between ǻJand ǻu for a
reaction is Rǻ
 c 
‡ Standard enthalpy change
± Standard states
‡ Pressure of 105 Pa
‡ Concentration of 1 M

± Standard enthalpy of reaction

‡ Value of ǻJfor a reaction occurring under
standard conditions (ǻJ (kJ or kJ mol±1
‡ Involves the actual numbers of MOLES
specified by the coefficients of the equation
 c 
‡ Standard enthalpy change
N2(g + 3H2(g ü 2NH3(g ǻJ 3 9238 kJ
± The above is a thermochemical equation
± Always gives the physical states of the
reactants and products
± Its value of ǻJ is only true when
coefficients of reactants and products
are numerically equal to the number of
moles of the corresponding substances
 c 
‡ Hess¶s law
± Method for combining known
thermochemical equations in a way that
allows us to calculate ǻJ for another
reaction
± One step
C(s + O2(g ü CO2(g ǻJ 3 ±3935 kJ
± Two step
Step 1: C(s + ½O2(g ü CO(g ǻJ 3 ± 1105 kJ
Step 2: CO(g + ½O2(g ü CO2(gǻJ 3 ± 2830 kJ
 c 
‡ Hess¶s law
2Fe(s + 3CO2(g ü Fe2O3(s + 3CO(g ǻJÎ 3 +26 kJ
3CO(g + O2(g ü 3CO2(g ǻJÎ 3 -8490 kJ
2Fe(s + O2(g ü Fe2O3(s ǻJÎ 3 -8223 kJ
± Rules for manipulating thermochemical
equations:
1 When an equation is reversed the sign of
ǻJÎ must also be reversed
Fe2O3(s + 3CO(g ü 2Fe(s + 3CO2(g ǻJÎ 3 -26 kJ
2Fe(s + 3CO2(g ü Fe2O3(s + 3CO(g ǻJÎ 3 +26 kJ
 c 
‡ Hess¶s law
2Fe(s + 3CO2(g ü Fe2O3(s + 3CO(g ǻJÎ 3 +26 kJ
3CO(g + O2(g ü 3CO2(g ǻJÎ 3 -8490 kJ
2Fe(s + O2(g ü Fe2O3(s ǻJÎ 3 -8223 kJ
± Rules for manipulating thermochemical
equations:
2 Formulae can be cancelled from both
sides of an equation only if the substance
is an identical physical state
 c 
‡ Hess¶s law
2Fe(s + 3CO2(g ü Fe2O3(s + 3CO(g ǻJÎ 3 +26 kJ
3CO(g + O2(g ü 3CO2(g ǻJÎ 3 -8490 kJ
2Fe(s + O2(g ü Fe2O3(s ǻJÎ 3 -8223 kJ
± Rules for manipulating thermochemical
equations:
3 If all the coefficients of an equation are
multiplied or divided by the same factor,
the value of ǻJÎ must likewise be
multiplied or divided by that factor
CO(g + ½O2(g ü CO2(g ǻJÎ 3 -2830 kJ
3CO(g + 3/2O2(g ü 3CO2(g ǻJÎ 3 -8490 kJ
 c 
‡ Standard enthalpy of combustion
a ǻcJÎ
± Enthalpy change at temperature when
1 mole of a substance is completely
burned in pure oxygen gas
± Combustion reactions are always
exothermic
a ǻcJÎ always negative
± kJ mol±1
 c 
‡ Standard enthalpy of formation (ǻfJÎ
± Enthalpy change when 1 mole of
substance is formed at 105 Pa and the
specified temperature from its elements in
their standard states
± An element is in its standard state when it
is in its most stable form and physical state
at 105 Pa and the specified temperature
a ǻfJÎ for the elements in their standard
states are 0
 c

‡ Standard enthalpy of formation
A + B ü YC + àD
 u ` Y  
u  à   u     u     u

 
± Hess¶s law equation
± Use either enthalpies of combustion or enthalpies of
formation
 c 
‡ Bond enthalpies
± A bond enthalpy is the enthalpy change on
breaking 1 mole of a particular chemical
bond to give electrically neutral fragments
± Atomisation enthalpy (ǻatJ is the enthalpy
change that occurs on rupturing all the
chemical bonds in 1 mole of gaseous
molecules
 c

‡ Bond enthalpies and Hess¶s law
 c

‡ Lattice enthalpies and Hess¶s law
± Lattice enthalpies for ionic solids calculable
using Hess¶s law and thermodynamic data
 c

‡ Entropy and probability

No energy is transferred

Two units of energy

One unit of energy is are transferred
transferred

Three units of energy

are transferred

± Spontaneous processes tend to proceed from states of

low probability to states of higher probability
± Spontaneous processes tend to disperse energy
 c 
‡ Entropy and entropy change
± Entropy (
 describes the number of
equivalent ways that energy can be
distributed in the system
± Entropy is a state function
ǻ

Rà Y

Y

± Any event that is accompanied by an

increase in the entropy of the system has
a tendency to occur spontaneously
 c

‡ Entropy and entropy change
 c

‡ Factors that affect entropy
± Often possible to predict whether ǻ
is positive
or negative for a particular change
± Volume
‡ For gases the entropy increases with increasing
volume
 c

‡ Factors that affect entropy
± Temperature
‡ The higher the temperature the higher the entropy
 c

‡ Factors that affect entropy
± Physical state
‡ One of the major factors that affects the entropy of a
system is its physical state
 c

‡ Factors that affect entropy
± Number of particles
‡ When all other things are equal, reactions that
increase the number of particles in the system tend
to have a positive entropy change
 c 
‡ The second law of thermodynamics
± Whenever a spontaneous event takes
place in our universe, the total entropy of
the universe increases (ǻ
totalG0
a ǻ
total 3 ǻ
system + ǻ
surroundings
   à
 
ÿ
  à
 

± qsurroundings 3 -qsystem
± qsystem 3 ǻJ
ÿ  

ÿ 
 

 c 
‡ Absolute entropy and the third law of
thermodynamics
± At absolute zero, the entropy of a perfectly
ordered pure crystalline substance is 0

3 0 at 3 0 K

± Point at which entropy equal to 0 is known,

hence by experimental measurement and
calculation entropy can be determined for
a substance at temperatures above 0 K
 c 
‡ Absolute entropy and the third law of
thermodynamics
± Standard entropy (
Î ± entropy of
1 mole of a substance determined under
standard conditions at temperature
of 298 K
± Standard entropy of reaction
aA + bB ü cC + dD
 u ` Y  
u    u     u     u

 
 c

 

  
‡ The sign of ǻO

ǻOÎ ǻJÎ ǻ
Î

ǻO  0 reaction
spontaneous
c    
 
 
‡ Standard Gibbs free energy change
± When ǻO is determined at 105 Pa, this is
called the standard free energy change
(ǻOÎ
± There are several ways for determining
ǻOÎ for a reaction
‡ ǻOÎ ǻJÎ ǻ
Î
‡ aA + bB ü cC + dD
 u ` Y  
u    u     u     u

 
 c

 

  
‡ Gibbs free energy and work

± Maximum conversion of chemical energy to work

occurs if a reaction is carried out under conditions
that are said to be thermodynamically reversible
c    
 
 
‡ Gibbs free energy and work
± The maximum amount of energy produced
by a reaction that can be
THEORETICALLY harnessed as work is
equal to ǻO
a ǻO0 the system is in a state of
equilibrium
Oproducts 3 Oreactants
± When ǻO0 the amount of work
available is 0
c    
 
 
‡ Gibbs free energy and work
± For phase changes such as
H2O(l ü H2O(s
equilibrium can be established only at
one particular temperature at
atmospheric pressure
ǻO0 3 ǻJ ǻ

ǻJ ǻ

ÿJ ÿ
ÿ

ÿ
 c

 

  

‡ Gibbs free
energy and
work