Spontaneity, Entropy & Free Energy
First Law of Thermodynamics
Basically the law of conservation of energy
energy can be neither created nor destroyed
i.e., the energy of the universe is constant
the total energy is constant
energy can be interchanged
e.g. potential energy (stored in chemical bonds) can be
converted to thermal energy in a chemical reaction
CH4 + O2 > CO2 + H2O + energy
Doesnt tell us why a reaction proceeds in a
particular direction
Spontaneity, Entropy & Free Energy
Spontaneous Processes and Entropy
Spontaneous processes occurs without
outside intervention
Spontaneous processes can be fast or slow
Spontaneity, Entropy & Free Energy
Thermodynamics
lets us predict whether a process will occur
tells us the direction a reaction will go
only considers the initial and final states
does not require knowledge of the pathway
taken for a reaction
Spontaneity, Entropy & Free Energy
Kinetics
depends on the pathway taken
tells us the speed of the process
depends on
activation energy
temperature
concentration
catalysts
Spontaneity, Entropy & Free Energy
Spontaneous Processes
a ball rolls downhill, but the ball never
spontaneously rolls uphill
steel rusts, but the rust never spontaneously
forms iron and oxygen
a gas fills its container, but a gas will never
spontaneously collect in one corner of the
container.
Water spontaneously freezes at temperatures
below 0o C
Spontaneity, Entropy & Free Energy
What thermodynamic principle explains why
these processes occur in one direction?
The driving force for a spontaneous reaction
is an increase in the entropy of the universe
Spontaneity, Entropy & Free Energy
Entropy
Symbol: S
A measure of randomness or disorder
The natural progression is from order to disorder
It is natural for disorder to increase
Entropy is a thermodynamic function
Describes the number of arrangements that are
available to a system in a given state
Spontaneity, Entropy & Free Energy
Entropy
The greater the number of possible
arrangements, the greater the entropy of a
system, i.e., there is a large positional
probability.
The positional probability or the entropy
increases as a solid changes from a liquid or
as a liquid changes to a gas
Spontaneity, Entropy & Free Energy
Ssolid < Sliquid < Sgas
Choose the substance with the higher
positional entropy:
CO2(s) or CO2(g)?
N2(g) at 1 atm and 25oC or N2(g) at .010 atm and
25oC?
Spontaneity, Entropy & Free Energy
Predict the sign of the entropy change
solid sugar is added to water
iodine vapor condenses onto a cold surface
forming crystals
Spontaneity, Entropy & Free Energy
Second Law of Thermodynamics
The entropy of the universe is increasing
The universe is made up of the system and
the surroundings
Suniverse = Ssystem + Ssurroundings
Spontaneity, Entropy & Free Energy
A process is spontaneous if the Suniverse is
positive
If the Suniverse is zero, there is no tendency
for the reaction to occur
Spontaneity, Entropy & Free Energy
The effect of temperature on spontaneity
H2O(l) > H2O(g)
water is the system, everything else is the
surroundings
Ssystem increases, i.e. Ssystem is positive, because
there are more positions for the water molecules
in the gas state than in the liquid state
Spontaneity, Entropy & Free Energy
What happens to the surrounding?
Heat leaves the surroundings, entering the system
to cause the liquid molecules to vaporize
When heat leaves the surroundings, the motion of
the molecules of the surroundings decrease, which
results in a decrease in the entropy of the
surroundings
Ssurroundings is negative
Spontaneity, Entropy & Free Energy
Sign of S depends on the heat flow
Exothermic Rxn: Ssurr >0
Endothermic Rxn: Ssurr< 0
Magnitude of S is determined by the temperature
Ssurr =  H
Spontaneity, Entropy & Free Energy
Signs of Entropy Changes
Ssys Ssurr Suniv Spontaneous?
+
+

+
+
Spontaneity, Entropy & Free Energy
Free Energy
aka Gibbs Free Energy
G
another thermodynamic function
related to spontaneity
G = H  TS
for a process that occurs at constant
temperature (i.e. for the system):
G = H  TS
Spontaneity, Entropy & Free Energy
How does the free energy related to spontaneity?
G = H  TS
G =  H + S
(remember,  H = Ssurr )
T
T
T
G = Ssurr + Ssys (remember, Ssurr + Ssys = Suniv)
T
G = Suniv
T
Spontaneity, Entropy & Free Energy
Suniv > 0 for a spontaneous reaction
G < 0 for a spontaneous reaction
G > 0 for a nonspontaneous reaction
Useful to look at G because many chemical
reactions take place under constant pressure
and temperature
Spontaneity, Entropy & Free Energy
H2O(s) > H2O(l)
Ho = 6.03 x 103J/mole
So = 22.1 J/K.mole
Calculate G, Ssurr, and Suniv at 10oC, 0oC,
and 10oC
Spontaneity, Entropy & Free Energy
For the melting of ice
Ssys and Ssurr oppose each other
spontaneity will depend on temperature
So is positive because of the increase in
positional entropy when the ice melts
Ssurr is negative because the reaction is
endothermic
Spontaneity, Entropy & Free Energy
At what temperatures is Br2(l) > Br2(g)
spontaneous?
What is the normal boiling point of Br 2?
HokJ/mol So = 93.0 J/K.mol
Spontaneity, Entropy & Free Energy
Entropy Changes in Chemical Reactions
Just like physical changes, entropy changes
in the surroundings are determined by heat
flow
Entropy changes in the system are
determined by positional entropy (the
change in the number of possible
arrangements)
Spontaneity, Entropy & Free Energy
N2 (g) + 3 H2(g) > 2 NH3 (g)
The entropy of the this system decreases
because
four reactant molecules form two product
molecules
there are less independent units in the system
less positional disorder, i.e. fewer possible
configurations
Spontaneity, Entropy & Free Energy
When a reaction involves gaseous
molecules:
the change in positional entropy is
determined by the relative numbers of
molecules of gaseous reactants and
products
I.e., if you have more product molecules
than reactant molecules, S will be positive
Spontaneity, Entropy & Free Energy
In thermodynamics, the change in a
function is usually what is important
usually we cant assign an absolute value to
a function like enthalpy or free energy
we can usually determine the change in
enthalpy and free energy
Spontaneity, Entropy & Free Energy
We can assign absolute entropy values,
i.e., we can find S
A perfect crystal at 0 K, while
unattainable, represents a standard
all molecular motion stops
all particles are in their place
the entropy of a perfect crystal at 0 K
is zero = third law of thermodynamics
Spontaneity, Entropy & Free Energy
Increase the temperature of our
perfect crystal
molecular motion increases
disorder increases
entropy varies with temperature
See thermodynamic tables for So values (at
298 K and 1 atm)
Spontaneity, Entropy & Free Energy
Entropy is a state function
entropy does not depend on the pathway
taken
Srxn = nSoproducts  nSoreactant
Spontaneity, Entropy & Free Energy
Calculate So at 25oC for
2NiS(s) + 3 O2(g) > 2 SO2(g) + 2 NiO(s)
Substance
SO2
So(J/K.mol)
248
NiO
O2
38
205
NiS
53
Spontaneity, Entropy & Free Energy
Calculate So for
Al2O3(s) + 3 H2(g) > 2 Al(s) + 3 H2O(g)
Substance
Al2O3
So (J/K.mol)
51
H2
131
Al
H2O
28
189
Spontaneity, Entropy & Free Energy
What did you expect the So to be?
Why is it large and positive?
H2O is nonlinear and triatomic
H2O has many rotational and vibrational motions
H2 is linear and diatomic
H2 has less rotational and vibrational motions
The more complex the molecule, the
higher the So
Spontaneity, Entropy & Free Energy
Free Energy and Chemical Reactions
Standard Free Energy Change
Go
the change in the free energy that occurs if the
reactants in their standard states are changed to
products in their standard states
cant be measured directly
calculate from other values
allows us to predict the tendency for a reaction to go
Spontaneity, Entropy & Free Energy
How do we calculate Go?
Go = Ho  TSo (for a reaction carried out
at constant temperature)
Use Hess Law
Use Gof (standard free energy of
formation)
Go = nGof (products)  nGof (reactants)
Spontaneity, Entropy & Free Energy
Calculate Go for the reaction at 25oC
2SO2(g) + O2(g) > 2 SO3(g)
Substance
Hof(kJ/mol)
So (J/K.mol)
SO2(g)
297
248
SO3
396
257
O2
205
Spontaneity, Entropy & Free Energy
Calculate Go for the reaction Cdia > Cgr
using the following data:
Cdia + O2 > CO2(g)
Go = 397 kJ
Cgr + O2 > CO2(g)
Go = 394 kJ
Spontaneity, Entropy & Free Energy
Calculate Go for the reaction
2CH3OH + 3 O2> 2 CO2 + 4 H2O
Substance
Gof(kJ/mol)
CH3OH
163
O2
CO2
394
H2O
229
Spontaneity, Entropy & Free Energy
The dependence of free energy on pressure
How does pressure affect enthalpy and entropy?
Pressure does not affect enthalpy
Pressure does affect entropy because pressure
depends on the volume
1 mole of a gas at 10.0 L has more positions available
than 1 mole of a gas at 1.0 L
Slarge volume > Ssmall volume
Slow pressure > Shigh pressure
Spontaneity, Entropy & Free Energy
Given that G = Go + RTln(P)
where G is the free energy at some P (not necessarily 1 atm)
where Go is the free energy at 1 atm
Ex: N2(g) + 3 H2(g) > 2 NH3(g)
(lots of equationslots of equations)
G = Go + RT ln Q
Q is the reaction quotient (from the law of mass action)
T is the temperature in K
R is the gas constant, 8.3145 J/mol.K
Spontaneity, Entropy & Free Energy
Calculate G at 25o C for the reaction
CO(g) + 2 H2(g) > CH3OH where carbon
monoxide is 5.0 atm and hydrogen gas
at 3.0 atm are converted to liquid
methanol.
What does the answer tell us about this
reaction under these conditions?
Spontaneity, Entropy & Free Energy
Free Energy and Equilibrium
Equilibrium occurs at the lowest value of free
energy available to the reaction system, i.e.,
when G = 0
At equilibrium, G = 0, Q = Keq so
G = 0 = Go + RT ln Keq
Go =  RT ln Keq
Use this equation to find Keq given Go, or to
find Go given Keq
Spontaneity, Entropy & Free Energy
Relationship between Go and Keq
Go
Keq
=0
1
<0
>1
>0
<1
Spontaneity, Entropy & Free Energy
For N2 + 3 H2 > 2 NH3, Go =  33.3 kJ per mole of
N2 consumed at 25oC. Predict the direction in which
the reaction will shift to reach equilibrium
a. PNH3 = 1.00 atm, PN2 = 1.47 atm, PH2 = 1.00 x 102 atm
b. PNH3 = 1.00 atm, PN2 = 1.00 atm, PH2 = 1.00 atm
Spontaneity, Entropy & Free Energy
4Fe + 3 O2 <====> 2Fe2O3 Calculate the
equilibrium constant using the following
information:
Substance
Hof (kJ/mol)
So(J/K.mol)
Fe2O3
826
90
Fe
O2
0
0
27
205
Spontaneity, Entropy & Free Energy
Keq and temperature
We used Le Chateliers Principle to determine
how Keq would change when temperature
changes
Use G to determine the new Keq at a new
temperature
Go = RT ln K = Ho  TSo
ln K =  Ho . 1 + So