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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 10-2 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