Key Concepts of Chapter

Identifying Spontaneous Processes.

Identifying reversible and irreversible processes.
Entropy and its relation to randomness.
Second Law of Thermodynamics.
Predicting Entropy Changes of a Process.
Third Law of Thermodynamics.
Relate temperature change to entropy change.
Calculating change in standard entropy.



Free energy in terms of enthalpy and entropy.
Relating free energy change to spontaneity.
Calculating standard free energy change.
Relationship between free energy and work.
Calculating free energy under nonstandard conditions.






The First law of Thermodynamics
- energy cannot be created or
destroyed only converted from one
form to another.
Chemical thermodynamics is the
study of energy relationships in
chemistry.
From Chapter 5
Enthalpy
heat transfer between the system and
its surroundings under const. press.
Enthalpy is a guide to whether a
reaction is likely to proceed.
It is not the only factor that
determines whether a reaction
proceeds.
Occur without outside intervention
Have a definite direction.
The reverse process is not spontaneous.
Temperature has an impact on
spontaneity.
Ex: Ice melting or forming
Ex: Hot metal cooling at room temp.
KI (aq) + Pb(NO
3
)
2
(aq) PbI
2
(s) + KNO
3
(aq)
When mixed Precipitate forms spontaneously.
*It does not reverse itself and become two clear solutions.
Reversible:
System changes state and can be restored by
reversing original process.
Ex: Water (s) Water (l)
Irreversible:
System changes state and must take a different
path to restore to original state.
Ex: CH
4
+ O
2
CO
2
+ H
2
O

Whenever a system is in equilibrium, the

reaction can go reversibly to reactants or
products (water water vapor at 100 C).

In a Spontaneous process, the path between
reactants and products is irreversible. (Reverse
of spontaneous process is not spontaneous).

*Scrambled eggs dont unscramble*
- The entropy of the universe
always increases in a spontaneous
process and remains unchanged in
an equilibrium process.

But ma, its not my fault the universe wants my room like this!>
A measure of randomness or disorder
S = entropy in J/K mole
Increasing disorder or increasing
randomness is increasing entropy.
Three types of movement can lead to
an increase in randomness.
Entropy is a state function
Change in entropy of a system
AS= S
final
- S
initial

Depends only on initial and final states, and
not the pathway.
-AS indicates a more ordered state
(think: < disorder or - disorder)
Positive (+) AS = less ordered state
(think: > disorder or + disorder)
Entropy, S
- a measure of disorder
S
solid
S
liquid
S
gas
< <
If entropy always increases, how can we account for the fact
that water spontaneously freezes when placed in the freezer?
Movement of compressor
+
Evaporation and condensation of refrigerant
+
Warming of air around container
Net increase in the entropy of the universe
On the AP exam, you will likely be asked to:
1) predict whether a process leads to an increase in entropy or a
decrease in entropy.
2) Determine if S is + or
3) Determine substances or reactions that have the highest
entropy.
Processes that lead to an Increase in Entropy
1) When a solid melts.
2) When a solid dissolves in solution.
3) When a solid or liquid becomes a gas.
4) When the temperature of a substance increases.
5) When a gaseous reaction produces more molecules.
6) If no net change in # of gas molecules, can be + or -, but small.

Predict whether the entropy change is
greater than or less than zero for each
of the following processes:
a) Freezing liquid bromine
b)Evaporating a beaker of
ethanol at room temperature
c) Dissolving sucrose in water
d)Cooling N
2
from 80C to 20C
AS<0
AS>0
AS>0
AS<0
Predict whether the entropy
change of the system in each of the
following reactions is positive or
negative:
1.) Ag
+
(aq)
+ Cl
-
(aq)
AgCl
(s)
2.) NH
4
Cl
(s)
NH
3(g)
+ HCl
(g)
3.) H
2(g)
+ Br
2(g)
2HBr
(g)

1)AS
2)AS+
3)AS?


According to the 2
nd
law of thermodynamics; the
entropy of the universe always increases.
?
What if the entire senior class assembles in the auditorium?
Arent we decreasing disorder, and therefore decreasing entropy?
If so, how can the second law of thermodynamics be true?



If we consider the senior class as the system, the
S of the system would indeed decrease.

S of the system is

In order for the students to gather, they would:
1) Metabolize food (entropy increase of surroundings)
2) Generate heat (entropy increase of surroundings)


The magnitude of the entropy increase of the surroundings will
always be greater than the entropy decrease of the system.



Theoretical values

AS
universe
= AS
system
+

AS
surroundings

AS
universe
= (-10) + (+20)

AS
universe
= +10

+ means entropy increases


The same can be considered in a chemical process.
When a piece of metal rusts:




4Fe(s) + O
2
(g) 2Fe
2
O
3
(s)
The entropy of the solid slowly decreases.
Although this is a slow process, it is exothermic,
and heat is released into the surroundings causing
an overall increase in entropy of the universe!
The Second Law of Thermodynamics
AS
universe
= AS
system
+

AS
surroundings


AS
universe
> 0 for spontaneous rxn

AS
universe
= 0 at equilibrium

- The entropy of the universe
increases in a spontaneous process
and remains unchanged in an
equilibrium process.

In terms of temperature, how would you describe
an object that has an entropy value of 0?
0 K
Perfect solid crystal with no motion
Only Theoretical
It is not possible to reach absolute 0!
Entropy of universe is always increasing!
3rd Law of Thermodynamics

the entropy of a perfect crystalline substance is zero at absolute zero

Handout3 Laws

*Based on 0 entropy as a reference point, and
calculations involving calculus beyond the scope of
this course, data has been tabulated for
Standard Molar Entropies
S
Pure substances, 1 atm pressure, 298 K
Standard Molar Entropies
S
1) Standard molar entropies of elements are not 0 (unlike H
f
).
(0 entropy is only theoretical; not really possible)
2) S.M.E of gases > S.M.E of liquids and solids.
(gases move faster than liquids)
3) S.M.E. increase with increasing molar mass.
(more potential vibrational freedom with more mass)
4) S.M.E. increase as the number of atoms in a formula increase.
(same as above)


Calculating the Entropy Change
AS
o
rxn =
n S
o
(products)
- m S
o
(reactants)

Units for AS
AS=J/molK
Since we are considering S
J/K are often used because moles are
assumed and cancel in the calculations
when considering standard states.
Calculate the standard entropy change
(AS) for the following reaction at 298K
Al
2
O
3(s)
+ 3H
2(g)
2Al
(s)
+ 3H
2
O
(g)

Substance S(J/mol-K) at 298K
Al 28.32
Al
2
O
3
51.00
H
2
O
(g)
188.8
H
2(g)
130.58
AS
o
= [2S(Al) + 3S(H
2
O)] -
[S(Al
2
O
3
) + 3S(H
2
)]

AS
o
rxn =
n S
o
(products)
- m S
o
(reactants)

Al
2
O
3(s)
+ 3H
2(g)
2Al
(s)
+ 3H
2
O
(g)

(

= A
K mol
J
K mol
J
K mol
J
K mol
J
S
) 58 . 130 ( 3 00 . 51 ) 8 . 188 ( 3 ) 32 . 28 ( 2
= 180.4 J/K
Predict the sign of S of the
following reaction.
2SO
2(g)
+ O
2(g)
2SO
3(g)
Entropy decreases, -
Lets Calculate
Calculate the standard entropy change
(AS) for the following reaction at 298K
2SO
2(g)
+ O
2(g)
2SO
3(g)

Substance S(J/mol-K) at 298K
SO
2
(g) 248.1
SO
3
(g) 256.7
O
2(g)
205.0
S = -187.8 J K
-1
Spontaneous reactions result in an
increase in entropy in the universe.
Rxs that have a large and negative AH
tend to occur spontaneously.
Spontaneity depends on enthalpy,
entropy, and temperature.

Provides a way to predict the spontaneity of a
reaction using a combination of enthalpy and
entropy of a reaction.
If Both T and P are constant, the relationship
between AG and spontaneity is:
1) AG is (-), rx is spon. forward
2) AG is 0, rx is at equilibrium
3) AG is (+) forward rx is not
spontaneous(requires work)
reverse rx is spontaneous.
) reactants ( ) products (
f f rxn
G m G n G A E A E = A
= A
rxn
G
(sum of standard free energies of formation of products)
minus
(sum of standard free energies of formation of reactants)
the sum of
Coefficients from
equation
The values of G
f
of elements in there most stable
form is 0, just as with enthalpy of formations.

Calculate the G
rxn
for the combustion of
methane at 298K and determine if the reaction is
spontaneous.
Substance G(KJ/mol) at 298K
CH
4
-50.8
CO
2
-394.4
H
2
O
(l)
-237.2
-818.0 KJ Spontaneous
Calculate the (AG) for the thermite reaction
(aluminum with iron(III) oxide).
Substance G(KJ/mol) at 298K
Al
2
O
3 (s)
-1576.5
Fe
2
O
3 (s)
-740.98
-835.5 KJ spontaneous
This equation allows us to determine if a process provides energy to do work. A
spontaneous reaction in the forward direction provides energy for work.
If not spontaneous, G equals the amount of energy needed to initiate the reaction.
Allows us to calculate the value of G as temperature changes.
Gibbs free energy (G) is a state function defined as:

G = H TS (Given on AP Exam)

T is the absolute temperature
G = H TS = G = H TS (when nonstandard)
If given a temperature change and asked to determine spontaneity or value
of G, this is the equation you would use.
Value of G tells us if a reaction is spontaneous.

AG = AH T(AS)

If we know the conditions of H and S,
we can predict the sign of AG.

We will see that:
Two conditions always produce the same result, and
two conditions depend on temperature.
Predicting Sign of G in Relation to Enthalpy and Entropy
H S G
- +
+ -
- -
+ +
Always negative (spontaneous)
Always positive (nonspontaneous)
Neg. (spontaneous) at low temp
Pos. (nonspontaneous) at high temp.
Pos. (nonspontaneous) at low temp
Neg. (spontaneous) at high temp.
H S G
- +
+ -
- -
+ +
Different sign, not temperature
dependent.
Same sign, temperature dependent.
Freezing
Melting
Some reactions are spontaneous because they
give off energy in the form of heat (H < 0).

Others are spontaneous because they lead to an
increase in the disorder of the system (S > 0).

Calculations of H and S can be used to probe
the driving force behind a particular reaction.
AG = AH T(AS)
Example 19.2 The entropy change of
the system is negative for the
precipitation reaction:

Ag
+
(aq)
+ Cl
-
(aq)
AgCl
(s)

AH
o
= -65 kJ
Since AS decreases rather than increases
in this reaction, why is this reaction
spontaneous?
Yes, entropy increases, which goes against the
second law. However, in this case, the entropy
decrease is minimal compared to the magnitude of
change in enthalpy. Therefore, the release of heat
drives the reaction to stability, which is why it is
spontaneous.

Theoretical Values

AG = AH TAS
AG = -65 298(-.030)
= -73.94
Problem

For a certain reaction, H = -13.65 KJ and S = -75.8 J K
-1
.

A) What is G at 298 K?
B) Will increasing or decreasing the temperature make the
reaction become spontaneous? If so, at what temperature
will it become spontaneous?
At 298 K the free energy is
G = H TS
G = -13.65 KJ 298(-.0758 KJ K
-1
) = +8.94 KJ
(Reaction is not spontaneous at 298 K)


Given: H = -13.65 KJ S = -75.8 J K-1 T = 298 K
A) What is G at 298 K?
Because enthalpy and entropy have the same signs,
spontaneity is indeed temperature dependent.
*Since going from not spontaneous to spontaneous crosses
the point of equilibrium, and G = 0 at equilibrium, we can
make G = to 0 to find the temperature at which equilibrium
is crossed.

B) Will increasing or decreasing the temperature make the
reaction become spontaneous? If so, at what temperature
will it become spontaneous?
0 = H TS
0 = -13.65 KJ T(-.0758 KJ K
-1
)
T = 13.65 KJ
0.0758 KJ K
-1


T = 180 K

Reaction is spontaneous below 180 K, not spontaneous above 180 K