AP Chemistry Chapter 19- Thermodynamics

19.1 Spontaneous Processes

Chemical thermodynamics is concerned with energy relationships in chemical reactions.
We consider enthalpy.
We also consider entropy in the reaction.
Recall the first law of thermodynamics: energy is conserved.
E= q + w
where E is the change in internal energy, q is the heat absorbed by the system from the surroundings, and w is the
work done.
Any process that occurs without outside intervention is a spontaneous process.
When two eggs are dropped they spontaneously break.
The reverse reaction (two eggs leaping into your hand with their shells back intact) is not spontaneous.
We can conclude that a spontaneous process has a direction.
A process that is spontaneous in one direction is nonspontaneous in the opposite direction.
Temperature may also affect the spontaneity of a process.

Reversible and Irreversible Processes

A reversible process is one that can go back and forth between states along the same path.
The reverse process restores the system to its original state.
The path taken back to the original state is exactly the reverse of the forward process.
There is no net change in the system or the surroundings when this cycle is completed.
Completely reversible processes are too slow to be attained in practice.
Consider the interconversion of ice and water at 1 atm, 0oC.
Ice and water are in equilibrium.
We now add heat to the system from the surroundings.
We melt 1 mole of ice to form 1 mole of liquid water. q=Hfus
To return to the original state we reverse the procedure.
We remove the same amount of heat from the system to the surroundings.
An irreversible process cannot be reversed to restore the system and surroundings back to their original state.
A different path (with different values of q and w) must be taken.
Consider a gas in a cylinder with a piston.
Remove the partition and the gas expands to fill the space.
No P-V work is done on the surroundings.
w = 0
Now use the piston to compress the gas back to the original state.
The surroundings must do work on the system.
w > 0
A different path is required to get the system back to its original state.
Note that the surroundings are NOT returned to their original conditions.
For a system at equilibrium, reactants and products can interconvert reversibly.
For a spontaneous process, the path between reactants and products is irreversible.
Consider the expansion of an ideal gas.
Consider an initial state: two 1-liter flasks connected by a closed stopcock.
One flask is evacuated and the other contains 1 atm of gas.
We open the stopcock while maintaining the system at constant temperature.
Initial state: an ideal gas confined to a cylinder kept at constant temperature in a water bath.
The process is isothermal at constant temperature.
E = 0 for an isothermal process.
Thus, q = w.
Allow the gas to expand from V1 to V2.
Pressure decreases from P1 to P2.
The final state: two flasks connected by an open stopcock.
Each flask contains gas at 0.5 atm.
Therefore, the gas does no work and heat is not transferred.
Why does the gas expand? Why is the process spontaneous? Why is the reverse process nonspontaneous?
When the gas molecules spread out into the 2 liter system there is an increase in the randomness or disorder.
Processes in which the disorder or entropy of the system increases tend to be spontaneous.

19.2 Entropy and the Second Law of Thermodynamics

Entropy Change
Entropy, S, is a thermodynamic term that reflects the disorder, or randomness, of the system.
The more disordered, or random, the system is, the larger the value of S.
Entropy is a state function.
It is independent of path.
For a system, S = Sfinal Sinitial.
If S > 0 the randomness increases, if S < 0 the order increases.
Suppose a system changes reversibly between state 1 and state 2.
Then, the change in entropy is given by:
q
!S = rev
T
Where qrev is the amount of heat added reversibly to the system.
The subscript rev reminds us that the path between states is reversible.
Example: A phase change occurs at constant temperature with the reversible addition of heat.

The Second Law of Thermodynamics

The second law of thermodynamics explains why spontaneous processes have a direction.
In any spontaneous process, the entropy of the universe increases.
The change in entropy of the universe is the sum of the change in entropy of the system and the
change in entropy of the surroundings.
Suniv = Ssystem + S surroundings
For a reversible process:
Suniv = Ssystem + S surroundings = 0
For a spontaneous process (i.e., irreversible):
Suniv = Ssystem + Ssurrroundings > 0
Entropy is not conserved: Suniv is continually increasing.
Note that the second law states that the entropy of the universe must increase in a spontaneous process.
It is possible for the entropy of a system to decrease as long as the entropy of the surroundings increases.

19.3 The Molecular Interpretation of Entropy

Molecular Motions and Energy
The entropy of a system indicates its disorder.
A gas is less ordered than a liquid, which is less ordered than a solid.
Any process that increases the number of gas molecules leads to an increase in entropy.
When NO(g) reacts with O2(g) to form NO2(g), the total number of gas molecules decreases.
2NO(g) + O2(g) 2NO2(g)
Therefore, the entropy decreases.
How can we relate changes in entropy to changes at the molecular level?
Formation of the new N-O bonds tie up more of the atoms in the products than in the reactants.
The degrees of freedom associated with the atoms have changed.
The greater the freedom of movement and degrees of freedom, the greater the entropy of the system.
Individual molecules have degrees of freedom associated with motions within the molecule.
There are three atomic modes of motion:
translational motion- The moving of a molecule from one point in space to another.
vibrational motion- The shortening and lengthening of bonds, including the change in bond angles.
rotational motion- The spinning of a molecule about some axis.
Energy is required to get a molecule
to translate, vibrate or rotate.
These forms of motion are ways
molecules can store energy.
The more energy stored in
translation, vibration, and
rotation, the greater the entropy.

Boltzmanns Equation and Microstates

Statistical thermodynamics is a field that uses statistics and probability to link the microscopic and macroscopic world.
Entropy may be connected to the behavior of atoms and molecules.

Envision a microstate: a snapshot of a single possible arrangement of the positions and kinetic energies of the gas
molecules. Other snapshots are possible (different microstates).
Each thermodynamic state has a characteristic number of microstates (W).
The Boltzmann equation shows how entropy (S) relates to W.
S = k lnW, where k is Boltzmanns constant (1.38 x 1023 J/K).
Entropy is thus a measure of how many microstates are associated with a particular macroscopic state.
Any change in the system that increases the number of microstates gives a positive value of S and vice versa.
The number of microstates will increase with an increase in volume, an increase in temperature, or an increase in the
number of molecules because any of these changes increases the possible positions and energies of the molecules.

Making Qualitative Predictions About S

Consider the melting of ice.
In ice, the molecules are held rigidly in a lattice.
When it melts, the molecules will have more freedom to move (increases the number of degrees of freedom).
The molecules are more randomly distributed.
Consider a KCl crystal dissolving in water.
The solid KCl has ions in a highly ordered arrangement.
When the crystal dissolves the ions have more freedom.
They are more randomly distributed.
However, now the water molecules are more ordered.
Some must be used to hydrate the ions.
Thus, this example involves both ordering and disordering.
The disordering usually predominates (for most salts).
In general, entropy will increase when:
liquids or solutions are formed from solids.
gases are formed from solids or liquids.
the number of gas molecules increases.

The Third Law of Thermodynamics

In a perfect crystal at 0 K there is no translation, rotation or vibration of molecules.
Therefore, this is a state of perfect order.
Third law of thermodynamics: The entropy of a perfect pure crystal at 0 K is zero.
Entropy will increase as we increase the temperature of the perfect crystal.
Molecules gain vibrational motion and the degrees of freedom increase.
As we heat a substance from absolute zero, the entropy must increase.
The entropy changes dramatically at a phase change.
When a solid melts, the molecules and atoms have a large increase in
freedom of movement.
Boiling corresponds to a much greater change in entropy than melting.

19.4 Entropy Changes in Chemical Reactions

Absolute entropy can be determined from complicated measurements.
Values are based on a reference point of zero for a perfect crystalline
solid at 0K (the 3rd law).
Standard molar entropy, So is the molar entropy of a substance in its
standard state. Similar in concept to H.
Units: J/mol-K.
Note that the units of H are kJ/mol.
Some observations about So values:
Standard molar entropies of elements are not zero.
Sogas > Soliquid or Sosolid.
So tends to increase with increasing molar mass of the substance.
So tends to increase with the number of atoms in
the formula of the substance.
For a chemical reaction that produces n products from m reactants:

#S =

! nS (products)" ! mS (reactants)

Example: Consider the reaction:

N2(g) + 3H2(g) 2NH3(g)
S= {2So(NH3) [S (N2) + 3So(H2)]}

Entropy Changes in the Surroundings

For an isothermal process,
Ssurr = qsys / T
For a reaction at constant pressure,
qsys = H
Example: consider the reaction:
N2(g) + 3H2(g) 2NH3(g)
The entropy gained by the surroundings is greater than the entropy lost by the system.
This is the sign of a spontaneous reaction: the overall entropy change of the universe is positive.
Suniv > 0

19.5 Gibbs Free Energy

For a spontaneous reaction the entropy of the universe must increase.
Reactions with large negative H values tend to be spontaneous.
How can we use S and H to predict whether a reaction is spontaneous?
The Gibbs free energy, (free energy), G, of a state is:
G = H TS
Free energy is a state function.
For a process occurring at constant temperature, the free energy change is:
G = H TS
The sign of G is important in predicting the spontaneity of the reaction.
If G < 0 then the forward reaction is spontaneous.
If G = 0 then the reaction is at equilibrium and no net reaction will occur.
If G > 0 then the forward reaction is not spontaneous.
However, the reverse reaction is spontaneous.
If G > 0, work must be supplied from the surroundings to drive the reaction.
The equilibrium position in a spontaneous process is given by the minimum free energy available to the system.
The free energy decreases until it reaches this minimum value.

Standard Free-Energy Changes

We can tabulate standard free energies of formation, Gf .
Standard states are pure solid, pure liquid, 1 atm (gas), 1 M concentration (solution), and G = 0 for elements.
We most often use 25oC (or 298 K) as the temperature.
The standard free-energy change for a process is given by:

"G =
n"G f (products )#
m"G f (reactants)
The quantity G for a reaction tells us whether a mixture of substances will spontaneously react
to produce more reactants (G > 0) or products (G < 0).

19.6 Free Energy and Temperature

The sign of G tells us if the reaction is spontaneous.
Focus on G = H TS.
If H <0 and TS <0:
G will always be <0.
Thus the reaction will be spontaneous.
If H >0 and TS >0:
G will always be >0.
Thus, the reaction will not be spontaneous.
If H and TS have different signs:
The sign of G will depend on the sign and magnitudes of the other terms.
Temperature will be an important factor.
For example, consider the following reaction:
H2 O(s) H2 O(l)
H >0, S > 0
At a temperature less than 0oC:
H > TS
G > 0
The melting of ice is not spontaneous when the temperature is less than 0oC.
At a temperature greater than 0C:
H < TS
G < 0
The melting of ice is spontaneous when the temperature is greater than 0oC.
o
At 0 C:
H = TS
G = 0
Ice and water are in equilibrium at 0C.
Even though a reaction has a negative G it may occur too slowly to be observed.
Thermodynamics gives us the direction of a spontaneous process; it does not give us the rate of the process.

19.7 Free Energy and the Equilibrium Constant

Recall that G and Keq (equilibrium constant) apply to standard conditions.
Recall that G and Q (equilibrium quotient) apply to any conditions.
It is useful to determine whether substances will react under specific conditions:
G = G + RTlnQ
At equilibrium, Q = Keq and G = 0, so:
G = G + RTlnQ
0 = G + RTlnK
G = RTlnK
From the above we can conclude:
If G < 0, then K > 1.
If G = 0, then K = 1.
If G > 0, then K < 1.

Driving Nonspontaneous Reactions

If G > 0, work must be supplied from the surroundings to drive the reaction.
Biological systems often use one spontaneous reaction to drive another nonspontaneous reaction.
These reactions are coupled reactions.
The energy required to drive most nonspontaneous reactions comes from the metabolism of foods.
Example: Consider the oxidation of glucose:
C6H12O6(s) + 6O2(g) 6CO2(g) + 6H2 O(l)
G = 2880 kJ.
The free energy released by glucose oxidation is used to convert low energy adenosine diphosphate (ADP) and
inorganic phosphate into high energy adenosine triphosphate (ATP).
When ATP is converted back to ADP the energy released may be used to drive other reactions.

Homework
1. Read Pages 802-819,
pg836 #1, 3, 7, 11, 21, 23, 27, 29, 31, 33, 35, 37, 39
2. Read Pages 820-829,
pg 836 #2, 4, 41, 47, 51, 53a, 55a&b, 57, 59, 61, 63
3. Read Pages 830-836,
pg 837 #5, 6, 71, 73, 75, 77, 79
Practice Problems
Use the table below to answer the questions that follow.
Thermodynamic Quantities for Selected Substances at 298.15 K (25C)
Substance

Gf (kJ/mol)

S (J/K-mol)

1.88
0
226.7
52.30
-84.68
-110.5
-393.5

2.84
0
209.2
68.11
-32.89
-137.2
-394.4

2.43
5.69
200.8
219.4
229.5
197.9
213.6

Hydrogen
H2( g)

130.58

Oxygen
O2 (g)
H2O (l)

0
-285.83

0
-237.13

205.0
69.91

Carbon
C (s, diamond)
C (s, graphite)
C2H2 (g)
C2H4 (g)
C2H4 (g)
CO (g)
CO2 (g)

Hf (kJ/mol)

1) The value of S for the catalytic hydrogenation of

acetylene to ethene,
C2H2 (g) + H2 (g) C2H4 (g)

1. D
2. E
3. D
4. E
5. B
6. A
7. D
8. E
9. C
10. E
11. A
12. E
13. A
14. D
15. B
16. C
17. C
18. C
19. D
20. B
21. A
22. E
23. E
24. C
25. C
26. D
27. C
28. D
29. A
30. E
31. A
32. 1367 K
33. 80 kJ/mol
34. TRUE
35. TRUE
36. TRUE

3) The value of S for the oxidation of carbon to carbon

monoxide,
2C (s, graphite) + O2 (g) 2CO (g)

is __________ J/K.
A) +18.6
B) +550.8
C) +112.0
D) -112.0
E) -18.6

is __________ J/K. Carbon monoxide is produced in the

combustion of carbon with limited oxygen.
A) -12.8
B) +408.6
C) -408.6
D) +179.4
E) +395.8

2) The combustion of acetylene in the presence of excess

oxygen yields carbon dioxide and water:

4) The value of S for the oxidation of carbon to carbon

dioxide,

2C2H2 (g) + 5O2 (g) 4CO2 (g) + 2H2O (l)

The value of S for this reaction is __________ J/K.
A) +689.3
B) +122.3
C) +432.4
D) -122.3
E) -432.4

C (s, graphite) + O2 (g) CO2 (g)

is __________ J/K. The combustion of carbon, as in charcoal
briquettes, in the presence of abundant oxygen produces
carbon dioxide.
A) +424.3
B) +205.0
C) -205.0
D) -2.9
E) +2.9

Use the table below to answer the questions that follow.

Thermodynamic Quantities for Selected Substances at 298.15 K (25C)
Substance
Calcium
Ca (s)
CaCl2 (s)
Ca2+ (aq)

Hf (kJ/mol)

Gf (kJ/mol)

S (J/K-mol)

0
-795.8

0
-748.1

41.4
104.6

226.7

209.2

200.8

Chlorine
Cl2 (g)
Cl- (aq)

0
-167.2

0
-131.2

222.96
56.5

Oxygen
O2 (g)
H2O (l)

0
-285.83

0
-237.13

205.0
69.91

Phosphorus
P2 (g)
PCl3 (g)
POCl3 (g)

144.3
-288.1
-542.2

103.7
-269.6
-502.5

218.1
311.7
325

Sulfur
S (s, rhombic)
SO2 (g)
SO3 (g)

0
-269.9
-395.2

0
-300.4
-370.4

31.88
248.5
256.2

5) The value of H for the oxidation of solid elemental sulfur

to gaseous sulfur trioxide,
2S (s, rhombic) + 3O2 (g) 2SO3 (g)

7) The value of G at 25 C for the oxidation of solid

elemental sulfur to gaseous sulfur trioxide,
2S (s, rhombic) + 3O2 (g) 2SO3 (g)

is __________ kJ/mol.
A) +790.4
B) -790.4
C) +395.2
D) -395.2
E) +105.1

is __________ kJ/mol.
A) +740.8
B) -370.4
C) +370.4
D) -740.8
E) +185.2

6) The value of H for the decomposition of gaseous sulfur

trioxide to its component elements,

8) The value of G at 25 C for the formation of calcium

chloride from its constituent elements,

2SO3 (g) 2S (s, rhombic) + 3O2 (g)

is __________ kJ/mol.
A) +790.4
B) -790.4
C) +395.2
D) -395.2
E) +105.1

Ca (s) + Cl2 (g) CaCl2 (s)

is __________ kJ/mol.
A) -795.8
B) +795.8
C) +763.7
D) +748.1
E) -748.1

9) A common name for methanol (CH3OH) is wood alcohol. The normal boiling point of methanol is 64.7 C and the molar enthalpy
of vaporization if 71.8 kJ/mol. The value of S when 2.15 mol of CH3OH (l) vaporizes
at 64.7 C is ________J/K.
A) 0.457
B) 5.21 107
C) 457
D) 2.39 103
E) 2.39

10) The value of G at 100.0 C for the oxidation of solid

elemental sulfur to gaseous sulfur dioxide,
S (s, rhombic) + O2 (g) SO2 (g)
is __________ kJ/mol. At 25.0 oC for this reaction, H is 269.9 kJ/mol, G is -300.4kJ/mol, and S
is +11.6 J/K.
A) -265.6
B) -1,430
C) -4,598
D) -271.1
E) -274.2
11) For a given reaction, H = -19.9 kJ/mol and S = -55.5
J/K-mol. The reaction will have G = 0 at ________K.
Assume that H and S do not vary with temperature.
A) 359
B) 2789
C) 298
D) 2.79
E) 0.359
12) In the Haber process, ammonia is synthesized from
nitrogen and hydrogen:
N2 (g) + 3H2 (g) 2NH3 (g)
G at 298 oK for this reaction is -33.3 kJ/mol. The value of
G at 298 K for a reaction mixture that consists
of 1.9 atm N2, 1.6 atm H2, and 0.65 atm NH3 is __________.
A) -1.8
B) -3.86 103
C) -7.25 103
D) -104.5
E) -40.5
13) The equilibrium constant for a reaction is 0.48 at 25 C.
What is the value of G (kJ/mol) at this temperature?
A) 1.8
B) -4.2
C) 1.5 102
D) 4.2
E) More information is needed.

14) Consider the reaction:

FeO (s) + Fe (s) + O2 (g) Fe2O3 (s)
Given the following table of thermodynamic data at 298 oK:
Substance
FeO(s)
Fe(s)
O2(g)
Fe2O3(s)

Hf(kJ/mol)
-271.9
0
0
-822.16

S(J/Kmol)
60.75
27.15
205.0
89.96

The value K for the reaction at 25 C is __________.

A) 370
B) 5.9 104
C) 3.8 10-14
D) 7.1 1085
E) 8.1 1019

15) A reaction that is spontaneous as written __________.

A) is very rapid
B) will proceed without outside intervention
C) is also spontaneous in the reverse direction
D) has an equilibrium position that lies far to the left
E) is very slow
16) Of the following, only __________ is not a state function.
A) S
B) H
C) q
D) E
E) T
17) Which one of the following is always positive when a
spontaneous process occurs?
A) Ssystem
B) Ssurroundings
C) Suniverse
D) Huniverse
E) Hsurroundings
18) The second law of thermodynamics states that ________.
A) E = q + w
n!Hof (products) m!Hof (reactants)
B) !Horxn =

"

"

C) for any spontaneous process, the entropy of the universe

increases
D) the entropy of a pure crystalline substance is zero at
absolute zero
E) S = qrev /T at constant temperature
19) Which one of the following processes produces a decrease
in the entropy of the system?
A) boiling water to form steam
B) dissolution of solid KCl in water
C) mixing of two gases into one container
D) freezing water to form ice
E) melting ice to form water
20) Which reaction produces an increase in Ssys?
A) Ag+ (aq) + Cl- (aq) AgCl (s)
B) CO2 (s) CO2 (g)
C) H2 (g) + Cl2 (g) 2 HCl (g)
D) N2 (g) + 3 H2 (g) 2 NH3 (g)
E) H2O (l) H2O (s)
21) S is negative for the reaction __________.
A) 2SO2 (g) + O2 (g) 2SO3 (g)
B) NH4 Cl (s) NH3 (g) + HCl (g)
C) PbCl2 (s) Pb2+ (aq) + 2Cl- (aq)
D) 2C (s) + O2 (g) 2CO2 (g)
E) H2O (l) H2O (g)
22) Consider a pure crystalline solid that is heated from
absolute zero to a temperature above the boiling point of the
liquid. Which of the following processes produces the greatest
increase in the entropy of the substance?
A) melting the solid
B) heating the liquid
C) heating the gas
D) heating the solid
E) vaporizing the liquid

23) Of the following, the entropy of __________ is the largest.

A) HCl (l)
B) HCl (s)
C) HCl (g)
D) HBr (g)
E) HI (g)
24) The standard Gibbs free energy of formation of
__________ is zero.
(a) H2O (l)
(b) O (g)
(c) H2 (g)
A) (a) only
B) (b) only
C) (c) only
D) (b) and (c)
E) (a), (b), and (c)
25) The equilibrium position corresponds to which letter on
the graph of G vs. f (course of reaction) below?

29) Given the following table of thermodynamic data,

Substance
PCl3(g)
PCl3(l)

26) For the reaction

C(s) + H2O (g) CO(g) + H2 (g)
H = 131.3 kJ/mol and S = 133.6 J/K mol at 298 K. At
temperatures greater than __________C this reaction is
spontaneous under standard conditions.
A) 273
B) 325
C) 552
D) 710
E) 983
27) For a reaction to be spontaneous under standard conditions
at all temperatures, the signs of H and S must be
__________ and __________, respectively.
A) +, +
B) +, C) -, +
D) -, E) +, 0
28) If G for a reaction is greater than zero, then
__________.
A) K = 0
B) K = 1
C) K > 1
D) K < 1
E) More information is needed.

S(J/Kmol)
311.7
217

complete the following sentence. The vaporization of PCl3 (l)

is __________.
A) nonspontaneous at low temperature and spontaneous at high
temperature
B) spontaneous at low temperature and nonspontaneous at high
temperature
C) spontaneous at all temperatures
D) nonspontaneous at all temperatures
E) not enough information given to draw a conclusion
30) Consider the reaction:
Ag+ (aq) + Cl- (aq) AgCl (s)
Given the following table of thermodynamic data,
Substance
Ag+(aq)
Cl-(aq)
AgCl(s)

A) A
B) B
C) C
D) D
E) E

Hf(kJ/mol)
-288.07
-319.6

Hf(kJ/mol)
105.90
-167.2
-127.0

S(J/Kmol)
73.93
56.5
96.11

determine the temperature (in C) above which the reaction is

nonspontaneous under standard conditions.
A) 1235
B) 150.5
C) 432.8
D) 133.0
E) 1641
31) With thermodynamics, one cannot determine __________.
A) the speed of a reaction
B) the direction of a spontaneous reaction
C) the extent of a reaction
D) the value of the equilibrium constant
E) the temperature at which a reaction will be spontaneous
32) Find the temperature above which a reaction with a
H of 123 .0 kJ/mol and a S of 90.00 J/Kmol becomes
spontaneous.
33) Calculate G for the autoionization of water at 25C.
Kw = 1.0 10-14
34) The melting of a substance at its melting point is an
isothermal process. TRUE or FALSE
35) The vaporization of a substance at its boiling point is an
isothermal process. TRUE or FALSE
36) The more negative G is for a given reaction, the larger
the value of the corresponding equilibrium constant, K.
TRUE or FALSE