Chapter 19: Chemical Thermodynamics

• review, spontaneity
• system and surroundings
• heat q, exothermic and endothermic reactions
• ΔH = qp
• spontaneity
• entropy S
• definition of S and its SI unit
• the third law of thermodynamics
• DS connection to heat q, DS = q/T (constant T)
• the second law of thermodynamics
• free energy G
• definition G = H – TS, DG = DH – TDS (constant T)
• predict spontaneity at constant T and P
• DG = DH – TDS < 0 reaction spontaneous
• DG = DH – TDS > 0 reaction not spontaneous; reverse reaction spontaneous
• DG = DH – TDS = 0 equilibrium condition
• connection between DG and the second law DG = – TDSuniverse
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 1. Review and spontaneity
Review:
• System: the part of the universe under study
• Surroundings: everything else that interacts with the system

• energy transfer between system and surroundings: heat (q) and work (w)

q > 0: heat absorbed by the system, or endothermic

q < 0: heat released by the system, or exothermic

• Enthalpy (H) and enthalpy change (DH)

ΔH = qp (constant P)

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Spontaneity: a process can take place without outside intervention.
Examples:
a. a falling rock, but the fallen rock does not rise back up
b. Iron rusts spontaneously in air, but the iron oxide does not spontaneously change back to iron and oxygen.
c. Heat flows spontaneously from a hot object to its surroundings.
d. Ice melts spontaneously at temperature > 0 °C.

Room T.

What makes a process spontaneous or non-spontaneous?

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 2. Entropy and entropy change
a. Entropy (S): a measure of the level of randomness (or disorder) of a system

messy room organized room

Entropy: [Link] (5 min) 4

 whole egg

Humpty Dumpty sat on a wall

Humpty Dumpty had a great fall
All the king's horses and all the king's men
Couldn't put Humpty together again broken egg

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molecular interpretation of S: a measure of the number of microstates of a system
microstates: possible arrangements of molecular position and kinetic energy

• it is entropically favored for the atoms to distribute between

two flasks so that the number of possible arrangements
(disorder) of the system increases from 1 to 4.
Effect of volume

• It is entropically favored to have one atom in each flask (2)

than to have both atoms in the same flask (1).
Even distribution

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b. S increases as # molecules, V, and T increase
i. number of molecules: Increasing the number of atoms/molecules also increases the number of
microstates, as there are more possible arrangements.
ii. V: Increasing the volume of a substance increases the number of positions where each molecule could
be, which increases the number of microstates.
iii. T: As a substance is heated, it gains kinetic energy, resulting in increased molecular motion and a broader
distribution of molecular speeds.

The Third Law: Every substance has a finite positive entropy, but at zero Kelvin the entropy may become
zero, and does so in the case of a perfectly crystalline substance. 7
c. Entropy change (ΔS): a measure of the change in disorder (number of microstates)

d. The Second Law: any spontaneous process increases the entropy of the universe

The three laws of thermodynamics:

1. You can’t win
2. You can’t break even
3. You can’t get out of the game

The second law: [Link] (7 min)

Michael Jackson: [Link] 8
Practice problem: For each of the following pairs, circle the substance with the higher entropy per mole
at a given temperature. Briefly justify your answer.

a. Ar (l) or Ar (g)

b. He (g) at 3 atm pressure or He (g) at 1.5 atm pressure

c. Ne (g) at 25 °C or Ne (g) at 35 °C

d. CO2 (g) or CO2 (s)

e.

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Practice problem: Predict the sign of the entropy change in the following reactions.

a. molten iron solidifies

Fe (l) → Fe (s)

b. LiCl (s) is formed from Li (s) and Cl2 (g)

2Li (s) + Cl2 (g) → 2LiCl (s)

c. zinc metal dissolves in HCl to form ZnCl2 (aq) and H2 (g)

Zn (s) + 2 HCl (aq) → ZnCl2 (aq) + H2 (g)

d. silver bromide precipitates upon mixing AgNO3 (aq) and KBr (aq)

AgNO3 (aq) + KBr (aq) → AgBr (s) + KNO3 (aq)

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Practice problem: The heat required to vaporize 1 mol of water at 100 °C and 1 atm is 40.7 kJ.
a) What is ΔHsys?
b) What is ΔSsys?
c) What is ΔSsurr assuming water absorbs the heat from surroundings?
d) What is ΔSuniverse?

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Chaos, Keep It Coming! by Heather Ryphemi Stregay
[Link]
Can you imagine how life would be You’d think a world sans entropy
If there were no entropy? Would be a lovely place to be.
Or, making matters even worse, I said this recently myself,
The laws of entropy were reversed? As all my books fell off their shelf.
Books would get straighter on their shelves, Yet pondering this ordered bliss,
And children’s rooms would clean themselves! I noticed things that I would miss,
And every rock or stick or tree Like rolling waves upon the sea,
Would form a crystal, perfectly. Or sugar for my morning tea:
There’d be no anarchy or war The sugar won’t dissolve, it’s true,
For everyone would know the score. That anti-entropy holds like glue.
Every thing and every face And after that, I saw with grief
Would have its certain time and place. There’d be no fractaled maple leaf:
Replacing every beach would pass No beauty in the summer wood,
An endless stretch of flawless glass. Should chaos disappear for good.
The sea would be the brightest blue, What a bore, to know each day
And every day the sky would too. Would turn out in the same old way.
How beautiful would be our world If entropy wold disappear
If order did command it. There’d be no fortune, fate or luck
If all were straight and never curled: And even after many years,
Perhaps we should demand it. Vegas wouldn’t make a buck. 12
 4. Gibbs free energy and its change – predict spontaneity
a. In most reactions, such as cellular respiration, both H and S change.

The Laws of Thermodynamics and Free Energy: [Link] (8 min) 13

b. Gibbs free energy (G): G is a state function

c. Gibbs free energy change (ΔG):

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Practice problem: At what temperature is the following process spontaneous at 1 bar?
𝐵𝑟! l → 𝐵𝑟! g
where ΔH° = 31.0 kJ/mol and ΔS° = 93.0 J/(K mol)

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Practice problem: Naphthalene, the active component of one variety of mothballs, sublimes at room
temperature. naphthalene(s) → naphthalene(g)
a) Is the process spontaneous?
b) What are the signs of ΔGrxn, ΔHrxn, and ΔSrxn?
c) What drives the reaction?

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Practice problem: Photosynthesis can be represented by the following reaction:
6 CO2 (g) + 6 H2O (l) → C6H12O6 (s) + 6 O2 (g)
a) Is the reaction exothermic or endothermic?
b) Does entropy increase or decrease during photosynthesis?
c) Based on your answers to a) and b), can you predict if photosynthesis is a spontaneous reaction? Is it
consistent with your understanding of the process?
d) What can you conclude about the sign of ΔSuniverse?

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Practice problem: A certain reaction is not spontaneous at -25 °C and ambient pressure. The entropy
change for the reaction is -95 J/K.
a) What can you conclude about the sign and magnitude of enthalpy change?
b) What can you conclude about the sign and magnitude of ΔSuniverse?
c) What can you conclude about the sign and magnitude of ΔSsurr?

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