Chemical

Thermodynamics
Thermo Part 2

Chemical
Thermodynamics
1
First Law of Thermodynamics

• You will recall from Chapter 5 that energy cannot

be created nor destroyed.
• Therefore, the total energy of the universe is a
constant.
• Energy can, however, be converted from one form
to another or transferred from a system to the
surroundings or vice versa.

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Thermodynamics
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Spontaneous Processes
• Spontaneous processes are
those that can proceed
without any outside
intervention.
• The gas in vessel B will
spontaneously effuse into
vessel A, but once the gas is
in both vessels, it will not
spontaneously go back to
one container 3
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Thermodynamics
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Spontaneous Processes

Processes that are

spontaneous in
one direction are
nonspontaneous in
the reverse
direction.

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Thermodynamics
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Spontaneous Processes
• Processes that are spontaneous at one temperature
may be nonspontaneous at other temperatures.
• Above 0C it is spontaneous for ice to melt.
• Below 0C the reverse process is spontaneous.

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 SAMPLE EXERCISE 19.1 Identifying Spontaneous Processes

Predict whether the following processes are spontaneous as described, spontaneous in the reverse
direction, or in equilibrium: (a) When a piece of metal heated to 150ºC is added to water at 40ºC,
the water gets hotter. (b) Water at room temperature decomposes into H 2(g) and O2(g). (c)
Benzene vapor, C6H6(g), at a pressure of 1 atm condenses to liquid benzene at the normal boiling
point of benzene, 80.1ºC.

PRACTICE EXERCISE
Under 1 atm pressure CO2(s) sublimes at –78ºC. Is the transformation of CO 2(s) to CO2(g) a
spontaneous process at –100ºC and 1 atm pressure?

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Reversible Processes
In a reversible
process the system
changes in such a
way that the system
and surroundings
can be put back in
their original states
by exactly
reversing the
process.
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Thermodynamics
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Irreversible Processes

• Irreversible processes cannot be undone by

exactly reversing the change to the system.
• Spontaneous processes are irreversible.
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Thermodynamics
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Entropy
• Entropy (S) is a term coined by Rudolph Clausius
in the 19th century.
• Clausius was convinced of the significance of the
ratio of heat delivered and the temperature at
which it is delivered,
q
T
• Entropy can be thought of as a measure of the
randomness of a system.
• It is related to the various modes of motion in
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molecules. Chemical
Thermodynamics
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Entropy

• Like total energy, E, and enthalpy, H,

entropy is a state function.
• Therefore,
S = Sfinal  Sinitial

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Thermodynamics
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Entropy

• For a process occurring at constant temperature

(an isothermal process), the change in entropy is
equal to the heat that would be transferred if the
process were reversible divided by the
temperature:

qrev
S =
T
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Thermodynamics
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Second Law of
Thermodynamics
The second law of thermodynamics states
that the entropy of the universe increases
for spontaneous processes, and the entropy
of the universe does not change for
reversible processes.

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Thermodynamics
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Second Law of
Thermodynamics
In other words:
For reversible processes:
Suniv = Ssystem + Ssurroundings = 0
For irreversible processes:
Suniv = Ssystem + Ssurroundings > 0
S is entropy. H is enthalpy. 13
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Second Law of
Thermodynamics
These last truths mean that as a
result of all spontaneous processes
the entropy of the universe
increases.

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Thermodynamics
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Entropy on the Molecular Scale
• Ludwig Boltzmann described the concept of
entropy on the molecular level.
• Temperature is a measure of the average kinetic
energy of the molecules in a sample.

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Thermodynamics
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Entropy on the Molecular Scale
• Molecules exhibit several types of motion:
• Translational: Movement of the entire molecule from one
place to another.
• Vibrational: Periodic motion of atoms within a molecule.
• Rotational: Rotation of the molecule on about an axis or
rotation about  bonds.

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Thermodynamics
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Entropy on the Molecular Scale
• Boltzmann envisioned the motions of a sample of
molecules at a particular instant in time.
• This would be akin to taking a snapshot of all the molecules.
• He referred to this sampling as a microstate of the
thermodynamic system.

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Entropy on the Molecular Scale
• Each thermodynamic state has a specific number of
microstates, W, associated with it.
• Entropy is
S = k lnW
where k is the Boltzmann constant, 1.38  1023 J/K.

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Entropy on the Molecular Scale

• The change in entropy for a process, then, is

S = k lnWfinal  k lnWinitial

lnWfinal
S = k ln
lnWinitial
• Entropy increases with the number of 19
microstates in the system. Chemical
Thermodynamics
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Entropy on the Molecular Scale
• The number of microstates and, therefore, the
entropy tends to increase with increases in
• Temperature.
• Volume.
• The number of independently moving
molecules.

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Thermodynamics
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Entropy and Physical States

• Entropy increases with

the freedom of motion of
molecules.
• Therefore,
S(g) > S(l) > S(s)

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Thermodynamics
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Solutions

Generally, when a
solid is dissolved in
a solvent, entropy
increases.

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Thermodynamics
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Entropy Changes

• In general, entropy
increases when
• Gases are formed from
liquids and solids.
• Liquids or solutions are
formed from solids.
• The number of gas molecules
increases.
• The number of moles
increases. 23
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SAMPLE EXERCISE 19.3 Predicting the Sign of S

Predict whether S is positive or negative for each of the following processes,

assuming each occurs at constant temperature:

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PRACTICE EXERCISE
Indicate whether each of the following processes produces an
increase or decrease in the entropy of the system:

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SAMPLE EXERCISE 19.4 Predicting Which Sample of Matter Has the Higher Entropy

Choose the sample of matter that has greater entropy in each pair, and explain your
choice: (a) 1 mol of NaCl(s) or 1 mol of HCl(g) at 25ºC, (b) 2 mol of HCl(g) or 1 mol
of HCl(g) at 25ºC, (c) 1 mol of HCl(g) or 1 mol of Ar(g) at 298 K.

PRACTICE EXERCISE
Choose the substance with the greater entropy in each case: (a) 1 mol of H2(g) at STP
or 1 mol of H2(g) at 100ºC and 0.5 atm, (b) 1 mol of H2O(s) at 0ºC or 1 mol of H2O(l)
at 25ºC, (c) 1 mol of H2(g) at STP or 1 mol of SO2(g) at STP, (d) 1 mol of N2O4(g) at
STP or 2 mol of NO2(g) at STP.

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Third Law of Thermodynamics

The entropy of a pure crystalline

substance at absolute zero is 0.

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Standard Entropies

• These are molar entropy values of

substances in their standard states.
• Standard entropies tend to
increase with increasing molar
mass.
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Standard Entropies

Larger and more complex molecules have

greater entropies. (More stuff, more entropy)

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Entropy Changes

Entropy changes for a reaction can be estimated in a manner

analogous to that by which H is estimated:

S° = nS°(products) - mS°(reactants)

where n and m are the coefficients in the balanced chemical
equation. 30
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 SAMPLE EXERCISE 19.5 Calculating S from Tabulated Entropies

Calculate S° for the synthesis of ammonia from N2(g) and H2(g) at 298 K:

Step 1 Formula with substitutions:

Step 2 Gather data from chart or question provided. We would fine these in
Appendix C of your book:

PRACTICE EXERCISE
Using the standard entropies in Appendix C, calculate the standard entropy change,
S°, for the following reaction at 298 K: Chemical
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Entropy Changes in
Surroundings
• Heat that flows into or out of the
system changes the entropy of the
surroundings.
• For an isothermal process:
qsys
Ssurr =
T
• At constant pressure, qsys is simply
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H for the system. Chemical
Thermodynamics
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Entropy Change in the
Universe
• The universe is composed of the system and the
surroundings.
• Therefore,
Suniverse = Ssystem + Ssurroundings
• For spontaneous processes
Suniverse > 0

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Entropy Change in the
Universe
• This becomes:
Suniverse = Ssystem + Hsystem
T
Multiplying both sides by T,
TSuniverse = Hsystem  TSsystem

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Gibbs Free Energy

• TSuniverse is defined as the Gibbs free

energy, G.
• When Suniverse is positive, G is negative.
• Therefore, when G is negative, a process
is spontaneous.

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Thermodynamics
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Gibbs Free Energy
1. If G is negative, the
forward reaction is
spontaneous.
2. If G is 0, the system is
at equilibrium.
3. If G is positive, the
reaction is spontaneous
in the reverse direction.
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Thermodynamics
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Standard Free Energy Changes

Analogous to standard enthalpies of formation are

standard free energies of formation, G.

G = nGf (products)  mGf (reactants)

f

where n and m are the stoichiometric

coefficients. 37
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SAMPLE EXERCISE 19.6 Calculating Standard Free-Energy Change
from Free Energies of Formation

(a) By using data from Appendix C, calculate the standard free-energy change for the following reaction at
298 K:

(b) What is Gºfor the reverse of the above reaction?

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PRACTICE EXERCISE
By using data from Appendix C, calculate Gº at 298 K for the combustion of methane:

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SAMPLE EXERCISE 19.7 Estimating and Calculating G°
In Section 5.7 we used Hess’s law to calculate Hº for the combustion of propane gas at 298 K:

(a) Without using data from Appendix C, predict whether Gº for this reaction is more negative or less negative
than Hº. (b) Use data from Appendix C to calculate the standard free-energy change for the reaction at 298 K.
Is your prediction from part (a) correct?

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PRACTICE EXERCISE
Consider the combustion of propane to form CO 2(g) and H2O(g) at 298 K:
Would you expect Gº to be more negative or less negative
than H°?

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Free Energy Changes

At temperatures other than 25°C,

G° = H  TS

How does G change with temperature?

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Thermodynamics
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Free Energy and Temperature

• There are two parts to the free energy equation:

• H— the enthalpy term
• TS — the entropy term
• The temperature dependence of free energy, then
comes from the entropy term.

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Free Energy and Temperature

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Thermodynamics
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SAMPLE EXERCISE 19.8 Determining the Effect of Temperature on Spontaneity

The Haber process for the production of ammonia involves the equilibrium

Assume that Hº and Sº for this reaction do not change with temperature. (a) Predict the direction in which
Gº for this reaction changes with increasing temperature. (b) Calculate the values of Gº for the reaction at
25ºC and 500ºC.

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SAMPLE EXERCISE 19.8 continued

PRACTICE EXERCISE
(a) Using standard enthalpies of formation and standard entropies in Appendix C, calculate Hº and Sº at
298 K for the following reaction: (b) Using the values obtained in part (a),
estimate Gº at 400 K.

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Free Energy and Equilibrium
Under any conditions, standard or nonstandard,
the free energy change can be found this way:

G = G + RT lnQ

(Under standard conditions, all concentrations are 1

M, so Q = 1 and lnQ = 0; the last term drops out.)

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Thermodynamics
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SAMPLE EXERCISE 19.9 Relating G to a Phase Change at Equilibrium

As we saw in Section 11.5, the normal boiling point is the temperature at which a pure liquid is in equilibrium
with its vapor at a pressure of 1 atm. (a) Write the chemical equation that defines the normal boiling point of
liquid carbon tetrachloride, CCl 4(l). (b) What is the value of Gº for the equilibrium in part (a)? (c) Use
thermodynamic data in Appendix C and Equation 19.20 to estimate the normal boiling point of CCl 4.

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PRACTICE EXERCISE
Use data in Appendix C to estimate the normal boiling point, in K, for elemental bromine, Br 2(l). (The
experimental value is given in Table 11.3.)

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SAMPLE EXERCISE 19.10 Calculating the Free-Energy Change Under
Nonstandard Conditions

We will continue to explore the Haber process for the synthesis of ammonia:

Calculate G at 298 K for a reaction mixture that consists of 1.0 atm N 2, 3.0 atm H2, and 0.50 atm NH3.

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PRACTICE EXERCISE
Calculate G at 298 K for the reaction of nitrogen and hydrogen to form ammonia if the reaction mixture
consists of 0.50 atm N2, 0.75 atm H2, and 2.0 atm NH3.

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Free Energy and Equilibrium
• At equilibrium, Q = K, and G = 0.
• The equation becomes
0 = G + RT lnK

• Rearranging, G = RT lnK

K = eG/RT 52
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SAMPLE EXERCISE 19.11 Calculating an Equilibrium Constant from G°
Use standard free energies of formation to calculate the equilibrium constant, K, at 25°C for the reaction
involved in the Haber process:

The standard free-energy change for this reaction was calculated in Sample Exercise 19.8: Gº = –33.3 kJ/mol
= –33,300 J/mol.

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PRACTICE EXERCISE
Use data from Appendix C to calculate the standard free-energy change, Gº, and the equilibrium constant,
K, at 298 K for the reaction

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SAMPLE INTEGRATIVE EXERCISE Putting Concepts Together

Consider the simple salts NaCl(s) and AgCl(s). We will examine the equilibria in which these salts dissolve in
water to form aqueous solutions of ions:

(a) Calculate the value of Gº at 298 K for each of the preceding reactions. (b) The two values from part (a) are
very different. Is this difference primarily due to the enthalpy term or the entropy term of the standard free-
energy change? (c) Use the values of Gº to calculate the Ksp values for the two salts at 298 K. (d) Sodium
chloride is considered a soluble salt, whereas silver chloride is considered insoluble. Are these descriptions
consistent with the answers to part (c)? (e) How will Gº for the solution process of these salts change with
increasing T? What effect should this change have on the solubility of the salts?

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