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Chapter 19- Chemical
     Thermodynamics
Sections 19.1 - 19.3
  Spontaneous processes & entropy
First Law of Thermodynamics




                            Chemical
                         Thermodynamics
First Law of Thermodynamics

• You will recall from Chapter 5 that
  energy cannot be created nor
  destroyed.




       ...
First Law of Thermodynamics

• You will recall from Chapter 5 that
  energy cannot be created nor
  destroyed.
• Therefore...
First Law of Thermodynamics

• You will recall from Chapter 5 that
  energy cannot be created nor
  destroyed.
• Therefore...
Spontaneous Processes




                           Chemical
                        Thermodynamics
Spontaneous Processes
• Spontaneous processes
  are those that can
  proceed without any
  outside intervention.




     ...
Spontaneous Processes
• Spontaneous processes
  are those that can
  proceed without any
  outside intervention.
• The gas...
Spontaneous Processes
 • Spontaneous processes
   are those that can
   proceed without any
   outside intervention.
 • Th...
Spontaneous Processes

            Processes that are
            spontaneous in one
            direction are
           ...
Melting a cube of water ice at −10°C
and atmospheric pressure is a
________ process.
1. Spontaneous

2. Nonspontaneous



...
Correct Answer:

                    Melting of an ice cube at
1. Spontaneous      1 atm pressure will only
              ...
Spontaneous Processes




                           Chemical
                        Thermodynamics
Spontaneous Processes
• Processes that are spontaneous at one
  temperature may be nonspontaneous at other
  temperatures....
Spontaneous Processes
• Processes that are spontaneous at one
  temperature may be nonspontaneous at other
  temperatures....
Spontaneous Processes
• Processes that are spontaneous at one
  temperature may be nonspontaneous at other
  temperatures....
Chemical
Thermodynamics
No. Nonspontaneous processes can occur with
    some external assistance.




                                            ...
SAMPLE EXERCISE 19.1 Identifying Spontaneous Processes

   Predict whether these processes are spontaneous as
   described...
SAMPLE EXERCISE 19.1 Identifying Spontaneous Processes

   Predict whether these processes are spontaneous as
   described...
PRACTICE EXERCISE
Under 1 atm pressure CO2(s) sublimes at
–78°C. Is the transformation of CO2(s) to
CO2(g) a spontaneous p...
PRACTICE EXERCISE
Under 1 atm pressure CO2(s) sublimes at
–78°C. Is the transformation of CO2(s) to
CO2(g) a spontaneous p...
Reversible Processes

            In a reversible
            process the system
            changes in such a
           ...
Irreversible Processes




                            Chemical
                         Thermodynamics
Irreversible Processes




• Irreversible processes cannot be undone by
  exactly reversing the change to the system.


  ...
Irreversible Processes




• Irreversible processes cannot be undone by
  exactly reversing the change to the system.
• Sp...
Chemical
Thermodynamics
No




        Chemical
     Thermodynamics
Entropy




             Chemical
          Thermodynamics
Entropy

• Entropy (S) is a term coined by Rudolph
  Clausius in the 19th century.




                                   ...
Entropy

• Entropy (S) is a term coined by Rudolph
  Clausius in the 19th century.
• Clausius was convinced of the
  signi...
Entropy




             Chemical
          Thermodynamics
Entropy

• Entropy can be thought of as a measure
  of the randomness of a system.




                                   ...
Entropy

• Entropy can be thought of as a measure
  of the randomness of a system.
• It is related to the various modes of...
Entropy




             Chemical
          Thermodynamics
Entropy

• Like total energy, E, and enthalpy, H,
  entropy is a state function.




                                     ...
Entropy

• Like total energy, E, and enthalpy, H,
  entropy is a state function.
• Therefore,




                        ...
Entropy

• Like total energy, E, and enthalpy, H,
  entropy is a state function.
• Therefore,
              ΔS = Sfinal − ...
Entropy

• For a process occurring at constant
  temperature (an isothermal process), the
  change in entropy is equal to ...
Entropy

• For a process occurring at constant
  temperature (an isothermal process), the
  change in entropy is equal to ...
Chemical
Thermodynamics
•        ΔS depends not merely on q but on qrev.
    There is only one reversible isothermal path
    between two states r...
SAMPLE EXERCISE 19.2 Calculating ΔS for a Phase Change


The element mercury, Hg, is a silvery liquid at
room temperature....
SAMPLE EXERCISE 19.2 Calculating ΔS for a Phase Change


The element mercury, Hg, is a silvery liquid at
room temperature....
SAMPLE EXERCISE 19.2 Calculating ΔS for a Phase Change


The element mercury, Hg, is a silvery liquid at
room temperature....
SAMPLE EXERCISE 19.2 Calculating ΔS for a Phase Change


The element mercury, Hg, is a silvery liquid at room temperature....
SAMPLE EXERCISE 19.2 continued


PRACTICE EXERCISE
The normal boiling point of ethanol,
C2H5OH, is 78.3°C (Figure 11.24), ...
SAMPLE EXERCISE 19.2 continued


PRACTICE EXERCISE
The normal boiling point of ethanol,
C2H5OH, is 78.3°C (Figure 11.24), ...
Second Law of Thermodynamics

  The second law of thermodynamics
  states that the entropy of the universe
  increases for...
Second Law of Thermodynamics




                            Chemical
                         Thermodynamics
Second Law of Thermodynamics

In other words:
For reversible processes:
         ΔSuniv = ΔSsystem + ΔSsurroundings = 0
Fo...
Second Law of Thermodynamics

These last truths mean that as a result of all
spontaneous processes

     the entropy of th...
Chemical
Thermodynamics
The entropy of the universe for the process must
increase by a greater amount than the entropy of the
system decreases.


...
Entropy on the Molecular Scale




                              Chemical
                           Thermodynamics
Entropy on the Molecular Scale
• Ludwig Boltzmann described the concept of
  entropy on the molecular level.




         ...
Entropy on the Molecular Scale
• Ludwig Boltzmann described the concept of
  entropy on the molecular level.
• Temperature...
Entropy on the Molecular Scale




                              Chemical
                           Thermodynamics
Entropy on the Molecular Scale
• Molecules exhibit several types of motion:
   Translational: Movement of the entire mole...
Chemical
Thermodynamics
A molecule can vibrate (atoms moving relative to
one another) and rotate (tumble); a single atom can
only rotate.




    ...
Entropy on the Molecular Scale




                              Chemical
                           Thermodynamics
Entropy on the Molecular Scale
• Boltzmann envisioned the motions of a sample of
  molecules at a particular instant in ti...
Entropy on the Molecular Scale




                              Chemical
                           Thermodynamics
Entropy on the Molecular Scale
• Each thermodynamic state has a specific number of
  microstates, W, associated with it.

...
Entropy on the Molecular Scale
• Each thermodynamic state has a specific number of
  microstates, W, associated with it.
•...
Entropy on the Molecular Scale
• Each thermodynamic state has a specific number of
  microstates, W, associated with it.
•...
Entropy on the Molecular Scale
• Each thermodynamic state has a specific number of
  microstates, W, associated with it.
•...
S = k lnW




               Chemical
            Thermodynamics
S = k lnW




S = 0




                       Chemical
                    Thermodynamics
Entropy on the Molecular Scale




                              Chemical
                           Thermodynamics
Entropy on the Molecular Scale

• The change in entropy for a process,
  then, is
     ΔS = k lnWfinal − k lnWinitial

   ...
Entropy on the Molecular Scale

• The change in entropy for a process,
  then, is
     ΔS = k lnWfinal − k lnWinitial

   ...
Entropy on the Molecular Scale




                              Chemical
                           Thermodynamics
Entropy on the Molecular Scale
• The number of microstates and,
  therefore, the entropy tends to increase
  with increase...
Entropy and Physical States




                             Chemical
                          Thermodynamics
Entropy and Physical States

• Entropy increases with
  the freedom of motion
  of molecules.




                        ...
Entropy and Physical States

• Entropy increases with
  the freedom of motion
  of molecules.
• Therefore,




           ...
Entropy and Physical States

• Entropy increases with
  the freedom of motion
  of molecules.
• Therefore,
  S(g) > S(l) >...
Solutions

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



        ...
Entropy Changes




                     Chemical
                  Thermodynamics
Entropy Changes

• In general, entropy
  increases when
   Gases are formed from
    liquids and solids.
   Liquids or s...
The sign of entropy change, ΔS,
associated with the boiling of water is
_______.
1. Positive

2. Negative

3. Zero




   ...
Correct Answer:

1. Positive       Vaporization of a liquid
                  to a gas leads to a large
2. Negative       ...
SAMPLE EXERCISE 19.3 Predicting the Sign of ΔS


Predict whether ΔS is positive or
negative for each of the following
proc...
SAMPLE EXERCISE 19.3 Predicting the Sign of ΔS


Predict whether ΔS is positive or negative for each of the following proc...
PRACTICE EXERCISE
Indicate whether each of the following
processes produces an increase or
decrease in the entropy of the ...
PRACTICE EXERCISE
Indicate whether each of the following
processes produces an increase or
decrease in the entropy of the ...
SAMPLE EXERCISE 19.4 Predicting Which Sample of Matter Has
the Higher Entropy



Choose the sample of matter that
has grea...
SAMPLE EXERCISE 19.4 Predicting Which Sample of Matter Has the Higher Entropy


Choose the sample of matter that has great...
SAMPLE EXERCISE 19.4 Predicting Which Sample of Matter Has the Higher Entropy


Choose the sample of matter that has great...
SAMPLE EXERCISE 19.4 Predicting Which Sample of Matter Has the Higher Entropy


Choose the sample of matter that has great...
SAMPLE EXERCISE 19.4 Predicting Which Sample of Matter Has the Higher Entropy


Choose the sample of matter that has great...
SAMPLE EXERCISE 19.4 Predicting Which Sample of Matter Has the Higher Entropy


Choose the sample of matter that has great...
PRACTICE EXERCISE
Choose the substance with the greater
entropy in each case:
(a) 1 mol of H2(g) at STP or 1 mol of
     H...
PRACTICE EXERCISE
     Choose the substance with the greater
     entropy in each case:
     (a) 1 mol of H2(g) at STP or ...
Which of the following would be
 expected to have the highest entropy?
1.   1 mole N2(l)
2.   1 mole N2(g)
3.   1 mole Ar(...
Correct Answer:
1.   1 mole N2(l)   Given the same amounts, gases
2.   1 mole N2(g)   have higher entropy than
           ...
Third Law of Thermodynamics

       The entropy of a pure crystalline
       substance at absolute zero is 0.




        ...
Chemical
Thermodynamics
It must be a perfect crystal at 0K (absolute zero).




                                                  Chemical
       ...
Chapter 19- Chemical
     Thermodynamics
Sections 19.4 - 19.6
All about Free Energy
Standard Entropies




                        Chemical
                     Thermodynamics
Standard Entropies

• These are molar
  entropy values of
  substances in their
  standard states.




                   ...
Standard Entropies

• These are molar
  entropy values of
  substances in their
  standard states.
• Standard entropies te...
Standard Entropies

Larger and more complex molecules have
greater entropies.




                                      Ch...
Which substance will
 have the highest
     entropy?
         1. Butane
         2. Isobutane
         3. Pentane
        ...
Which substance will
 have the highest
     entropy?
         1. Butane
         2. Isobutane
         3. Pentane
        ...
Predict whether entropy increases,
decreases, or stays constant for:
       2 NO2(g) → 2 NO(g) + O2(g)


1. Increases
2. D...
Predict whether entropy increases,
  decreases, or stays constant for:
         2 NO2(g) → 2 NO(g) + O2(g)


  1. Increase...
Which process will have a
          negative ΔS?
1. Dissolving a substance
2. Melting
3. Falling leaves
4. Oxidation of a ...
Which process will have a
          negative ΔS?
1. Dissolving a substance
2. Melting
3. Falling leaves
4. Oxidation of a ...
Entropy Changes




                     Chemical
                  Thermodynamics
Entropy Changes

Entropy changes for a reaction can be
estimated in a manner analogous to that by
which ΔH is estimated:

...
SAMPLE EXERCISE 19.5 Calculating ΔS from Tabulated Entropies



Calculate ΔS° for the
synthesis of ammonia
from N2(g) and ...
SAMPLE EXERCISE 19.5 Calculating ΔS from Tabulated Entropies


  Calculate ΔS° for the synthesis of ammonia from N2(g) and...
PRACTICE EXERCISE
Using the standard
entropies in Appendix C,
calculate the standard
entropy change, ΔS°, for
the followin...
PRACTICE EXERCISE
Using the standard
entropies in Appendix C,
calculate the standard
entropy change, ΔS°, for
the followin...
Calculate ΔS° for the equation below using the
standard entropy data given:
             2 NO(g) + O2(g) → 2 NO2(g)
ΔS° va...
Correct Answer:
1. +176 J/mol             3. −147 J/mol
2. +147 J/mol             4. −76 J/mol


ΔS° = Σ ΔS ° (products) −...
Entropy Changes in Surroundings




                              Chemical
                           Thermodynamics
Entropy Changes in Surroundings
 • Heat that flows into or out of the
   system changes the entropy of the
   surroundings...
Entropy Changes in Surroundings
 • Heat that flows into or out of the
   system changes the entropy of the
   surroundings...
Entropy Changes in Surroundings
 • Heat that flows into or out of the
   system changes the entropy of the
   surroundings...
−qsys
               ΔSsurr =
                         T
• At constant pressure, qsys is simply
  ΔH° for the system.     ...
always increase



                             −qsys
                    ΔSsurr =
                              T
• At co...
Entropy Change in the Universe




                              Chemical
                           Thermodynamics
Entropy Change in the Universe

• The universe is composed of the system
  and the surroundings.




                     ...
Entropy Change in the Universe

• The universe is composed of the system
  and the surroundings.
• Therefore,




        ...
Entropy Change in the Universe

• The universe is composed of the system
  and the surroundings.
• Therefore,
     ΔSunive...
Entropy Change in the Universe

• The universe is composed of the system
  and the surroundings.
• Therefore,
     ΔSunive...
Entropy Change in the Universe

• The universe is composed of the system
  and the surroundings.
• Therefore,
     ΔSunive...
Entropy Change in the Universe




                              Chemical
                           Thermodynamics
Entropy Change in the Universe

• This becomes:
                             −ΔHsystem
     ΔSuniverse = ΔSsystem +
      ...
Gibbs Free Energy




                       Chemical
                    Thermodynamics
Gibbs Free Energy

• −TΔSuniverse is defined as the Gibbs free
  energy, ΔG.




                                         ...
Gibbs Free Energy

• −TΔSuniverse is defined as the Gibbs free
  energy, ΔG.
• When ΔSuniverse is positive, ΔG is negative...
Gibbs Free Energy

• −TΔSuniverse is defined as the Gibbs free
  energy, ΔG.
• When ΔSuniverse is positive, ΔG is negative...
Chemical
Thermodynamics
Entropy of universe increases and free energy of
the system decreases.




                                               ...
Entropy of universe increases and free energy of
the system decreases.




                                               ...
Gibbs Free Energy




                       Chemical
                    Thermodynamics
Gibbs Free Energy
         1. If ΔG is negative, the
            forward reaction is
            spontaneous.




        ...
Gibbs Free Energy
         1. If ΔG is negative, the
            forward reaction is
            spontaneous.
         2. ...
Gibbs Free Energy
         1. If ΔG is negative, the
            forward reaction is
            spontaneous.
         2. ...
Standard Free Energy Changes

 Analogous to standard enthalpies of
 formation are standard free energies of
 formation, ΔG...
Standard Free Energy Changes

 Analogous to standard enthalpies of
 formation are standard free energies of
 formation, ΔG...
Calculate ΔG° for the equation below using
the Gibbs free energy data given:
           2 SO2(g) + O2(g)  2 SO3(g)
ΔG° va...
Correct Answer:
   1.    +70 kJ
   2.    +140 kJ
   3.    −140 kJ
   4.    −70 kJ

ΔG ° =    ∑ΔGf° (products) − ∑ ΔGf° (re...
Chemical
Thermodynamics
It indicates the process has taken place under standard
      conditions.




                                            ...
It indicates the process has taken place under standard
      conditions.




                                            ...
It indicates the process has taken place under standard
      conditions.


298K = 25°C      this is NOT STP (273K)




  ...
It indicates the process has taken place under standard
      conditions.


298K = 25°C       this is NOT STP (273K)
1 atm...
It indicates the process has taken place under standard
      conditions.


298K = 25°C        this is NOT STP (273K)
1 at...
Calculate ΔG° for the equation below using
the thermodynamic data given:
           N2(g) + 3 H2(g) → 2 NH3(g)
ΔH° (NH3) =...
Correct Answer:

1.   +33 kJ
                         ΔH° = −92 kJ
2.   +66 kJ         ΔS° = −198.7J/mol − K
3.   −66 kJ  ...
SAMPLE EXERCISE 19.6 Calculating Standard Free-Energy
Change from Free Energies of Formation


(a) By using data from Appe...
SAMPLE EXERCISE 19.6 Calculating Standard Free-Energy Change
                                         from Free Energies o...
PRACTICE EXERCISE
By using data from Appendix C,
calculate ΔG° at 298 K for the
combustion of methane:




               ...
PRACTICE EXERCISE
By using data from Appendix C,
calculate ΔG° at 298 K for the
combustion of methane:



 Answer: –800.7 ...
SAMPLE EXERCISE 19.7 Estimating and Calculating ΔG°

In Section 5.7 we used Hess’s law to
calculate ΔH° for the combustion...
SAMPLE EXERCISE 19.7 Estimating and Calculating ΔG°
 In Section 5.7 we used Hess’s law to calculate ΔH° for the combustion...
PRACTICE EXERCISE
Consider the combustion of propane to
form CO2(g) and H2O(g) at 298 K:

Would you expect ΔG° to be more
...
PRACTICE EXERCISE
Consider the combustion of propane to
form CO2(g) and H2O(g) at 298 K:

Would you expect ΔG° to be more
...
Free Energy Changes




                         Chemical
                      Thermodynamics
Free Energy Changes

At temperatures other than 25°C,

          ΔG° = ΔH° − TΔS°

How does ΔG° change with temperature?

...
Free Energy and Temperature




                            Chemical
                         Thermodynamics
Free Energy and Temperature

• There are two parts to the free energy
  equation:
  ΔH°— the enthalpy term
  TΔS° — the ...
Upon heating, limestone (CaCO3) decomposes to
CaO and CO2. Speculate on the sign of ΔH and
ΔS for this process.
   CaCO3(s...
Upon heating, limestone (CaCO3) decomposes to
CaO and CO2. Speculate on the sign of ΔH and
ΔS for this process.
   CaCO3(s...
Free Energy and Temperature




                            Chemical
                         Thermodynamics
Chemical
Thermodynamics
ΔH < TΔS




              Chemical
           Thermodynamics
ΔH < TΔS
ΔG(Negative/spontaneous)=




                               Chemical
                            Thermodynamics
ΔH < TΔS
ΔG(Negative/spontaneous)=
 ΔH (Positive/vaporization) - TΔS (positive/liquid to gas)



                         ...
ΔH < TΔS
ΔG(Negative/spontaneous)=
 ΔH (Positive/vaporization) - TΔS (positive/liquid to gas)
                            ...
Both the entropy, ΔS° and the enthalpy ΔH°
have positive values. Near absolute zero (0 K),
will the process be spontaneous...
Correct Answer:
     1. Spontaneous

     2. Nonspontaneous

At low temperatures, the enthalpy
term dominates the entropy ...
A reaction will be spontaneous at
lower temperatures when the sign
          of ΔH and ΔS is




                         ...
A reaction will be spontaneous at
lower temperatures when the sign
          of ΔH and ΔS is




                         ...
SAMPLE EXERCISE 19.8 Determining the Effect of Temperature
on Spontaneity

The Haber process for the production
of ammonia...
SAMPLE EXERCISE 19.8 continued

    Solution
    Analyze: In part (a) we are asked to predict the direction in which ΔG° f...
PRACTICE EXERCISE
(a) Using standard enthalpies of
     formation and standard entropies in
    Appendix C, calculate ΔH° ...
PRACTICE EXERCISE
 (a) Using standard enthalpies of
      formation and standard entropies in
     Appendix C, calculate Δ...
Chapter 19- Chemical
     Thermodynamics
Section 19.7
  Free Energy & Keq
Free Energy and Equilibrium




                            Chemical
                         Thermodynamics
Free Energy and Equilibrium
 Under any conditions, standard or
 nonstandard, the free energy change
 can be found this way...
SAMPLE EXERCISE 19.9 Relating ΔG to a Phase Change at Equilibrium

The normal boiling point is the temperature
at which a ...
SAMPLE EXERCISE 19.9 Relating ΔG to a Phase Change at Equilibrium


As we saw in Section 11.5, the normal boiling point is...
SAMPLE EXERCISE 19.9 continued

Solving the equation for Tb, we obtain


Strictly speaking, we would need the values of ΔH...
PRACTICE EXERCISE
Use data in Appendix C to estimate the
normal boiling point, in K, for elemental
bromine, Br2(l). (The e...
PRACTICE EXERCISE
Use data in Appendix C to estimate the
normal boiling point, in K, for elemental
bromine, Br2(l). (The e...
SAMPLE EXERCISE 19.10 Calculating the Free-Energy Change
Under Nonstandard Conditions


We will continue to explore the Ha...
SAMPLE EXERCISE 19.10 Calculating the Free-Energy Change Under Nonstandard Conditions
   We will continue to explore the H...
PRACTICE EXERCISE
Calculate ΔG at 298 K for the reaction
of nitrogen and hydrogen to form
ammonia if the reaction mixture
...
PRACTICE EXERCISE
Calculate ΔG at 298 K for the reaction
of nitrogen and hydrogen to form
ammonia if the reaction mixture
...
Decomposition of CaCO3 has a ΔH° =
178.3 kJ/mol and ΔS° = 159 J/mol • K.
At what temperature does this become
spontaneous?...
Correct Answer:

1.   121°C               T = ΔH°/ΔS°
2.   395°C
3.   848°C    T = 178.3 kJ/mol/0.159 kJ/mol • K
4.   1121...
Free Energy and Equilibrium




                            Chemical
                         Thermodynamics
Free Energy and Equilibrium

• At equilibrium, Q = K, and ΔG = 0.




                                          Chemical
 ...
Free Energy and Equilibrium

• At equilibrium, Q = K, and ΔG = 0.
• The equation becomes




                             ...
Free Energy and Equilibrium

• At equilibrium, Q = K, and ΔG = 0.
• The equation becomes
              0 = ΔG° + RT lnK


...
Free Energy and Equilibrium

• At equilibrium, Q = K, and ΔG = 0.
• The equation becomes
              0 = ΔG° + RT lnK
• ...
Free Energy and Equilibrium

• At equilibrium, Q = K, and ΔG = 0.
• The equation becomes
              0 = ΔG° + RT lnK
• ...
Free Energy and Equilibrium

• At equilibrium, Q = K, and ΔG = 0.
• The equation becomes
              0 = ΔG° + RT lnK
• ...
Free Energy and Equilibrium

• At equilibrium, Q = K, and ΔG = 0.
• The equation becomes
              0 = ΔG° + RT lnK
• ...
Suppose ΔG° is a large, positive value.
What then will be the value of the
equilibrium constant, K?

1.   K=0
2.   K=1
3. ...
Correct Answer:

                       ΔG° = −RTlnK
1.   K=0
             Thus, large positive values of ΔG°
2.   K=1
   ...
N2(g) + 3 H2(g)  2 NH3(g)      ΔH° = -92.4 kJ/mol
If the temperature is decreased, what is the effect
        on the equi...
N2(g) + 3 H2(g)  2 NH3(g)      ΔH° = -92.4 kJ/mol
If the temperature is decreased, what is the effect
        on the equi...
SAMPLE EXERCISE 19.11 Calculating an Equilibrium Constant from ΔG°

 Use standard free energies of
 formation to calculate...
SAMPLE EXERCISE 19.11 Calculating an Equilibrium Constant from ΔG°
 Use standard free energies of formation to calculate t...
SAMPLE EXERCISE 19.11 Calculating an Equilibrium Constant from ΔG°
 Use standard free energies of formation to calculate t...
SAMPLE EXERCISE 19.11 Calculating an Equilibrium Constant from ΔG°
 Use standard free energies of formation to calculate t...
SAMPLE EXERCISE 19.11 Calculating an Equilibrium Constant from ΔG°
 Use standard free energies of formation to calculate t...
SAMPLE EXERCISE 19.11 Calculating an Equilibrium Constant from ΔG°
 Use standard free energies of formation to calculate t...
SAMPLE EXERCISE 19.11 Calculating an Equilibrium Constant from ΔG°
    Use standard free energies of formation to calculat...
PRACTICE EXERCISE
Use data from Appendix C to calculate
the standard free-energy change, ΔG°,
and the equilibrium constant...
PRACTICE EXERCISE
Use data from Appendix C to calculate
the standard free-energy change, ΔG°,
and the equilibrium constant...
SAMPLE INTEGRATIVE EXERCISE Putting Concepts Together
Consider the equilibria in which these salts dissolve in water to fo...
SAMPLE INTEGRATIVE EXERCISE Putting Concepts Together


Consider the simple salts NaCl(s) and AgCl(s). We will examine the...
SAMPLE INTEGRATIVE EXERCISE continued

   (b) We can write                 as the sum of an enthalpy term,                ...
SAMPLE INTEGRATIVE EXERCISE continued


     (d) A soluble salt is one that dissolves appreciably in water. • (Section 4.2...
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Chapter 19 Lecture- Thermodynamics

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Transcript of "Chapter 19 Lecture- Thermodynamics"

  1. 1. Chapter 19- Chemical Thermodynamics Sections 19.1 - 19.3 Spontaneous processes & entropy
  2. 2. First Law of Thermodynamics Chemical Thermodynamics
  3. 3. First Law of Thermodynamics • You will recall from Chapter 5 that energy cannot be created nor destroyed. Chemical Thermodynamics
  4. 4. 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. Chemical Thermodynamics
  5. 5. 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. Chemical Thermodynamics
  6. 6. Spontaneous Processes Chemical Thermodynamics
  7. 7. Spontaneous Processes • Spontaneous processes are those that can proceed without any outside intervention. Chemical Thermodynamics
  8. 8. 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 return Chemical Thermodynamics
  9. 9. 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 return A process is either spontaneous, Chemical non-spontaneous, or at equilibrium. Thermodynamics
  10. 10. Spontaneous Processes Processes that are spontaneous in one direction are nonspontaneous in the reverse direction. Chemical Thermodynamics
  11. 11. Melting a cube of water ice at −10°C and atmospheric pressure is a ________ process. 1. Spontaneous 2. Nonspontaneous Chemical Thermodynamics
  12. 12. Correct Answer: Melting of an ice cube at 1. Spontaneous 1 atm pressure will only be spontaneous above 2. Nonspontaneous the freezing point (0°C). Chemical Thermodynamics
  13. 13. Spontaneous Processes Chemical Thermodynamics
  14. 14. Spontaneous Processes • Processes that are spontaneous at one temperature may be nonspontaneous at other temperatures. Chemical Thermodynamics
  15. 15. 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. Chemical Thermodynamics
  16. 16. 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. Chemical Thermodynamics
  17. 17. Chemical Thermodynamics
  18. 18. No. Nonspontaneous processes can occur with some external assistance. Chemical Thermodynamics
  19. 19. SAMPLE EXERCISE 19.1 Identifying Spontaneous Processes Predict whether these processes are spontaneous as described, spontaneous in the reverse direction, or in equilibrium: (a) When a piece of metal heated to 150°C is added to water at 40°C, the water gets hotter. (b) Water at room temperature decomposes into H2(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, 80.1°C.
  20. 20. SAMPLE EXERCISE 19.1 Identifying Spontaneous Processes Predict whether these processes are spontaneous as described, spontaneous in the reverse direction, or in equilibrium: (a) When a piece of metal heated to 150°C is added to water at 40°C, the water gets hotter. (b) Water at room temperature decomposes into H2(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, 80.1°C. Analyze: We are asked to judge whether each process will proceed spontaneously in the direction indicated, in the reverse direction, or in neither direction. Plan: We need to think about whether each process is consistent with our experience about the natural direction of events or whether it is the reverse process that we expect to occur. Solve: (a) This process is spontaneous. Whenever two objects at different temperatures are brought into contact, heat is transferred from the hotter object to the colder one. In this instance heat is transferred from the hot metal to the cooler water. The final temperature, after the metal and water achieve the same temperature (thermal equilibrium), will be somewhere between the initial temperatures of the metal and the water. (b) Experience tells us that this process is not spontaneous—we certainly have never seen hydrogen and oxygen gas bubbling up out of water! Rather, the reverse process—the reaction of H2 and O2 to form H2O—is spontaneous once initiated by a spark or flame. (c) By definition, the normal boiling point is the temperature at which a vapor at 1 atm is in equilibrium with its liquid. Thus, this is an equilibrium situation. Neither the condensation of benzene vapor nor the reverse process is spontaneous. If the temperature were below 80.1°C, condensation would be spontaneous.
  21. 21. PRACTICE EXERCISE Under 1 atm pressure CO2(s) sublimes at –78°C. Is the transformation of CO2(s) to CO2(g) a spontaneous process at –100ºC and 1 atm pressure? Chemical Thermodynamics
  22. 22. PRACTICE EXERCISE Under 1 atm pressure CO2(s) sublimes at –78°C. Is the transformation of CO2(s) to CO2(g) a spontaneous process at –100ºC and 1 atm pressure? Answer: No, the reverse process is spontaneous at this temperature. Chemical Thermodynamics
  23. 23. 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. Chemical Thermodynamics
  24. 24. Irreversible Processes Chemical Thermodynamics
  25. 25. Irreversible Processes • Irreversible processes cannot be undone by exactly reversing the change to the system. Chemical Thermodynamics
  26. 26. Irreversible Processes • Irreversible processes cannot be undone by exactly reversing the change to the system. • Spontaneous processes are irreversible. Chemical Thermodynamics
  27. 27. Chemical Thermodynamics
  28. 28. No Chemical Thermodynamics
  29. 29. Entropy Chemical Thermodynamics
  30. 30. Entropy • Entropy (S) is a term coined by Rudolph Clausius in the 19th century. Chemical Thermodynamics
  31. 31. 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 Chemical Thermodynamics
  32. 32. Entropy Chemical Thermodynamics
  33. 33. Entropy • Entropy can be thought of as a measure of the randomness of a system. Chemical Thermodynamics
  34. 34. Entropy • Entropy can be thought of as a measure of the randomness of a system. • It is related to the various modes of motion in molecules. Chemical Thermodynamics
  35. 35. Entropy Chemical Thermodynamics
  36. 36. Entropy • Like total energy, E, and enthalpy, H, entropy is a state function. Chemical Thermodynamics
  37. 37. Entropy • Like total energy, E, and enthalpy, H, entropy is a state function. • Therefore, Chemical Thermodynamics
  38. 38. Entropy • Like total energy, E, and enthalpy, H, entropy is a state function. • Therefore, ΔS = Sfinal − Sinitial Chemical Thermodynamics
  39. 39. 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: Chemical Thermodynamics
  40. 40. 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 ΔS = T Chemical Thermodynamics
  41. 41. Chemical Thermodynamics
  42. 42. • ΔS depends not merely on q but on qrev. There is only one reversible isothermal path between two states regardless of the number of possible paths. Chemical Thermodynamics
  43. 43. SAMPLE EXERCISE 19.2 Calculating ΔS for a Phase Change The element mercury, Hg, is a silvery liquid at room temperature. The normal freezing point of mercury is –38.9ºC, and its molar enthalpy of fusion is ΔΗfusion = 2.29 kJ/mol. What is the entropy change of the system when 50.0 g of Hg(l) freezes at the normal freezing point? Chemical Thermodynamics
  44. 44. SAMPLE EXERCISE 19.2 Calculating ΔS for a Phase Change The element mercury, Hg, is a silvery liquid at room temperature. The normal freezing point of mercury is –38.9ºC, and its molar enthalpy of fusion is ΔΗfusion = 2.29 kJ/mol. What is the entropy change of the system when 50.0 g of Hg(l) freezes at the normal freezing point? Chemical Thermodynamics
  45. 45. SAMPLE EXERCISE 19.2 Calculating ΔS for a Phase Change The element mercury, Hg, is a silvery liquid at room temperature. The normal freezing point of mercury is –38.9ºC, and its molar enthalpy of fusion is ΔΗfusion = 2.29 kJ/mol. What is the entropy change of the system when 50.0 g of Hg(l) freezes at the normal freezing point? Chemical Thermodynamics
  46. 46. SAMPLE EXERCISE 19.2 Calculating ΔS for a Phase Change The element mercury, Hg, is a silvery liquid at room temperature. The normal freezing point of mercury is –38.9ºC, and its molar enthalpy of fusion is ΔΗfusion = 2.29 kJ/mol. What is the entropy change of the system when 50.0 g of Hg(l) freezes at the normal freezing point? Solution Analyze: We first recognize that freezing is an exothermic process; heat is transferred from the system to the surroundings when a liquid freezes (q < 0). The enthalpy of fusion is ΔΗ for the melting process. Because freezing is the reverse of melting, the enthalpy change that accompanies the freezing of 1 mol of Hg is –ΔΗfusion = 2.29 kJ/mol. Plan: We can use –ΔΗfusion and the atomic weight of Hg to calculate q for freezing 50.0 g of Hg: We can use this value of q as qrev in Equation 19.2. We must first, however, convert the temperature to K: Solve: We can now calculate the value of ΔSsys: Check: The entropy change is negative because heat flows from the system making qrev negative. Comment: The procedure we have used here can be used to calculate ΔS for other isothermal phase changes, such as the vaporization of a liquid at its boiling point. Chemical Thermodynamics
  47. 47. SAMPLE EXERCISE 19.2 continued PRACTICE EXERCISE The normal boiling point of ethanol, C2H5OH, is 78.3°C (Figure 11.24), and its molar enthalpy of vaporization is 38.56 kJ/mol. What is the change in entropy in the system when 68.3 g of C2H5OH(g) at 1 atm condenses to liquid at the normal boiling point? Chemical Thermodynamics
  48. 48. SAMPLE EXERCISE 19.2 continued PRACTICE EXERCISE The normal boiling point of ethanol, C2H5OH, is 78.3°C (Figure 11.24), and its molar enthalpy of vaporization is 38.56 kJ/mol. What is the change in entropy in the system when 68.3 g of C2H5OH(g) at 1 atm condenses to liquid at the normal boiling point? Answer: –163 J/K Chemical Thermodynamics
  49. 49. 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. Chemical Thermodynamics
  50. 50. Second Law of Thermodynamics Chemical Thermodynamics
  51. 51. Second Law of Thermodynamics In other words: For reversible processes: ΔSuniv = ΔSsystem + ΔSsurroundings = 0 For irreversible processes: ΔSuniv = ΔSsystem + ΔSsurroundings > 0 Chemical Thermodynamics
  52. 52. Second Law of Thermodynamics These last truths mean that as a result of all spontaneous processes the entropy of the universe increases. Chemical Thermodynamics
  53. 53. Chemical Thermodynamics
  54. 54. The entropy of the universe for the process must increase by a greater amount than the entropy of the system decreases. Chemical Thermodynamics
  55. 55. Entropy on the Molecular Scale Chemical Thermodynamics
  56. 56. Entropy on the Molecular Scale • Ludwig Boltzmann described the concept of entropy on the molecular level. Chemical Thermodynamics
  57. 57. 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. Chemical Thermodynamics
  58. 58. Entropy on the Molecular Scale Chemical Thermodynamics
  59. 59. 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 σ bonds. Chemical Thermodynamics
  60. 60. Chemical Thermodynamics
  61. 61. A molecule can vibrate (atoms moving relative to one another) and rotate (tumble); a single atom can only rotate. Chemical Thermodynamics
  62. 62. Entropy on the Molecular Scale Chemical Thermodynamics
  63. 63. 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. Chemical Thermodynamics
  64. 64. Entropy on the Molecular Scale Chemical Thermodynamics
  65. 65. Entropy on the Molecular Scale • Each thermodynamic state has a specific number of microstates, W, associated with it. Chemical Thermodynamics
  66. 66. Entropy on the Molecular Scale • Each thermodynamic state has a specific number of microstates, W, associated with it. • Entropy is Chemical Thermodynamics
  67. 67. Entropy on the Molecular Scale • Each thermodynamic state has a specific number of microstates, W, associated with it. • Entropy is S = k lnW Chemical Thermodynamics
  68. 68. 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. Chemical Thermodynamics
  69. 69. S = k lnW Chemical Thermodynamics
  70. 70. S = k lnW S = 0 Chemical Thermodynamics
  71. 71. Entropy on the Molecular Scale Chemical Thermodynamics
  72. 72. Entropy on the Molecular Scale • The change in entropy for a process, then, is ΔS = k lnWfinal − k lnWinitial lnWfinal ΔS = k ln lnWinitial Chemical Thermodynamics
  73. 73. Entropy on the Molecular Scale • The change in entropy for a process, then, is ΔS = k lnWfinal − k lnWinitial lnWfinal ΔS = k ln lnWinitial • Entropy increases with the number of microstates in the system. Chemical Thermodynamics
  74. 74. Entropy on the Molecular Scale Chemical Thermodynamics
  75. 75. 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. Chemical Thermodynamics
  76. 76. Entropy and Physical States Chemical Thermodynamics
  77. 77. Entropy and Physical States • Entropy increases with the freedom of motion of molecules. Chemical Thermodynamics
  78. 78. Entropy and Physical States • Entropy increases with the freedom of motion of molecules. • Therefore, Chemical Thermodynamics
  79. 79. Entropy and Physical States • Entropy increases with the freedom of motion of molecules. • Therefore, S(g) > S(l) > S(s) Chemical Thermodynamics
  80. 80. Solutions Generally, when a solid is dissolved in a solvent, entropy increases. Chemical Thermodynamics
  81. 81. Entropy Changes Chemical Thermodynamics
  82. 82. 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. Chemical Thermodynamics
  83. 83. The sign of entropy change, ΔS, associated with the boiling of water is _______. 1. Positive 2. Negative 3. Zero Chemical Thermodynamics
  84. 84. Correct Answer: 1. Positive Vaporization of a liquid to a gas leads to a large 2. Negative increase in volume and hence entropy; ΔS 3. Zero must be positive. Chemical Thermodynamics
  85. 85. SAMPLE EXERCISE 19.3 Predicting the Sign of ΔS Predict whether ΔS is positive or negative for each of the following processes, assuming each occurs at constant temperature: Chemical Thermodynamics
  86. 86. SAMPLE EXERCISE 19.3 Predicting the Sign of ΔS Predict whether ΔS is positive or negative for each of the following processes, assuming each occurs at constant temperature: Solution Analyze: We are given four equations and asked to predict the sign of ΔS for each chemical reaction. Plan: The sign of ΔS will be positive if there is an increase in temperature, an increase in the volume in which the molecules move, or an increase in the number of gas particles in the reaction. The question states that the temperature is constant. Thus, we need to evaluate each equation with the other two factors in mind. Solve: (a) The evaporation of a liquid is accompanied by a large increase in volume. One mole of water (18 g) occupies about 18 mL as a liquid and 22.4 L as a gas at STP. Because the molecules are distributed throughout a much larger volume in the gaseous state than in the liquid state, an increase in motional freedom accompanies vaporization. Therefore, ΔS is positive. (b) In this process the ions, which are free to move throughout the volume of the solution, form a solid in which they are confined to a smaller volume and restricted to more highly constrained positions. Thus, ΔS is negative. (c) The particles of a solid are confined to specific locations and have fewer ways to move (fewer microstates) than do the molecules of a gas. Because O2 gas is converted into part of the solid product Fe2O3, ΔS is negative. (d) The number of moles of gases is the same on both sides of the equation, and so the entropy change will be small. The sign of ΔS is impossible to predict based on our discussions thus far, but we can predict that ΔS will be close to zero.
  87. 87. PRACTICE EXERCISE Indicate whether each of the following processes produces an increase or decrease in the entropy of the system: Chemical Thermodynamics
  88. 88. PRACTICE EXERCISE Indicate whether each of the following processes produces an increase or decrease in the entropy of the system: Answers: (a) increase, (b) decrease, (c) decrease, (d) decrease Chemical Thermodynamics
  89. 89. 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 25°C, (b) 2 mol of HCl(g) or 1 mol of HCl(g) at 25°C, (c) 1 mol of HCl(g) or 1 mol of Ar(g) at 298 K. Chemical Thermodynamics
  90. 90. 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 25°C, (b) 2 mol of HCl(g) or 1 mol of HCl(g) at 25°C, (c) 1 mol of HCl(g) or 1 mol of Ar(g) at 298 K. Chemical Thermodynamics
  91. 91. 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 25°C, (b) 2 mol of HCl(g) or 1 mol of HCl(g) at 25°C, (c) 1 mol of HCl(g) or 1 mol of Ar(g) at 298 K. Solution Analyze: We need to select the system in each pair that has the greater entropy. Plan: To do this, we examine the state of the system and the complexity of the molecules it contains. Chemical Thermodynamics
  92. 92. 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 25°C, (b) 2 mol of HCl(g) or 1 mol of HCl(g) at 25°C, (c) 1 mol of HCl(g) or 1 mol of Ar(g) at 298 K. Solution Analyze: We need to select the system in each pair that has the greater entropy. Plan: To do this, we examine the state of the system and the complexity of the molecules it contains. Solve: (a) Gaseous HCl has the higher entropy because gases have more available motions than solids. (b) The sample containing 2 mol of HCl has twice the number of molecules as the sample containing 1 mol. Thus, the 2-mol sample has twice the number of microstates and twice the entropy. (c) The HCl sample has the higher entropy because the HCl molecule is capable of storing energy in more ways than is Ar. HCl molecules can rotate and vibrate; Ar atoms cannot. Chemical Thermodynamics
  93. 93. 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 25°C, (b) 2 mol of HCl(g) or 1 mol of HCl(g) at 25°C, (c) 1 mol of HCl(g) or 1 mol of Ar(g) at 298 K. Solution Analyze: We need to select the system in each pair that has the greater entropy. Plan: To do this, we examine the state of the system and the complexity of the molecules it contains. Solve: (a) Gaseous HCl has the higher entropy because gases have more available motions than solids. (b) The sample containing 2 mol of HCl has twice the number of molecules as the sample containing 1 mol. Thus, the 2-mol sample has twice the number of microstates and twice the entropy. (c) The HCl sample has the higher entropy because the HCl molecule is capable of storing energy in more ways than is Ar. HCl molecules can rotate and vibrate; Ar atoms cannot. 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 100°C and 0.5 atm, (b) 1 mol of H2O(s) at 0°C or 1 mol of H2O(l) at 25°C, (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. Chemical Thermodynamics
  94. 94. 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 25°C, (b) 2 mol of HCl(g) or 1 mol of HCl(g) at 25°C, (c) 1 mol of HCl(g) or 1 mol of Ar(g) at 298 K. Solution Analyze: We need to select the system in each pair that has the greater entropy. Plan: To do this, we examine the state of the system and the complexity of the molecules it contains. Solve: (a) Gaseous HCl has the higher entropy because gases have more available motions than solids. (b) The sample containing 2 mol of HCl has twice the number of molecules as the sample containing 1 mol. Thus, the 2-mol sample has twice the number of microstates and twice the entropy. (c) The HCl sample has the higher entropy because the HCl molecule is capable of storing energy in more ways than is Ar. HCl molecules can rotate and vibrate; Ar atoms cannot. 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 100°C and 0.5 atm, (b) 1 mol of H2O(s) at 0°C or 1 mol of H2O(l) at 25°C, (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. Answers: (a) 1 mol of H2(g) at 100°C and 0.5 atm, (b) 1 mol of H2O(l) at 25°C, (c) 1 mol of SO2(g) at STP, (d) 2 mol NO2(g) of at STP Chemical Thermodynamics
  95. 95. 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 100°C and 0.5 atm, (b) 1 mol of H2O(s) at 0°C or 1 mol of H2O(l) at 25°C, (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.
  96. 96. 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 100°C and 0.5 atm, (b) 1 mol of H2O(s) at 0°C or 1 mol of H2O(l) at 25°C, (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. Answers: (a) 1 mol of H (g) at 100°C and 0.5 atm, 2 (b) 1 mol of H2O(l) at 25°C, (c) 1 mol of SO2(g) at STP, (d) 2 mol NO (g) of at STP
  97. 97. Which of the following would be expected to have the highest entropy? 1. 1 mole N2(l) 2. 1 mole N2(g) 3. 1 mole Ar(g) 4. 1 mole Ar(s) Chemical Thermodynamics
  98. 98. Correct Answer: 1. 1 mole N2(l) Given the same amounts, gases 2. 1 mole N2(g) have higher entropy than liquids, which have higher 3. 1 mole Ar(g) entropy than solids. Of the 4. 1 mole Ar(s) gases, N2 has greater entropy than Ar because N2 is a molecule that can store energy in ways not possible for Ar. Chemical Thermodynamics
  99. 99. Third Law of Thermodynamics The entropy of a pure crystalline substance at absolute zero is 0. Chemical Thermodynamics
  100. 100. Chemical Thermodynamics
  101. 101. It must be a perfect crystal at 0K (absolute zero). Chemical Thermodynamics
  102. 102. Chapter 19- Chemical Thermodynamics Sections 19.4 - 19.6 All about Free Energy
  103. 103. Standard Entropies Chemical Thermodynamics
  104. 104. Standard Entropies • These are molar entropy values of substances in their standard states. Chemical Thermodynamics
  105. 105. Standard Entropies • These are molar entropy values of substances in their standard states. • Standard entropies tend to increase with increasing molar mass. Chemical Thermodynamics
  106. 106. Standard Entropies Larger and more complex molecules have greater entropies. Chemical Thermodynamics
  107. 107. Which substance will have the highest entropy? 1. Butane 2. Isobutane 3. Pentane 4. Isopentane 5. Neopentane Chemical Thermodynamics
  108. 108. Which substance will have the highest entropy? 1. Butane 2. Isobutane 3. Pentane 4. Isopentane 5. Neopentane Chemical Thermodynamics
  109. 109. Predict whether entropy increases, decreases, or stays constant for: 2 NO2(g) → 2 NO(g) + O2(g) 1. Increases 2. Decreases 3. Stays constant Chemical Thermodynamics
  110. 110. Predict whether entropy increases, decreases, or stays constant for: 2 NO2(g) → 2 NO(g) + O2(g) 1. Increases 2. Decreases 3. Stays constant The entropy increases because two molecules of gas react to form three molecules of gas, leading to more disorder. Chemical Thermodynamics
  111. 111. Which process will have a negative ΔS? 1. Dissolving a substance 2. Melting 3. Falling leaves 4. Oxidation of a metal 5. Decomposition of water into H2 and O2 Dissolution of NaCl Chemical Thermodynamics
  112. 112. Which process will have a negative ΔS? 1. Dissolving a substance 2. Melting 3. Falling leaves 4. Oxidation of a metal 5. Decomposition of water Dissolution of NaCl into H2 and O2 Chemical Thermodynamics
  113. 113. Entropy Changes Chemical Thermodynamics
  114. 114. Entropy Changes Entropy changes for a reaction can be estimated in a manner analogous to that by which ΔH is estimated: ΔS° = ΣnΔS°(products) - ΣmΔS°(reactants) where n and m are the coefficients in the balanced chemical equation. Chemical Thermodynamics
  115. 115. SAMPLE EXERCISE 19.5 Calculating ΔS from Tabulated Entropies Calculate ΔS° for the synthesis of ammonia from N2(g) and H2(g) at 298 K: Chemical Thermodynamics
  116. 116. SAMPLE EXERCISE 19.5 Calculating ΔS from Tabulated Entropies Calculate ΔS° for the synthesis of ammonia from N2(g) and H2(g) at 298 K: Solution Analyze: We are asked to calculate the entropy change for the synthesis of NH3(g) from its constituent elements. Plan: We can make this calculation using Equation 19.8 and the standard molar entropy values for the reactants and the products that are given in Table 19.2 and in Appendix C. Solve: Using Equation 19.8, we have Substituting the appropriate S° values from Table 19.2 yields Chemical Thermodynamics Check: The value for ΔS° is negative, in agreement with our qualitative prediction based on the decrease in the number of molecules of gas during the reaction.
  117. 117. PRACTICE EXERCISE Using the standard entropies in Appendix C, calculate the standard entropy change, ΔS°, for the following reaction at 298 K: Chemical Thermodynamics
  118. 118. PRACTICE EXERCISE Using the standard entropies in Appendix C, calculate the standard entropy change, ΔS°, for the following reaction at 298 K: Answer: 180.39 J/K Chemical Thermodynamics
  119. 119. Calculate ΔS° for the equation below using the standard entropy data given: 2 NO(g) + O2(g) → 2 NO2(g) ΔS° values (J/mol-K): NO2(g) = 240, NO(g) = 211, O2(g) = 205. 1. +176 J/mol 3. −147 J/mol 2. +147 J/mol 4. −76 J/mol Chemical Thermodynamics
  120. 120. Correct Answer: 1. +176 J/mol 3. −147 J/mol 2. +147 J/mol 4. −76 J/mol ΔS° = Σ ΔS ° (products) − Σ ΔS ° (reactants) ΔS° = 2(240) − [2(211) + 205] ΔS° = 480 − [627] ΔS° = − 147 Chemical Thermodynamics
  121. 121. Entropy Changes in Surroundings Chemical Thermodynamics
  122. 122. Entropy Changes in Surroundings • Heat that flows into or out of the system changes the entropy of the surroundings. Chemical Thermodynamics
  123. 123. Entropy Changes in Surroundings • Heat that flows into or out of the system changes the entropy of the surroundings. • For an isothermal process: −qsys ΔSsurr = T Chemical Thermodynamics
  124. 124. Entropy Changes in Surroundings • Heat that flows into or out of the system changes the entropy of the surroundings. • For an isothermal process: −qsys ΔSsurr = T • At constant pressure, qsys is simply ΔH° for the system. Chemical Thermodynamics
  125. 125. −qsys ΔSsurr = T • At constant pressure, qsys is simply ΔH° for the system. Chemical Thermodynamics
  126. 126. always increase −qsys ΔSsurr = T • At constant pressure, qsys is simply ΔH° for the system. Chemical Thermodynamics
  127. 127. Entropy Change in the Universe Chemical Thermodynamics
  128. 128. Entropy Change in the Universe • The universe is composed of the system and the surroundings. Chemical Thermodynamics
  129. 129. Entropy Change in the Universe • The universe is composed of the system and the surroundings. • Therefore, Chemical Thermodynamics
  130. 130. Entropy Change in the Universe • The universe is composed of the system and the surroundings. • Therefore, ΔSuniverse = ΔSsystem + ΔSsurroundings Chemical Thermodynamics
  131. 131. Entropy Change in the Universe • The universe is composed of the system and the surroundings. • Therefore, ΔSuniverse = ΔSsystem + ΔSsurroundings • For spontaneous processes Chemical Thermodynamics
  132. 132. Entropy Change in the Universe • The universe is composed of the system and the surroundings. • Therefore, ΔSuniverse = ΔSsystem + ΔSsurroundings • For spontaneous processes ΔSuniverse > 0 Chemical Thermodynamics
  133. 133. Entropy Change in the Universe Chemical Thermodynamics
  134. 134. Entropy Change in the Universe • This becomes: −ΔHsystem ΔSuniverse = ΔSsystem + T Multiplying both sides by −T, −TΔSuniverse = ΔHsystem − TΔSsystem Chemical Thermodynamics
  135. 135. Gibbs Free Energy Chemical Thermodynamics
  136. 136. Gibbs Free Energy • −TΔSuniverse is defined as the Gibbs free energy, ΔG. Chemical Thermodynamics
  137. 137. Gibbs Free Energy • −TΔSuniverse is defined as the Gibbs free energy, ΔG. • When ΔSuniverse is positive, ΔG is negative. Chemical Thermodynamics
  138. 138. Gibbs Free Energy • −TΔSuniverse is defined as the Gibbs free energy, ΔG. • When ΔSuniverse is positive, ΔG is negative. • Therefore, when ΔG is negative, a process is spontaneous. Chemical Thermodynamics
  139. 139. Chemical Thermodynamics
  140. 140. Entropy of universe increases and free energy of the system decreases. Chemical Thermodynamics
  141. 141. Entropy of universe increases and free energy of the system decreases. Chemical Thermodynamics
  142. 142. Gibbs Free Energy Chemical Thermodynamics
  143. 143. Gibbs Free Energy 1. If ΔG is negative, the forward reaction is spontaneous. Chemical Thermodynamics
  144. 144. Gibbs Free Energy 1. If ΔG is negative, the forward reaction is spontaneous. 2. If ΔG is 0, the system is at equilibrium. Chemical Thermodynamics
  145. 145. Gibbs Free Energy 1. If ΔG is negative, the forward reaction is spontaneous. 2. If ΔG is 0, the system is at equilibrium. 3. If ΔG is positive, the reaction is spontaneous in the reverse direction. Chemical Thermodynamics
  146. 146. Standard Free Energy Changes Analogous to standard enthalpies of formation are standard free energies of formation, ΔG°. f Chemical Thermodynamics
  147. 147. Standard Free Energy Changes Analogous to standard enthalpies of formation are standard free energies of formation, ΔG°. f ΔG° = ΣnΔG°(products) − ΣmΔG°(reactants) f f where n and m are the stoichiometric coefficients. Chemical Thermodynamics
  148. 148. Calculate ΔG° for the equation below using the Gibbs free energy data given: 2 SO2(g) + O2(g)  2 SO3(g) ΔG° values (kJ): SO2(g) = −300.4, SO3(g) = −370.4 1. +70 kJ 2. +140 kJ 3. −140 kJ 4. −70 kJ Chemical Thermodynamics
  149. 149. Correct Answer: 1. +70 kJ 2. +140 kJ 3. −140 kJ 4. −70 kJ ΔG ° = ∑ΔGf° (products) − ∑ ΔGf° (reactants) ΔG° = (2 × −370.4) − [(2 × −300.4) + 0] ΔG° = −740.8 − [−600.8] = −140 Chemical Thermodynamics
  150. 150. Chemical Thermodynamics
  151. 151. It indicates the process has taken place under standard conditions. Chemical Thermodynamics
  152. 152. It indicates the process has taken place under standard conditions. Chemical Thermodynamics
  153. 153. It indicates the process has taken place under standard conditions. 298K = 25°C this is NOT STP (273K) Chemical Thermodynamics
  154. 154. It indicates the process has taken place under standard conditions. 298K = 25°C this is NOT STP (273K) 1 atm for gases Chemical Thermodynamics
  155. 155. It indicates the process has taken place under standard conditions. 298K = 25°C this is NOT STP (273K) 1 atm for gases 1M for solutions Chemical Thermodynamics
  156. 156. Calculate ΔG° for the equation below using the thermodynamic data given: N2(g) + 3 H2(g) → 2 NH3(g) ΔH° (NH3) = −46 kJ; ΔS° values (J/mol-K) are NH3 = 192.5, N2 = 191.5, H2 = 130.6. 1. +33 kJ 3. −66 kJ 2. +66 kJ 4. −33 kJ Chemical Thermodynamics
  157. 157. Correct Answer: 1. +33 kJ ΔH° = −92 kJ 2. +66 kJ ΔS° = −198.7J/mol − K 3. −66 kJ ΔG° = ΔH° − TΔS° 4. −33 kJ ΔG° = (−92) − (298)(−0.1987) ΔG° = (−92) + (59.2) = −33 Chemical Thermodynamics
  158. 158. 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 ΔG° for the reverse of the above reaction? Chemical Thermodynamics
  159. 159. 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 ΔG° for the reverse of the above reaction? Solution Analyze: We are asked to calculate the free-energy change for the indicated reaction, and then to determine the free- energy change of its reverse. Plan: To accomplish our task, we look up the free-energy values for the products and reactants and use Equation 19.13: We multiply the molar quantities by the coefficients in the balanced equation, and subtract the total for the reactants from that for the products. Solve: (a) Cl2(g) is in its standard state, so is zero for this reactant. P4(g), however, is not in its standard state, so is not zero for this reactant. From the balanced equation and using Appendix C, we have: The fact that ΔG° is negative tells us that a mixture of P4(g), Cl2(g), and PCl3(g), at 25°C, each present at a partial pressure of 1 atm, would react spontaneously in the forward direction to form more PCl3. Remember, however, that the value of ΔG° tells us nothing about the rate at which the reaction occurs. (b) Remember that ΔG = G (products) – G (reactants). If we reverse the reaction, we reverse the roles of the reactants and products. Thus, reversing the reaction changes the sign of ΔG, just as reversing the reaction changes the sign of ΔH. • (Section 5.4) Hence, Chemical using the result from part (a): Thermodynamics
  160. 160. PRACTICE EXERCISE By using data from Appendix C, calculate ΔG° at 298 K for the combustion of methane: Chemical Thermodynamics
  161. 161. PRACTICE EXERCISE By using data from Appendix C, calculate ΔG° at 298 K for the combustion of methane: Answer: –800.7 kJ Chemical Thermodynamics
  162. 162. SAMPLE EXERCISE 19.7 Estimating and Calculating ΔG° In Section 5.7 we used Hess’s law to calculate ΔH° for the combustion of propane gas at 298 K: (a) Without using data from Appendix C, predict whether ΔG° for this reaction is more negative or less negative than ΔH°. (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?
  163. 163. SAMPLE EXERCISE 19.7 Estimating and Calculating ΔG° In Section 5.7 we used Hess’s law to calculate ΔH° for the combustion of propane gas at 298 K: (a) Without using data from Appendix C, predict whether ΔG° for this reaction is more negative or less negative than ΔH °. (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? Solution Analyze: In part (a) we must predict the value for ΔG° relative to that for ΔH° on the basis of the balanced equation for the reaction. In part (b) we must calculate the value for ΔG° and compare with our qualitative prediction. Plan: The free-energy change incorporates both the change in enthalpy and the change in entropy for the reaction (Equation 19.11), so under standard conditions: ΔG° = ΔH° – TΔS° To determine whether ΔG° is more negative or less negative than ΔH° we need to determine the sign of the term TΔS°. T is the absolute temperature, 298 K, so it is a positive number. We can predict the sign of ΔS° by looking at the reaction. Solve: (a) We see that the reactants consist of six molecules of gas, and the products consist of three molecules of gas and four molecules of liquid. Thus, the number of molecules of gas has decreased significantly during the reaction. By using the general rules we discussed in Section 19.3, we would expect a decrease in the number of gas molecules to lead to a decrease in the entropy of the system—the products have fewer accessible microstates than the reactants. We therefore expect ΔS° and TΔS° to be negative numbers. Because we are subtracting TΔS°, which is a negative number, we would predict that ΔG° is less negative than ΔH°. (b) Using Equation 19.13 and values from Appendix C, we can calculate the value of ΔG°: Chemical Notice that we have been careful to use the value of as in the calculation of ΔH values, the Thermodynamics phases of the reactants and products are important. As we predicted, ΔG° is less negative than ΔH° because of the decrease in entropy during the reaction.
  164. 164. PRACTICE EXERCISE Consider the combustion of propane to form CO2(g) and H2O(g) at 298 K: Would you expect ΔG° to be more negative or less negative than ΔH°? Chemical Thermodynamics
  165. 165. PRACTICE EXERCISE Consider the combustion of propane to form CO2(g) and H2O(g) at 298 K: Would you expect ΔG° to be more negative or less negative than ΔH°? Answer: more negative Chemical Thermodynamics
  166. 166. Free Energy Changes Chemical Thermodynamics
  167. 167. Free Energy Changes At temperatures other than 25°C, ΔG° = ΔH° − TΔS° How does ΔG° change with temperature? Chemical Thermodynamics
  168. 168. Free Energy and Temperature Chemical Thermodynamics
  169. 169. Free Energy and Temperature • There are two parts to the free energy equation: ΔH°— the enthalpy term TΔS° — the entropy term • The temperature dependence of free energy, then comes from the entropy term. Chemical Thermodynamics
  170. 170. Upon heating, limestone (CaCO3) decomposes to CaO and CO2. Speculate on the sign of ΔH and ΔS for this process. CaCO3(s) CaO(s) + CO2(g) Limestone Cave Carlsbad Caverns, New Mexico Chemical Thermodynamics
  171. 171. Upon heating, limestone (CaCO3) decomposes to CaO and CO2. Speculate on the sign of ΔH and ΔS for this process. CaCO3(s) CaO(s) + CO2(g) Limestone Cave Carlsbad Caverns, New Mexico Chemical Thermodynamics
  172. 172. Free Energy and Temperature Chemical Thermodynamics
  173. 173. Chemical Thermodynamics
  174. 174. ΔH < TΔS Chemical Thermodynamics
  175. 175. ΔH < TΔS ΔG(Negative/spontaneous)= Chemical Thermodynamics
  176. 176. ΔH < TΔS ΔG(Negative/spontaneous)= ΔH (Positive/vaporization) - TΔS (positive/liquid to gas) Chemical Thermodynamics
  177. 177. ΔH < TΔS ΔG(Negative/spontaneous)= ΔH (Positive/vaporization) - TΔS (positive/liquid to gas) ↑must be larger Chemical Thermodynamics
  178. 178. Both the entropy, ΔS° and the enthalpy ΔH° have positive values. Near absolute zero (0 K), will the process be spontaneous or nonspontaneous? 1. Spontaneous 2. Nonspontaneous Chemical Thermodynamics
  179. 179. Correct Answer: 1. Spontaneous 2. Nonspontaneous At low temperatures, the enthalpy term dominates the entropy term, leading to a positive ΔG and a nonspontaneous process. Chemical Thermodynamics
  180. 180. A reaction will be spontaneous at lower temperatures when the sign of ΔH and ΔS is Chemical Thermodynamics
  181. 181. A reaction will be spontaneous at lower temperatures when the sign of ΔH and ΔS is Chemical Thermodynamics
  182. 182. SAMPLE EXERCISE 19.8 Determining the Effect of Temperature on Spontaneity The Haber process for the production of ammonia involves the equilibrium Assume that ΔH° and ΔS° for this reaction do not change with temperature. (a) Predict the direction in which ΔG° for this reaction changes with increasing temperature. (b) Calculate the values of ΔG° for the reaction at 25°C and 500°C.
  183. 183. SAMPLE EXERCISE 19.8 continued Solution Analyze: In part (a) we are asked to predict the direction in which ΔG° for the ammonia synthesis reaction changes as temperature increases. In part (b) we need to determine ΔG° for the reaction at two different temperatures. Plan: In part (a) we can make this prediction by determining the sign of ΔS° for the reaction and then using that information to analyze Equation 19.20. In part (b) we need to calculate ΔH° and ΔS° for the reaction by using the data in Appendix C. We can then use Equation 19.20 to calculate ΔG°. Solve: (a) Equation 19.20 tells us that ΔG° is the sum of the enthalpy term ΔH° and the entropy term –TΔS°. The temperature dependence of ΔG° comes from the entropy term. We expect ΔS° for this reaction to be negative because the number of molecules of gas is smaller in the products. Because ΔS° is negative, the term –TΔS° is positive and grows larger with increasing temperature. As a result, ΔG° becomes less negative (or more positive) with increasing temperature. Thus, the driving force for the production of NH3 becomes smaller with increasing temperature. (b) We calculated the value of ΔH° in Sample Exercise 15.14, and the value of ΔS° was determined in Sample Exercise 19.5: ΔH° = –92.38 kJ and ΔS° = –198.4 J/K. If we assume that these values don’t change with temperature, we can calculate ΔG° at any temperature by using Equation 19.20. At T = 298 K we have: Notice that we have been careful to convert –TΔS° into units of kJ so that it can be added to ΔH°, which has units of kJ. Comment: Increasing the temperature from 298 K to 773 K changes ΔG° from –33.3 kJ to +61 kJ. Of course, the result at 773 K depends on the assumption that ΔH° and ΔS° do not change with temperature. In fact, these values do change slightly with temperature. Nevertheless, the result at 773 K should be a reasonable approximation. The positive increase in ΔG° with increasing T agrees with our prediction in part (a) of this exercise. Our result indicates that a mixture of N2(g), H2(g), and NH3(g), each present at a partial pressure of 1 atm, will react spontaneously at 298 K to form more NH3(g). In contrast, at 773 K the positive value of ΔG° tells us that the reverse reaction is spontaneous. Thus, when the mixture of three gases, each at a partial pressure of 1 atm, is heated to 773 K, some of the NH (g) spontaneously decomposes into N (g) and H (g).
  184. 184. PRACTICE EXERCISE (a) Using standard enthalpies of formation and standard entropies in Appendix C, calculate ΔH° and ΔS° at 298 K for the following reaction: (b) Using the values obtained in part (a), estimate ΔG° at 400 K.
  185. 185. PRACTICE EXERCISE (a) Using standard enthalpies of formation and standard entropies in Appendix C, calculate ΔH° and ΔS° at 298 K for the following reaction: (b) Using the values obtained in part (a), estimate ΔG° at 400 K. Answer: (a) ΔH° = –196.6 kJ, ΔS° = –189.6 J/K; (b) ΔG° = –120.8 kJ
  186. 186. Chapter 19- Chemical Thermodynamics Section 19.7 Free Energy & Keq
  187. 187. Free Energy and Equilibrium Chemical Thermodynamics
  188. 188. Free Energy and Equilibrium Under any conditions, standard or nonstandard, the free energy change can be found this way: ΔG = ΔG° + RT lnQ (Under standard conditions, all concentrations are 1 M, so Q = 1 and lnQ = 0; the last term drops out.) Chemical Thermodynamics
  189. 189. SAMPLE EXERCISE 19.9 Relating ΔG to a Phase Change at Equilibrium 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, CCl4(l). (b) What is the value of ΔG° for the equilibrium in part (a)? (c) Use thermodynamic data in Appendix C and Equation 19.20 to estimate the normal boiling point of CCl4.
  190. 190. SAMPLE EXERCISE 19.9 Relating ΔG 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, CCl4(l). (b) What is the value of ΔG° for the equilibrium in part (a)? (c) Use thermodynamic data in Appendix C and Equation 19.20 to estimate the normal boiling point of CCl4. Solution Analyze: (a) We must write a chemical equation that describes the physical equilibrium between liquid and gaseous CCl4 at the normal boiling point. (b) We must determine the value of ΔG° for CCl4 in equilibrium with its vapor at the normal boiling point. (c) We must estimate the normal boiling point of CCl4, based on available thermodynamic data. Plan: (a) The chemical equation will merely show the change of state of CCl4 from liquid to solid. (b) We need to analyze Equation 19.21 at equilibrium (ΔG = 0). (c) We can use Equation 19.20 to calculate T when ΔG = 0. Solve: (a) The normal boiling point of CCl4 is the temperature at which pure liquid CCl4 is in equilibrium with its vapor at a pressure of 1 atm: (b) At equilibrium ΔG = 0. In any normal boiling-point equilibrium both the liquid and the vapor are in their standard states (Table 19.2). As a consequence, Q = 1, ln Q = 0, and ΔG = ΔG° for this process. Thus, we conclude that ΔG° = 0 for the equilibrium involved in the normal boiling point of any liquid. We would also find that ΔG° = 0 for the equilibria relevant to normal melting points and normal sublimation points of solids. (c) Combining Equation 19.20 with the result from part (b), we see that the equality at the normal boiling point, Tb, of CCl4(l) or any other pure liquid is Chemical Thermodynamics
  191. 191. SAMPLE EXERCISE 19.9 continued Solving the equation for Tb, we obtain Strictly speaking, we would need the values of ΔH° and ΔS° for the equilibrium between CCl4(l) and CCl4(g) at the normal boiling point to do this calculation. However, we can estimate the boiling point by using the values of ΔH° and ΔS° for CCl4 at 298 K, which we can obtain from the data in Appendix C and Equations 5.31 and 19.8: Notice that, as expected, the process is endothermic (ΔH > 0) and produces a gas in which energy can be more spread out (ΔS > 0). We can now use these values to estimate Tb for CCl4(l): Note also that we have used the conversion factor between J and kJ to make sure that the units of ΔH ° and ΔS° match. Check: The experimental normal boiling point of CCl (l) is 76.5°C. The small deviation of our 4 estimate from the experimental value is due to the assumption that ΔH° and ΔS° do not change with temperature. Chemical Thermodynamics
  192. 192. PRACTICE EXERCISE Use data in Appendix C to estimate the normal boiling point, in K, for elemental bromine, Br2(l). (The experimental value is given in Table 11.3.) Chemical Thermodynamics
  193. 193. PRACTICE EXERCISE Use data in Appendix C to estimate the normal boiling point, in K, for elemental bromine, Br2(l). (The experimental value is given in Table 11.3.) Answer: 330 K Chemical Thermodynamics
  194. 194. 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 ΔG at 298 K for a reaction mixture that consists of 1.0 atm N2, 3.0 atm H2, and 0.50 atm NH3. Chemical Thermodynamics
  195. 195. 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 ΔG at 298 K for a reaction mixture that consists of 1.0 atm N2, 3.0 atm H2, and 0.50 atm NH3. Solution Analyze: We are asked to calculate ΔG under nonstandard conditions. Plan: We can use Equation 19.21 to calculate ΔG. Doing so requires that we calculate the value of the reaction quotient Q for the specified partial pressures of the gases and evaluate ΔG°, using a table of standard free energies of formation. Solve: Solving for the reaction quotient gives: In Sample Exercise 19.8 we calculated ΔG° = 33.3 kJ for this reaction. We will have to change the units of this quantity in applying Equation 19.21, however. In order for the units in Equation 19.21 to work out, we will use kJ/mol as our units for ΔG°, where “per mole” means “per mole of the reaction as written.” Thus, ΔG° = –33.3kJ/mol implies per 1 mol of N2, per 3 mol of H2, and per 2 mol of NH3. We can now use Equation 19.21 to calculate ΔG for these nonstandard conditions: Comment: We see that ΔG becomes more negative, changing from –33.3 kJ/mol to –44.9 kJ/mol as the pressures of N2, H2, and NH3 are changed from 1.0 atm each (standard conditions, ΔG° ) to 1.0 atm, 3.0 atm, and 0.50 atm, respectively. The larger negative value for ΔG indicates a larger “driving force” to produce NH3. We would have made the same prediction on the basis of Le Châtelier’s principle. • (Section 15.6) Relative to standard conditions, we have increased the pressure of a reactant (H2) and decreased the pressure of the product (NH3). Le Châtelier’s principle predicts that both of these changes should shift the reaction more to the product side, thereby forming more NH3.
  196. 196. PRACTICE EXERCISE Calculate ΔG 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. Chemical Thermodynamics
  197. 197. PRACTICE EXERCISE Calculate ΔG 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. Answer: –26.0 kJ/mol Chemical Thermodynamics
  198. 198. Decomposition of CaCO3 has a ΔH° = 178.3 kJ/mol and ΔS° = 159 J/mol • K. At what temperature does this become spontaneous? 1. 121°C 2. 395°C 3. 848°C 4. 1121°C Chemical Thermodynamics
  199. 199. Correct Answer: 1. 121°C T = ΔH°/ΔS° 2. 395°C 3. 848°C T = 178.3 kJ/mol/0.159 kJ/mol • K 4. 1121°C T = 1121 K T (°C) = 1121 – 273 = 848 Chemical Thermodynamics
  200. 200. Free Energy and Equilibrium Chemical Thermodynamics
  201. 201. Free Energy and Equilibrium • At equilibrium, Q = K, and ΔG = 0. Chemical Thermodynamics
  202. 202. Free Energy and Equilibrium • At equilibrium, Q = K, and ΔG = 0. • The equation becomes Chemical Thermodynamics
  203. 203. Free Energy and Equilibrium • At equilibrium, Q = K, and ΔG = 0. • The equation becomes 0 = ΔG° + RT lnK Chemical Thermodynamics
  204. 204. Free Energy and Equilibrium • At equilibrium, Q = K, and ΔG = 0. • The equation becomes 0 = ΔG° + RT lnK • Rearranging, this becomes Chemical Thermodynamics
  205. 205. Free Energy and Equilibrium • At equilibrium, Q = K, and ΔG = 0. • The equation becomes 0 = ΔG° + RT lnK • Rearranging, this becomes ΔG° = −RT lnK Chemical Thermodynamics
  206. 206. Free Energy and Equilibrium • At equilibrium, Q = K, and ΔG = 0. • The equation becomes 0 = ΔG° + RT lnK • Rearranging, this becomes ΔG° = −RT lnK or, Chemical Thermodynamics
  207. 207. Free Energy and Equilibrium • At equilibrium, Q = K, and ΔG = 0. • The equation becomes 0 = ΔG° + RT lnK • Rearranging, this becomes ΔG° = −RT lnK or, K = e−ΔG°/RT Chemical Thermodynamics
  208. 208. Suppose ΔG° is a large, positive value. What then will be the value of the equilibrium constant, K? 1. K=0 2. K=1 3. 0<K<1 4. K>1 Chemical Thermodynamics
  209. 209. Correct Answer: ΔG° = −RTlnK 1. K=0 Thus, large positive values of ΔG° 2. K=1 lead to large negative values of lnK. 3. 0<K<1 The value of K itself, then, is very 4. K>1 small, approaching zero. Chemical Thermodynamics
  210. 210. N2(g) + 3 H2(g)  2 NH3(g) ΔH° = -92.4 kJ/mol If the temperature is decreased, what is the effect on the equilibrium constant and ΔG? 1. K increases, ΔG increases 2. K decreases, ΔG decreases 3. K increases, ΔG decreases 4. K decreases, ΔG increases 5. Temperature does not affect Josiah Willard Gibbs equilibrium or ΔG (1839-1903) Chemical Thermodynamics
  211. 211. N2(g) + 3 H2(g)  2 NH3(g) ΔH° = -92.4 kJ/mol If the temperature is decreased, what is the effect on the equilibrium constant and ΔG? 1. K increases, ΔG increases 2. K decreases, ΔG decreases 3. K increases, ΔG decreases 4. K decreases, ΔG increases 5. Temperature does not affect Josiah Willard Gibbs equilibrium or ΔG (1839-1903) Chemical Thermodynamics
  212. 212. SAMPLE EXERCISE 19.11 Calculating an Equilibrium Constant from ΔG° 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: ΔG° = –33.3 kJ/mol = –33,300 J/mol.
  213. 213. SAMPLE EXERCISE 19.11 Calculating an Equilibrium Constant from ΔG° 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: ΔG° = –33.3 kJ/mol = –33,300 J/mol. Comment: This is a large equilibrium constant, which indicates that the product, NH3, is greatly favored in the equilibrium mixture at 25°C. The equilibrium constants for temperatures in the range of 300°C to 600°C, given in Table 15.2, are much smaller than the value at 25°C. Clearly, a low-temperature equilibrium favors the production of ammonia more than a high-temperature one. Nevertheless, the Haber process is carried out at high temperatures because the reaction is extremely slow at room temperature.
  214. 214. SAMPLE EXERCISE 19.11 Calculating an Equilibrium Constant from ΔG° 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: ΔG° = –33.3 kJ/mol = –33,300 J/mol. Solution Analyze: We are asked to calculate K for a reaction, given ΔG°. Plan: We can use Equation 19.23 to evaluate the equilibrium constant, which in this case takes the form Comment: This is a large equilibrium constant, which indicates that the product, NH3, is greatly favored in the equilibrium mixture at 25°C. The equilibrium constants for temperatures in the range of 300°C to 600°C, given in Table 15.2, are much smaller than the value at 25°C. Clearly, a low-temperature equilibrium favors the production of ammonia more than a high-temperature one. Nevertheless, the Haber process is carried out at high temperatures because the reaction is extremely slow at room temperature.
  215. 215. SAMPLE EXERCISE 19.11 Calculating an Equilibrium Constant from ΔG° 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: ΔG° = –33.3 kJ/mol = –33,300 J/mol. Solution Analyze: We are asked to calculate K for a reaction, given ΔG°. Plan: We can use Equation 19.23 to evaluate the equilibrium constant, which in this case takes the form In this expression the gas pressures are expressed in atmospheres. (Remember that we use kJ/mol as the units of ΔG° when using Equations 19.21, 19.22, or 19.23). Comment: This is a large equilibrium constant, which indicates that the product, NH3, is greatly favored in the equilibrium mixture at 25°C. The equilibrium constants for temperatures in the range of 300°C to 600°C, given in Table 15.2, are much smaller than the value at 25°C. Clearly, a low-temperature equilibrium favors the production of ammonia more than a high-temperature one. Nevertheless, the Haber process is carried out at high temperatures because the reaction is extremely slow at room temperature.
  216. 216. SAMPLE EXERCISE 19.11 Calculating an Equilibrium Constant from ΔG° 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: ΔG° = –33.3 kJ/mol = –33,300 J/mol. Solution Analyze: We are asked to calculate K for a reaction, given ΔG°. Plan: We can use Equation 19.23 to evaluate the equilibrium constant, which in this case takes the form In this expression the gas pressures are expressed in atmospheres. (Remember that we use kJ/mol as the units of ΔG° when using Equations 19.21, 19.22, or 19.23). Solve: Solving Equation 19.22 for the exponent –ΔG°/RT, we have Comment: This is a large equilibrium constant, which indicates that the product, NH3, is greatly favored in the equilibrium mixture at 25°C. The equilibrium constants for temperatures in the range of 300°C to 600°C, given in Table 15.2, are much smaller than the value at 25°C. Clearly, a low-temperature equilibrium favors the production of ammonia more than a high-temperature one. Nevertheless, the Haber process is carried out at high temperatures because the reaction is extremely slow at room temperature.
  217. 217. SAMPLE EXERCISE 19.11 Calculating an Equilibrium Constant from ΔG° 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: ΔG° = –33.3 kJ/mol = –33,300 J/mol. Solution Analyze: We are asked to calculate K for a reaction, given ΔG°. Plan: We can use Equation 19.23 to evaluate the equilibrium constant, which in this case takes the form In this expression the gas pressures are expressed in atmospheres. (Remember that we use kJ/mol as the units of ΔG° when using Equations 19.21, 19.22, or 19.23). Solve: Solving Equation 19.22 for the exponent –ΔG°/RT, we have We insert this value into Equation 19.23 to obtain K: Comment: This is a large equilibrium constant, which indicates that the product, NH3, is greatly favored in the equilibrium mixture at 25°C. The equilibrium constants for temperatures in the range of 300°C to 600°C, given in Table 15.2, are much smaller than the value at 25°C. Clearly, a low-temperature equilibrium favors the production of ammonia more than a high-temperature one. Nevertheless, the Haber process is carried out at high temperatures because the reaction is extremely slow at room temperature.
  218. 218. SAMPLE EXERCISE 19.11 Calculating an Equilibrium Constant from ΔG° 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: ΔG° = –33.3 kJ/mol = –33,300 J/mol. Solution Analyze: We are asked to calculate K for a reaction, given ΔG°. Plan: We can use Equation 19.23 to evaluate the equilibrium constant, which in this case takes the form In this expression the gas pressures are expressed in atmospheres. (Remember that we use kJ/mol as the units of ΔG° when using Equations 19.21, 19.22, or 19.23). Solve: Solving Equation 19.22 for the exponent –ΔG°/RT, we have We insert this value into Equation 19.23 to obtain K: Comment: This is a large equilibrium constant, which indicates that the product, NH3, is greatly favored in the equilibrium mixture at 25°C. The equilibrium constants for temperatures in the range of 300°C to 600°C, given in Table 15.2, are much smaller than the value at 25°C. Clearly, a low-temperature equilibrium favors the production of ammonia more than a high-temperature one. Nevertheless, the Haber process is carried out at high temperatures because the reaction is extremely slow at room temperature. Thermodynamics can tell us the direction and extent of a reaction, but tells us nothing about the rate at which it occurs. If a catalyst were found that would permit the reaction to proceed at a rapid rate at room temperature, high pressures would not be needed to force the equilibrium toward NH3.
  219. 219. PRACTICE EXERCISE Use data from Appendix C to calculate the standard free-energy change, ΔG°, and the equilibrium constant, K, at 298 K for the reaction Chemical Thermodynamics
  220. 220. PRACTICE EXERCISE Use data from Appendix C to calculate the standard free-energy change, ΔG°, and the equilibrium constant, K, at 298 K for the reaction Answer: ΔG° = –106.4 kJ/mol, K = 5 × 1018 Chemical Thermodynamics
  221. 221. SAMPLE INTEGRATIVE EXERCISE Putting Concepts Together Consider the equilibria in which these salts dissolve in water to form aqueous solutions of ions: (a) Calculate the value of ΔG° 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 ΔG° 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 ΔG° for the solution process of these salts change with increasing T? What effect should this change have on the solubility of the salts?
  222. 222. 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 ΔG° 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 ΔG° 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 ΔG° for the solution process of these salts change with increasing T? What effect should this change have on the solubility of the salts? Solution (a) We will use Equation 19.13 along with values from Appendix C to calculate the values for each equilibrium. (As we did in Section 13.1, we use the subscript “soln” to indicate that these are thermodynamic quantities for the formation of a solution.) We find Chemical Thermodynamics
  223. 223. SAMPLE INTEGRATIVE EXERCISE continued (b) We can write as the sum of an enthalpy term, and an entropy term, We can calculate the values of and by using Equations 5.31 and 19.8. We can then calculate at T = 298 K. All these calculations are now familiar to us. The results are summarized in the following table: The entropy terms for the solution of the two salts are very similar. That seems sensible because each solution process should lead to a similar increase in randomness as the salt dissolves, forming hydrated ions. • (Section 13.1) In contrast, we see a very large difference in the enthalpy term for the solution of the two salts. The difference in the values of is dominated by the difference in the values of (c) The solubility product, Ksp, is the equilibrium constant for the solution process. • (Section 17.4) As such, we can relate Ksp directly to by using Equation 19.23: We can calculate the Ksp values in the same way we applied Equation 19.23 in Sample Exercise 19.13. We use the values we obtained in part (a), remembering to convert them from to J/mol: Chemical Thermodynamics The value calculated for the Ksp of AgCl is very close to that listed in Appendix D.
  224. 224. SAMPLE INTEGRATIVE EXERCISE continued (d) A soluble salt is one that dissolves appreciably in water. • (Section 4.2) The Ksp value for NaCl is greater than 1, indicating that NaCl dissolves to a great extent. The Ksp value for AgCl is very small, indicating that very little dissolves in water. Silver chloride should indeed be considered an insoluble salt. (e) As we expect, the solution process has a positive value of ΔS for both salts (see the table in part b). As such, the entropy term of the free-energy change, is negative. If we assume that and do not change much with temperature, then an increase in T will serve to make more negative. Thus, the driving force for dissolution of the salts will increase with increasing T, and we therefore expect the solubility of the salts to increase with increasing T. In Figure 13.17 we see that the solubility of NaCl (and that of nearly any salt) increases with increasing temperature. • (Section 13.3) Chemical Thermodynamics
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