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![Page 1: Ch 17 Free Energy and Thermodynamics - Moorpark Collegesunny.moorparkcollege.edu/~dfranke/chemistry_1B/thermodynamics.pdf · F r e e E n e r g y a n d T h e r m o d y n a m i c s](https://reader033.fdocuments.in/reader033/viewer/2022051720/5a76b12e7f8b9a93088d54b6/html5/thumbnails/1.jpg)
F r e e E n e r g y a n d T h e r m o d y n a m i c s : C h 1 8 P a g e | 1
Ch 18 Free Energy and Thermodynamics:
Homework: Read Ch 18, Work out sample/practice exercises in the sections as you read,
Ch 18: 27, 31, 33, 41, 43, 47, 51, 55, 61, 63, 67, 71, 77, 87
Check for MasteringChemistry due dates.
Turn in your Research topic by the due date
Chemical Thermodynamics:
Chemical Thermodynamics studies energy relationships between Enthalpy,
Entropy, Equilibrium, and Gibbs free energy. Thermodynamics can predict the
spontaneous direction of a reaction under specified conditions, but not the rate of
the reaction.
Thermodynamics vs. Kinetics:
Which one deals with state functions, independent of path?
![Page 2: Ch 17 Free Energy and Thermodynamics - Moorpark Collegesunny.moorparkcollege.edu/~dfranke/chemistry_1B/thermodynamics.pdf · F r e e E n e r g y a n d T h e r m o d y n a m i c s](https://reader033.fdocuments.in/reader033/viewer/2022051720/5a76b12e7f8b9a93088d54b6/html5/thumbnails/2.jpg)
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Spontaneous Processes:
Spontaneous process: A spontaneous process is one that proceeds in a specific
direction on its own without any outside assistance under specified conditions (T,
P). The products are considered thermodynamically more stable. The reverse
reaction is nonspontaneous. Some reactions are always spontaneous, others are
never spontaneous and many reactions can be either, depending on conditions. Most
spontaneous reactions favor exothermic processes (-H) and increased entropy
(+S). Often one factor may override the other. Equilibrium reactions can shift to
be spontaneous in the forward or reverse direction with just slight changes in the
environment/conditions. A spontaneous process always moves a reaction mixture
toward equilibrium.
Reversible process will restore all components to the original conditions and states
with no net change to the system or surroundings, an example that is reversible is
the melting or freezing of ice at 1 atm and 0°C. Reversible processes only occur for
situations at equilibrium, Suniv = .
Irreversible process will not restore to original, an example is to mix equal portions
of hot and cold liquid together that end with an in between final temperature. Any
spontaneous process is irreversible,Suniv > .
HISTORY: Carnot Engine: In 1824 a French Engineer, Sadi Carnot published an
analysis of factors that determine efficiency of a steam engine. An ideal engine that
converts all the energy content of fuel to useable work is impossible because heat is
always lost to the surroundings. This study led to engineering more efficient
engines and was the first study that led to the discipline thermodynamics. Rudolph
Clausius: Forty years later the ratio of qp/T (entropy) was found to have a special
significance and was comparable to energy.
Ideal Engine: An ideal engine that has maximum efficiency operates under ideal
conditions in which all processes are reversible.
The Energy Tax: Every energy transition results in a “loss” of energy, heating up
the surroundings. An ideal engine is not possible.
Heat Tax: Fewer steps are generally more efficient.
The heating of your home with natural gas directly (1 step) is much more efficient
than heating with electricity, which may take 5 or more steps.
![Page 3: Ch 17 Free Energy and Thermodynamics - Moorpark Collegesunny.moorparkcollege.edu/~dfranke/chemistry_1B/thermodynamics.pdf · F r e e E n e r g y a n d T h e r m o d y n a m i c s](https://reader033.fdocuments.in/reader033/viewer/2022051720/5a76b12e7f8b9a93088d54b6/html5/thumbnails/3.jpg)
F r e e E n e r g y a n d T h e r m o d y n a m i c s : C h 1 8 P a g e | 3
Entropy, S:
Second Law: Entropy Principle: Every spontaneous change increases the total
entropy change of the universe. This does not mean local decreases in
entropy cannot take place. For the entropy of a system to decrease, the
entropy of the surroundings must increase more. Suniv > The
universe tends toward greater randomness.
for reversible process Suniv = 0
Third Law: Zero Entropy Established: The entropy of a pure, perfect, crystalline
substance (no disorder) is zero at the temperature of absolute zero, 0
Kelvin.
![Page 4: Ch 17 Free Energy and Thermodynamics - Moorpark Collegesunny.moorparkcollege.edu/~dfranke/chemistry_1B/thermodynamics.pdf · F r e e E n e r g y a n d T h e r m o d y n a m i c s](https://reader033.fdocuments.in/reader033/viewer/2022051720/5a76b12e7f8b9a93088d54b6/html5/thumbnails/4.jpg)
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Entropy: Entropy is a state function that measures randomness, ways of being.
This includes all possible motions: Vibration, rotation, translation.
S= qp/T = H/T
S = klnW (entropy = Boltzmann’s constant, 1.38 x 10-23 J/K time
the natural log of the ways of being, number of microstates)
S= Sfinal – Sinital (S, entropy values can be found in the Appendix)
S= klnW final – klnW inital = kln(Wfinal/Winitial)
Entropy has units of J/mol K and can be found in Appendix C.
Be aware that the units for entropy are in J and not kJ!
Predicting the sign for S: (+ more ways, favorable)
1) Phase changes: s l g… H2O (l) H2O (g) (+S)
![Page 5: Ch 17 Free Energy and Thermodynamics - Moorpark Collegesunny.moorparkcollege.edu/~dfranke/chemistry_1B/thermodynamics.pdf · F r e e E n e r g y a n d T h e r m o d y n a m i c s](https://reader033.fdocuments.in/reader033/viewer/2022051720/5a76b12e7f8b9a93088d54b6/html5/thumbnails/5.jpg)
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2) Temp: warming… +S O2 (g) 25°C O2 (g) 80°C
3) Volume: expanding… +S 10 ml gas 1.0 liter of same gas
4) Mixing: dissolving ... +S NaCl (s) + H2O (l) NaCl (aq)
5) Rearrange to create more ways of being…
+S H2 (g) + Cl2 (g) 2 HCl (g)
6) # parts: increase… +S 10 g rock 10 g sand
7) More moles gas… +S N2O4 (g) 2 NO2 (g)
Example 1:
a) What is the entropy of a system with only 1 microstate?
S = klnW
b) What sign is S for the following:
Temperature decreases
Volume increases
gas liquid
increase the moles of gas
Dissolving sugar in hot tea
N2 (g) + 3H2 (g) 2 NH3 (g)
Ag+(aq) + Cl-1(aq) AgCl (s)
c) Circle the one with the higher entropy in each of the following pairs.
1 mole O2 (g) ; 25°C or 1 mole O2 (g) ; 50°C
1 mole N2O4 gas or 2 mole NO2 gas
NaCl (s) or NaCl (aq)
1 mol N2 gas in 22.4 L or 1 mol N2 gas in 2.2 L
1 mol H2O (l) or 1 mol H2O (s)
![Page 6: Ch 17 Free Energy and Thermodynamics - Moorpark Collegesunny.moorparkcollege.edu/~dfranke/chemistry_1B/thermodynamics.pdf · F r e e E n e r g y a n d T h e r m o d y n a m i c s](https://reader033.fdocuments.in/reader033/viewer/2022051720/5a76b12e7f8b9a93088d54b6/html5/thumbnails/6.jpg)
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Solving Srxn: Just like enthalpy, entropy can be solved using the Appendix values.
S°rxn= nS°products - nS°reactants
Example 2: S° for CO2 (g) = 213.8 J/mol K
a) Predict the sign of the standard entropy change for the reaction…
CH4(g) + 2 O2 (g) CO2 (g)+ 2 H2O (l)
b) Calculate S° using the appendix values.
Example 3:
a) Predict the sign of the entropy change for the vaporization of water…
b) Calculate S° using the appendix values.
![Page 7: Ch 17 Free Energy and Thermodynamics - Moorpark Collegesunny.moorparkcollege.edu/~dfranke/chemistry_1B/thermodynamics.pdf · F r e e E n e r g y a n d T h e r m o d y n a m i c s](https://reader033.fdocuments.in/reader033/viewer/2022051720/5a76b12e7f8b9a93088d54b6/html5/thumbnails/7.jpg)
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Trouton’s Law: Most liquids follow Trouton’s Law- the molar heat of entropy of
vaporization is approximately 88 J/mol K; Svap= 88+/- 5J/mol K
Example 4:
Most liquids follow Trouton’s rule. Normal boiling points and enthalpies of
vaporization of several organic liquids are in the table.
Substance Normal Boiling Pt
(˚C)
Hvap (kJ/mol)
Acetone, (CH3)2CO 56.1 29.1
Dimethyl ether,
(CH3)2O
-24.8 21.5
Ethanol, C2H5OH 78.4 38.6
Octane, C8H18 125.6 34.4
Pyridine, C5H5N 115.3 35.1
a) Estimate Svap for each liquid using … Svap= Hvap/Tbp
Acetone, (CH3)2CO
Dimethyl ether, (CH3)2O
Ethanol, C2H5OH
Octane, C8H18
Pyridine, C5H5N
b) Which do not follow Trouton’s Law?
c) Explain the exceptions using intermolecular forces?
d) Should water follow Trouton’s Law? Check the accuracy of your
conclusion using the Appendix.
e) Chlorobenzene boils at 131.5˚C, estimate the Hvap for C6H5Cl.
![Page 8: Ch 17 Free Energy and Thermodynamics - Moorpark Collegesunny.moorparkcollege.edu/~dfranke/chemistry_1B/thermodynamics.pdf · F r e e E n e r g y a n d T h e r m o d y n a m i c s](https://reader033.fdocuments.in/reader033/viewer/2022051720/5a76b12e7f8b9a93088d54b6/html5/thumbnails/8.jpg)
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Example 5: Estimate the normal boiling point in degrees Celsius of CCl4. Use the
appendix values.
Gibbs Free Energy:
Gibbs Free Energy is the maximum amount of useful energy obtainable in the form
of work. It uses both enthalpy and entropy to predict spontaneity.
Gf˚ , Gibbs Free Energy can be found in the Appendix
G = H - TS (remember to convert S into kJ for consistency)
G°rxn= nG°f (products) - nG°f(reactants)
G under nonstandard conditions is a reliable indicator of spontaneity.
G > 0; a positive free energy is nonspontaneous
G= 0; a zero free energy is at equilibrium
G< 0; a negative free energy is spontaneous
![Page 9: Ch 17 Free Energy and Thermodynamics - Moorpark Collegesunny.moorparkcollege.edu/~dfranke/chemistry_1B/thermodynamics.pdf · F r e e E n e r g y a n d T h e r m o d y n a m i c s](https://reader033.fdocuments.in/reader033/viewer/2022051720/5a76b12e7f8b9a93088d54b6/html5/thumbnails/9.jpg)
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Example 6:
Predict the sign and calculate the Gibbs free energy change under standard
conditions (25˚C) for the reaction… Use the appendix values.
CH4(g) + 2 O2 (g) CO2 (g)+ 2 H2O (l)
a) From this equation G°rxn= nG°f (products) - nG°f (reactants)
b) From this equation G°rxn= H°rxn - TS°rxn
Gibbs Free Energy and Temperature: Hf° andS° data do not significantly change with varying temperatures.
H
(kJ/mol)
S
(kJ/mol)
G = H - TS Spontaneity conditions
_ + _ Spontaneous at all Temps
-196 +126 _ 2H2O2 (l) 2 H2O (l) + O2 (g)
+ _ + Nonspontaneous at all Temps
+285 -137 + 3 O2 (g) 2 O3 (g)
_ _ + or - Spontaneous at low Temps
Nonspontaneous at high Temps
-233 -424 Equil T = ? 2H2S (g) + SO2 (g)
2 H2O (l) + 3 S (s)
+ + + or - Spontaneous at high Temps
Nonspontaneous at low Temps
+176 +285 Equil T = ? NH4Cl (s) NH3(g) + HCl (g)
The equilibrium temperature can be found for the bottom two conditions by setting
G to zero; H = TS; = H /S (use kJ, T is in Kelvin)
![Page 10: Ch 17 Free Energy and Thermodynamics - Moorpark Collegesunny.moorparkcollege.edu/~dfranke/chemistry_1B/thermodynamics.pdf · F r e e E n e r g y a n d T h e r m o d y n a m i c s](https://reader033.fdocuments.in/reader033/viewer/2022051720/5a76b12e7f8b9a93088d54b6/html5/thumbnails/10.jpg)
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Example 7:
Solve for the equilibrium temperatures in the table above. Specify the
spontaneous temperature range/conditions at 1 atm, (above or below
equilibrium temperature).
Example 8:
An important reaction in the production of sulfuric acid is the oxidation of
sulfur dioxide gas into sulfur trioxide gas.
a) Write the chemical reaction.
b) Use appendix: Solve for G°rxn
c) Is the reaction spontaneous at standard conditions?
d) Solve H°f and S°
e) Will this reaction be spontaneous at 900°C?
f) Solve for the equilibrium temperature and determine the spontaneity
conditions.
![Page 11: Ch 17 Free Energy and Thermodynamics - Moorpark Collegesunny.moorparkcollege.edu/~dfranke/chemistry_1B/thermodynamics.pdf · F r e e E n e r g y a n d T h e r m o d y n a m i c s](https://reader033.fdocuments.in/reader033/viewer/2022051720/5a76b12e7f8b9a93088d54b6/html5/thumbnails/11.jpg)
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Gibbs Free Energy and Equilibrium Constant, Keq:
G = G° + RTlnQeq
and at equilibrium
G° = -RTlnKeq
For a spontaneous reactions…G< 0 is negative and K >>1 is very large.
![Page 12: Ch 17 Free Energy and Thermodynamics - Moorpark Collegesunny.moorparkcollege.edu/~dfranke/chemistry_1B/thermodynamics.pdf · F r e e E n e r g y a n d T h e r m o d y n a m i c s](https://reader033.fdocuments.in/reader033/viewer/2022051720/5a76b12e7f8b9a93088d54b6/html5/thumbnails/12.jpg)
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Example 9:
Consider the reaction 2 NO2 (g) N2O4 (g)
a) Calculate G˚ at 25˚C using Appendix values.
b) Calculate G at 25˚C if the partial pressures of NO2 and N2O4 are 0.40 atm and
1.60 atm, respectively.
Example 10:
Consider the decomposition of barium carbonate, BaCO3(s) BaO(s)+ CO2(g)
a) Calculate the equilibrium pressure of CO2 using Appendix values at 25˚C.
b) Calculate the equilibrium pressure of CO2 at 1100 K.
![Page 13: Ch 17 Free Energy and Thermodynamics - Moorpark Collegesunny.moorparkcollege.edu/~dfranke/chemistry_1B/thermodynamics.pdf · F r e e E n e r g y a n d T h e r m o d y n a m i c s](https://reader033.fdocuments.in/reader033/viewer/2022051720/5a76b12e7f8b9a93088d54b6/html5/thumbnails/13.jpg)
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Example 11:
The Ka for HNO2 = 4.5 x 10-4.
a) Write the Ka equation for HNO2.
b) Calculate G˚ at 25˚C using Ka.
c) What is G at equilibrium.
d) What is G when [NO2-1] = 6.0 x 10-4M, [HNO2] = 0.20 M, and pH = 1.30
Calculate Coupling Reactions:
Consider the direct decomposition of rust to iron…
2 Fe2O3 (s) 4 Fe (s) + 3 O2 (g) : G = +1487 kJ
This large positive value for free energy tells us the reaction is nonspontaneous.
However this does not mean you cannot change the rust back to pure iron; you just
need to do some useful work to reduce it by coupling with a reaction with a large
negative free energy.
2 CO (g) + O2 (g) 2 CO2 (g) : G = -514 kJ
The common term in both reactions is O2 (g). Notice we have 3 as product in the
rust decomposition and 1 O2 (g) in the CO (g) combustion.
2 Fe2O3 (s) 4 Fe (s) + 3 O2 (g) : G = +1487 kJ
3 x [2 CO (g) + O2 (g) 2 CO2 (g) : G = -514 kJ]
Overall: 2 Fe2O3 (s) + 6 CO (g) 4 Fe (s) + 6 CO2 (g) ;G = -56 kJ
This reaction occurs in a blast furnace.
In Biochemistry ATP provides the coupling energy necessary to accomplish many
reactions in a cell.
ATP + H2O (l) ADP + HPO4-2 (aq) ; G = -30.5 kJ
Glucose + Fructose sucrose + H2O (l) ; G = +29.3 kJ
Glucose + Fructose + ATP sucrose + ADP + HPO4-2 (aq); G = -1.2 kJ
![Page 14: Ch 17 Free Energy and Thermodynamics - Moorpark Collegesunny.moorparkcollege.edu/~dfranke/chemistry_1B/thermodynamics.pdf · F r e e E n e r g y a n d T h e r m o d y n a m i c s](https://reader033.fdocuments.in/reader033/viewer/2022051720/5a76b12e7f8b9a93088d54b6/html5/thumbnails/14.jpg)
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Example 12:
Given the two step reaction to form methane gas from CO and H2...
Step 1 CO (g) + 2 H2 (g) CH3OH (l)
Step 2 CH3OH (l) CH4 (g) + 1/2 O2 (g)
And using only the information on the table solve all parts in this problem.
compound H°f S°f G°f
CO(g) ------ ------ -137.2 kJ/mol
H2 (g) you know this! ------ you know this!
CH3OH (l) -238.7 kJ/mol 126.8 J/mol K -166.3 kJ/mol
CH4 (g) -74.87 kJ/mol 186.1 J/mol K ------
O2 (g) you know this! 205.0 J/mol K you know this!
a) What is H°f and G°f for H2 (g) and O2 (g)?
b) Calculate G°rxn in kJ/mol for step 1 (25°C)
Step 1 CO (g) + 2 H2 (g) CH3OH (l)
c) Is step 1 spontaneous under standard conditions?
d) Given that H° is negative and you have the ability to predict the sign of S,
answer under what conditions is step 1 spontaneous?
(always, at low temperatures, at high temperatures, never)
e) Calculate H°rxn in kJ/mol for step 2
Step 2 CH3OH (l) CH4 (g) + 1/2 O2 (g)
f) Calculate S°rxn in J/mol*K for step 2
Step 2 CH3OH (l) CH4 (g) + 1/2 O2 (g)
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g) Calculate G°rxn in kJ/mol for step 2 (25°C)
h) Is step 2 spontaneous under standard conditions?
i) At what temperature will step 2 have G = 0?
j) Specifically, what temperature range is step 2 spontaneous?
k) Write the overall coupled reaction of step 1 and step 2 when together and
Calculate the coupled overall G° under standard condition, 25°C.
Step 1 CO (g) + 2 H2 (g) CH3OH (l) G°
Step 2 CH3OH (l) CH4 (g) + 1/2 O2 (g) G°
Coupled reaction G°
l) Is the coupled reaction spontaneous under standard conditions, 25°C?
m) You are designing a production facility. Considering the information above,
would you carry out the reactions in separate steps under different
temperature conditions or coupled simultaneously together in the same
vessel under the same conditions.