Chapter 15 - Entropy and Gibbs Energy
Chapter 15 Overview
• 15.1 – Spontaneous Processes
• 15.2 – Entropy
• 15.3 – Entropy Changes in a System
• 15.4 – Entropy Changes in the Universe
• 15.5 – Predicting Spontaneity
• 15.6 – Thermodynamics in Living Systems
• 21.5 – Global Warming
15.1 - Spontaneous Processes
Spontaneity
• Processes that occur under a certain set of conditions are ____________________________________________________.
○ Can be given initial ___________________________, but must continue ___________________________________.
• Processes that do not occur under a certain set of conditions are ______________________________________________.
○ __________________________________________________________ of a spontaneous process is nonspontaneous.
Spontaneity Variables
• Spontaneity is affected by ___________________________________________________________________ and pressure:
○ When T > 0 °C, _____________________________________________________________________ is spontaneous.
○ When T < 0 °C, _____________________________________________________________________ is spontaneous.
Exothermic processes are _________________________________________________________________ for spontaneity.
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• Exothermic processes are _________________________________________________________________ for spontaneity.
15.2 - Entropy
Entropy
• Entropy (S) – Measure of _____________________________________________________________________ in a system.
○ ________________________________________________________________________________________________.
• A _______________________________ is any single possible arrangement of positions and kinetic energies of particles.
○ Entropy ________________________________________________________ with increasing number of microstates.
○ Entropy ______________________________________________________ with larger container volumes (for gases).
Textbook Questions for Extra Practice
• End-of-Chapter: 15.69
15.3 - Entropy Changes in a System
Motional Energy
• Atoms/molecules can have three types of motional energy:
○ ________________________________________________________ – Movement of particle along the x, y, or z axis.
○ ________________________________________________________ – Rotation of molecule along the x, y, or z axis.
○ ____________________________________________ – Compression, stretching, or bending of bonds in a molecule.
• Maximum of _________________________ translations & _________________________ rotations for a given molecule.
○ One for _________________________________________________________________________________________.
• More complex molecules have more vibrational modes.
Vibrational Modes of H2O
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Standard Molar Entropies
• Entropy of a substance quantified as standard molar entropies (S°).
○ Units of entropy typically __________________________________________________________________________.
○ Unlike _________________________, S° values for elements in their standard states are not _________________________.
○ In general, S° values…
▪ …increase going from _________________________________________________________________________.
▪ …increase with ____________________________________________________________________ molar mass.
▪ …increase with _________________________ complexity of structure (________________ vibrational modes).
• Like ΔH°f, S° values can be used to determine entropy change for a reaction (ΔS°rxn):
Molar Entropies of Hydrocarbons
Qualitatively Predicting ∆S°rxn
• Sign of ∆S°rxn is an important aspect of spontaneity:
○ Processes that increase entropy (∆S°rxn > 0) are ___________________________________________ for spontaneity.
○ Processes decrease entropy (∆S°rxn < 0) are ______________________________________________ for spontaneity.
• As temperature increases, system entropy ________________________________________________________________.
○ Larger distribution of ______________________________________________________________________ possible.
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Gases and ∆S°rxn
• Processes which result in net increase in moles of gas will have _________________________________________ ∆S°rxn.
○ Gases have highest entropies!
• Δn = _______________________________________________________________________________________________.
○ When Δn > 0, ∆S°rxn ______________________________________________________________________________.
○ When Δn < 0, ∆S°rxn ______________________________________________________________________________.
CO2(s) CO2(g) U(s) + 3F2(g) UF6(g)
Dissolving Solids and Entropy
• Dissolving solutes have two contributions to entropy change:
○ Separation of particles from the lattice ________________________________________________________ entropy.
○ Solvation of solute particles _________________________________________________________________ entropy.
▪ In water, an ion is typically solvated by _______ water molecules, reducing available volume they can occupy.
• Dissolving molecular solutes tends to _________________________________________________ entropy of the system.
• Dissolving ionic compounds containing…
○ …large ions with small charges tend to ____________________________________________ entropy of the system.
○ … small ions with large charges tend to ____________________________________________ entropy of the system.
Hydration Spheres
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Entropies of Solution
Qualitatively Predicting ∆H°rxn
• Predicting ∆H°rxn is not as straightforward, but can be done in certain circumstances:
○ Known reactions
▪ Combustion: Reaction with ____________________________________________________________________.
□ For hydrocarbons (compounds primarily composed of _________________________________________),
complete combustion produces _____________________________________________________________.
○ Simple reactions
▪ Breaking bonds require an absorption of energy (__________________________________________________).
▪ Forming bonds release energy (_________________________________________________________________).
○ Phase changes
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Molecular Interpretation of Entropy - Example Question
• For each of the following processes, indicate whether or not the entropy change will be positive, negative, or zero:
○ Heating a tank of neon gas at 100 °C to 200 °C.
○ Reacting solid calcium hydride with water, producing calcium hydroxide and hydrogen.
○ Dissolving solid benzoic acid in water.
○ Dissolving solid cesium iodide in water.
○ Dissolving solid aluminum phosphate in water.
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ALEKS Topics
• Predicting qualitatively how entropy changes with temperature and volume
• Qualitatively predicting reaction entropy
• Calculating reaction entropy using the standard molar entropies of reactants
Textbook Questions for Extra Practice
• Worked Examples: 15.2 AB, 15.3 AB
• Section Review: 15.3.1 - 15.3.4
• End-of-Chapter: 15.15, 15.17, 15.55
15.4 - Entropy Changes in the Universe
Entropy of System & Surroundings
• For a given process, change in entropy of system (∆Ssys) generally affects change in entropy of surroundings (∆Ssurr):
The 2nd Law of Thermodynamics
• Entropy change of the universe (∆Suniv) is sum of ∆Ssys and ∆Ssurr:
• 2nd Law of Thermodynamics – Any spontaneous process results in an ____________________________________ in ∆Suniv.
○ Entropy is _______________________________________________________________________________________!
○ Processes can be spontaneous if ΔSsys ________________________________________________________________.
• When ΔSuniv = 0, process is in a state of __________________________________________________________________.
Protein Folding & 2nd Law & Protein Structure Types
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H-Bonding and Protein Secondary Structure
The 3rd Law of Thermodynamics
• At absolute zero (0 K), particles of a substance will have ____________________________________________________.
○ Since there is no motion, only ______________________________________________________________________:
• The 3rd Law of Thermodynamics – For a pure crystalline substance at absolute zero, _______________________________.
○ All substances have _______________________________________________________________________________.
○ S° for ions relative to _______________________________________, so can be _____________________________.
Entropy and Temperature
• As substance is heated, entropy _________________________________________________________________________.
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Water Phases and Entropy
Standard Entropies & Entropy of the Universe - Example Question
• Using the table below for the combustion of methane at 25.0 ° C:
○ Qualitatively predict the sign of ∆S°rxn. What does this tell you about the spontaneity of the reaction?
○ Qualitatively predict the sign of ∆H°rxn. What does this tell you about the spontaneity of the reaction?
○ Calculate the ΔS°univ for this reaction. What does this tell you about the spontaneity of the reaction?
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ALEKS Topics
• Using the Second Law to predict spontaneous change
Textbook Questions for Extra Practice
• Worked Examples: 15.4 AB
• Section Review: 15.4.1 - 15.4.5
• End-of-Chapter: 15.21, 15.23, 15.65, 15.67
15.5 - Predicting Spontaneity
Conditions for Spontaneity
• Review of current factors affecting spontaneity:
○ Enthalpy of system (ΔH°rxn):
▪ Exothermic processes (ΔH°rxn < 0) are ___________________________________________________________.
▪ Endothermic processes (ΔH°rxn > 0) are __________________________________________________________.
○ Entropy of system (ΔS°rxn):
Increasing entropy of the system (ΔS°rxn > 0) is ____________________________________________________.
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▪ Increasing entropy of the system (ΔS°rxn > 0) is ____________________________________________________.
▪ Decreasing entropy of the system (ΔS°rxn < 0) is ___________________________________________________.
○ Entropy of universe (ΔS°univ):
▪ Increasing entropy of the universe (ΔS°univ > 0) is __________________________________________________.
▪ Decreasing entropy of the universe (ΔS°univ < 0) is __________________________________________________.
Gibbs Free Energy
• Spontaneity of a reaction can be predicted based on properties of system alone:
• ∆G°rxn is Gibbs free energy – energy available to _____________________________________________________________.
○ Exergonic reactions (ΔG°rxn < 0) are _________________________________________________________________.
○ Endergonic reactions (ΔG°rxn > 0) are ________________________________________________________________.
Temperature Effects on Spontaneity
• How temperature affects spontaneity depends on the _________________________________________ of ΔH° and ΔS°:
○ The temperature is always positive since it is in ________________________________________________________!
• ΔH° < 0, ΔS° < 0:
○ ΔH° ___________________________________________, ΔS° ____________________________________________.
○ __________________________ driven; spontaneous at __________________________________________________.
• ΔH° > 0, ΔS° > 0:
○ ΔH° ___________________________________________, ΔS° ____________________________________________.
○ __________________________ driven; spontaneous at __________________________________________________.
• ΔH° < 0, ΔS° > 0:
○ ΔH° ___________________________________________, ΔS° ____________________________________________.
○ Forward reaction _________________________________________________________________ at all temperatures;
reverse reaction __________________________________________________________________ at all temperatures.
• ΔH° > 0, ΔS° < 0:
○ ΔH° ___________________________________________, ΔS° ____________________________________________.
○ Forward reaction _________________________________________________________________ at all temperatures;
reverse reaction __________________________________________________________________ at all temperatures.
Temperature for Spontaneity
• A process goes from spontaneous (∆G° < 0) to nonspontaneous (∆G° > 0) when ∆G° ____________________________:
○ To determine the temperature at which a process becomes spontaneous:
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ΔG°f
• Like ΔHf° and S°, ΔGf°‘s can be used to calculate ΔG°rxn:
• Like ΔH°f, for an element in its standard state, __________________________________________________________________________________.
○ For ions, ΔG°f defined relative to ____________________________________________________________________.
• Since ΔG° is dependent on temperature, using ΔG°f‘s only valid ______________________________________________.
○ At other temperatures, use ___________________________________________________________________________________________________
(ΔH° and ΔS° are assumed to be nearly constant with respect to temperature).
ΔH°rxn from ΔH°f’s
ΔS°rxn from ΔS°’s
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ΔG°rxn from ΔG°f’s
Temperature and Spontaneity - Example Question
• Given the reaction and data below:
○ Calculate ΔG°rxn, in kilojoules per mole, for the reaction at 25.0 °C.
○ Calculate ΔG°rxn, in kilojoules per mole, for the reaction at 250. °C.
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Gibbs Free Energy - Example Question
• Given the following reactions and thermochemical data, for each reaction:
○ Calculate the ΔG°rxn, in kilojoules per mole, at 298 K.
○ Calculate the temperature, in Kelvins, at which the reaction becomes spontaneous, and comment on how the
temperature affects the spontaneity of the reaction.
Thermodynamic Quantities - Example Question
• Explain the trends in the thermodynamic properties for the following pairs of substances and comment on their
thermodynamic stability:
○ F(g) & F2(g)
○ CS2(l) & CS2(g)
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○ ClF(g) & ClF3(g)
ALEKS Topics
• Using the general properties of Gibbs free energy
• Calculating dG from dH and dS
• Using the conditions of spontaneity to deduce the signs of ΔH and ΔS
• Calculating standard reaction free energy from standard free energies of formation
• Estimating a phase transition temperature from standard thermodynamic data
Textbook Questions for Extra Practice
• Worked Examples: 15.5 AB, 15.6 AB, 15.7 AB
• Section Review: 15.5.1 - 15.5.4
• End-of-Chapter: 15.31, 15.33, 15.35, 15.37, 15.39, 15.41, 15.43, 15.47, 15.49, 15.51, 15.53, 15.57, 15.59
15.6 - Thermodynamics in Living Systems
Modifying ΔG°rxn and Coupling Reactions
• Modifying reactions changes ΔG°rxn values similarly to ΔH°rxn :
○ When multiplying an equation by some factor, the ΔG°rxn is _____________________________ by the same factor.
○ When reversing an equation, the __________________________________________________ of ΔG°rxn is reversed.
○ When adding (coupling) equations, ΔG°rxn‘s are ________________________________________________________.
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Standard Free Energy of Formation - Example Question
• The first step in the metabolism of glucose in the human body is the phosphorylation of glucose (Equation 1, ∆G°rxn =
+12.7 kJ/mol), which is accompanied by hydrolysis of adenosine 5’-triphosphate (ATP) into adenosine 5’-diphosphate
(ADP) (Equation 2, ∆G°rxn = -37.6 kJ/mol). Given the following equations and data:
○ Calculate ∆G°f, in kilojoules per mole, for ATP.
○ Calculate ∆G°rxn, in kilojoules per mole, for the phosphorylation of glucose in the presence of ATP.
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Phosphorylation of Glucose & Hydrolysis of ATP
Textbook Questions for Extra Practice
• End-of-Chapter: 15.61
• Key Skills: 15.1 - 15.4
21.5 - Global Warming
IR Active & Inactive Vibrations
• Like energy levels in atoms, energy levels in molecules are __________________________________________________.
• Energy difference between vibrational levels in a molecule correspond to ______________________________ radiation.
○ Vibrations which result in a _______________________________________________________________________ of
the molecule absorb the radiation (IR active).
○ Vibrations which do not result in a change in the dipole moment of the molecule ____________________________
the radiation (not IR active).
▪ Changes _______________________________________________________________________ of the molecule.
Bromine Example
Bromine in visible and IR light
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Greenhouse Gases
• Greenhouse gases are molecules in the atmosphere that _______________________________________________________.
○ Prevent some IR radiation from escaping earth’s atmosphere.
Environmental Aspects
• Amount of CO2 in Earth’s atmosphere has been steadily rising since industrial revolution.
○ Some is natural, but much is _______________________________________________________________________.
• Global temperatures have been rising over a similar span.
IR Absorption by CO2 & H2O
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Infrared Spectroscopy
• Certain bonds/functional groups vibrate at characteristic frequencies.
○ Typically measured in wavenumbers (cm -1).
IR Spectra of H2O & CH4
Pulse Oximetry
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