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Chapter 16 Entropy
•Thermodynamics lets us predict whether a
Spontaneity, process will occur but gives no information
Entropy, about the amount of time required for the
process.
and
Free Energy •A spontaneous process is one that occurs
without outside intervention.
Figure 16.2:
The rate of a reaction
depends on the pathway
First Law of Thermodynamics
from reactants to products; • The First Law of Thermodynamics states
this is the domain of that the energy of the universe is constant.
kinetics. Thermodynamics Ea
tells us whether a reaction
While energy may change in form (heat,
is spontaneous based only work, etc.) and be exchanged between the
on the properties of the system & surroundings - the total energy
reactants and products.
The predictions of
remains constant. To describe the system:
thermodynamics do not Work done by the system is negative.
require knowledge of the
Work done on the system is positive.
pathway between reactants
and products. Heat evolved by the system is negative.
Heat absorbed by the system is positive.
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Spontaneous Processes and
Enthalpy and Enthalpy Change
Entropy
• In Chapter 6, we tentatively defined • A spontaneous process is a physical or
enthalpy in terms of the relationship of ∆H chemical change that occurs by itself .
to the heat at constant pressure. • Examples include:
• The standard enthalpy change for a reaction is A rock at the top of a hill rolls down.
Heat flows from a hot object to a cold one.
∆H o = ∑ n∆H of (products ) − ∑ m∆H of (reactants )
An iron object rusts in moist air.
• These processes occur without requiring an
outside force and continue until equilibrium
is reached.
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Figure 16.4: Possible
For two molecules,
arrangements (states)
A & B, there are of four molecules
four microstates in a two-bulbed flask.
•Ssolid < Sliquid << Sgas • The net change in entropy of the system, ∆S ,
equals the sum of the entropy created during
Solid: Only a few Gas: Many allowed the spontaneous process and the change in
“allowed” positions, positions, molecules energy associated with the heat flow.
molecules or atoms are far apart.
close together
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Entropy and the
Some examples of entropy changes: Second Law of Thermodynamics
Does entropy of the system increase or decrease for the following? So for any process: )Suniverse > 0, process is spontaneous
2 H2 (g) + O2 (g) º 2 H2O (g) at constant pressure and 25oC )Suniverse = 0, process tends not to occur,
at equilibrium
Decreases – simple molecules form more complex molecule, )Suniverse < 0, reverse process occurs
So )Ssystem is - spontaneously
Na (s) + heat º Na (l) at the m.p. temperature of Na We can determine )Ssystem – How can we determine )Ssurroundings?
)Ssurroundings determined primarily by heat flow between system
Increases – atoms of Na have more “available positions” in
the liquid state. )Ssystem is + & surroundings. If heat flows into the surroundings (i.e., when
a reaction is exothermic) the random motions of the molecules
H 2O in the surroundings increase. Thus, the entropy of the
NaCl (s) º Na+ (aq) + Cl- (aq) for 10 g NaCl in 1L H2O at 25 oC surroundings increases.
Increases – ions formed from NaCl are more simple in
structure and have more available position. )Ssystem is +
Entropy and the Second Law of Entropy and the Second Law of
Thermodynamics Thermodynamics
• The second law of thermodynamics states • The second law of thermodynamics states
that the total entropy of the universe always that the total entropy of the universe always
increases for a spontaneous process. increases for a spontaneous process.
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Entropy Change for a Phase Entropy Change for a Phase
Transition Transition
• If during a phase transition, such as ice • If during a phase transition, such as ice
melting, heat is slowly absorbed by the system, melting, heat is slowly absorbed by the system,
it remains near equilibrium as the ice melts. it remains near equilibrium as the ice melts.
• Under these conditions, no significant amount • Other phase changes, such as vaporization of a
of entropy is created. liquid, also occur under equilibrium conditions.
• The entropy results entirely from the absorption • Therefore, you can use the previous equation to
of heat. Therefore, obtain the )Ssys for a phase change. For the
q melting of 1 mole of ice at 0oC, the )Ssys is
∆S = (For an equilibrium process)
T )Ssys = +6.03 kJ/273 K = +0.0221 kJ/(mole K)
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Standard entropy of methyl chloride, CH3Cl, at various
temperatures.
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Entropy Change for a Reaction Entropy Change for a Reaction
• You can calculate the entropy change for • You can calculate the entropy change for
a reaction using a summation law, similar to a reaction using a summation law, similar to
the way you obtained ∆Ho. the way you obtained ∆Ho.
∆S o = ∑ nS o ( products ) − ∑ mS o ( reactants )
• The entropy usually increases in the following
situations:
• Even without knowing the values for the 1. A reaction in which a molecule is broken
entropies of substances, you can sometimes into two or more smaller molecules.
predict the sign of ∆So for a reaction.
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A Problem To Consider A Problem To Consider
• Calculate the change in entropy, ∆So, at 25 oC for the • Calculate the change in entropy, ∆So, at 25 oC for the
reaction in which urea is formed from NH3 and CO2. reaction in which urea is formed from NH3 and CO2.
The standard entropy of NH2CONH2 is 174 J/(mol.K). The standard entropy of NH2CONH2 is 174 J/(mol.K).
See Appendix 4 for other values. See Appendix 4 for other values.
2NH 3 (g ) + CO 2 (g ) → NH 2CONH 2 (aq ) + H 2O(l ) 2NH 3 (g ) + CO 2 (g ) → NH 2CONH 2 (aq ) + H 2O(l )
• We can now use the summation law to • We can now use the summation law to
calculate the entropy change. calculate the entropy change.
∆S o = ∑ nS o ( products ) − ∑ mS o ( reactants) ∆So = [(174 + 70) − ( 2 × 193 + 214)]J / K = −356 J/K
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Effect of ∆H and ∆S on
Spontaneity Standard Free-Energy Change
∆H ∆S Result
• The standard free energy change, ∆Go, is
− + spontaneous at all temps the free energy change that occurs when
reactants and products are in their standard
+ + spontaneous at high temps states.
− − spontaneous at low temps • The next example illustrates the calculation of
the standard free energy change, ∆Go, from
+ − not spontaneous at any temp ∆Ho and ∆So.
∆ G = ∆ H − T∆ S ∆ G o = ∆ H o − T∆ S o
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Standard Free Energies of
Formation
• The standard free energy of formation, ∆Gfo,
of a substance is the free energy change that
occurs when 1 mol of a substance is formed
from its elements in their stablest states at 1 atm
pressure and 25 oC.
• By tabulating ∆Gfo for substances, as in
Appendix 4, you can calculate the ∆Go for a
reaction by using a summation law.
∆G o = ∑ n∆G of (products ) − ∑ m∆G of (reactants)
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∆Go as a Criteria for ∆Go as a Criteria for
Spontaneity Spontaneity
• The following rules are useful in judging • The following rules are useful in judging
the spontaneity of a reaction. the spontaneity of a reaction.
2. When ∆Go is a large positive number (more 3. When ∆Go is a small negative or positive
positive than about +10 kJ), the reaction is value (less than about 10 kJ), the reaction
nonspontaneous as written, and reactants do gives an equilibrium mixture with
not give significant amounts of product at significant amounts of both reactants and
equilibrium. products.
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Free-energy change during a nonspontaneous reaction.
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A Problem To Consider
• Find the value for the equilibrium constant, K, at 25 oC
(298 K) for the following reaction. The standard free-
energy change, ∆Go, at 25 oC equals –13.6 kJ.
2NH 3 (g ) + CO 2 (g ) NH 2CONH 2 (aq) + H 2O(l )
∆G o
ln K =
− RT
∆G oT = ∆H o − T∆So
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A Problem To Consider A Problem To Consider
• Find the ∆Go for the following reaction at 25 oC • Find the ∆Go for the following reaction at 25 oC
and 1000 oC. Relate this to reaction spontaneity. and 1000 oC. Relate this to reaction spontaneity.
CaCO 3 (s ) → CaO(s ) + CO 2 (g ) CaCO 3 (s ) → CaO(s ) + CO 2 (g )
∆Hfo: -1206.9 -635.1 -393.5 kJ ∆Hfo: -1206.9 -635.1 -393.5 kJ
So: 92.9 38.2 213.7 J/K So: 92.9 38.2 213.7 J/K
∆H = ∑
o
n∆H of (products) − ∑ m∆H of (reactants) ∆S = ∑ n∆S (products) − ∑ m∆S o (reactants)
o o
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A Problem To Consider A Problem To Consider
• Find the ∆Go for the following reaction at 25 oC • Find the ∆Go for the following reaction at 25 oC
and 1000 oC. Relate this to reaction spontaneity. and 1000 oC. Relate this to reaction spontaneity.
CaCO 3 (s ) → CaO(s ) + CO 2 (g ) CaCO 3 (s ) → CaO(s ) + CO 2 (g )
∆Hfo: -1206.9 -635.1 -393.5 kJ ∆Hfo: -1206.9 -635.1 -393.5 kJ
So: 92.9 38.2 213.7 J/K So: 92.9 38.2 213.7 J/K
• Now you substitute ∆Ho, ∆So (=0.1590 kJ/K), • Now we’ll use 1000 oC (1273 K) along with
and T (=298K) into the equation for ∆Gfo. our previous values for ∆Ho and ∆So.
So the reaction is
∆G oT = 130.9 kJ nonspontaneous ∆G oT = 178.3kJ − (1273 K )(0.1590 kJ / K )
at 25 oC.
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Temperature Dependence of K
Maximum Work
)Go = - RTlnK = )Ho - T )So and dividing both sides by T & R,
multiply both sides by -1
• Often reactions are not carried out in a way
that does useful work.
∆ H° • As a spontaneous precipitation reaction occurs,
•y = mx + b
R obtained.
• In principle, if a reaction is carried out to obtain
•(∆H° and S° ≈ independent of temperature the maximum useful work, no entropy is
over a small temperature range) produced.
Reversible v. Irreversible
Maximum Work Processes
• Often reactions are not carried out in a way
•Reversible: The universe is exactly the same
that does useful work.
• It can be shown that the maximum useful work, as it was before the cyclic process.
wmax , for a spontaneous reaction is ∆G. •Irreversible: The universe is different after
the cyclic process.
wmax = ∆G •All real processes are irreversible -- (some
• The term free energy comes from this result. work is changed to heat).
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