CH 17

Chemistry: A Molecular Approach, 2nd Ed.
Nivaldo Tro
Chapter 17
Free Energy
and
Thermodynamics
Roy Kennedy
Massachusetts Bay Community College
Wellesley Hills, MA
Copyright  2011 Pearson Education, Inc.
First Law of Thermodynamics
• You can’t win!

• First Law of Thermodynamics: Energy
cannot be created or destroyed
the total energy of the universe cannot change
though you can transfer it from one place to another
 DEuniverse = 0 = DEsystem + DEsurroundings
Tro: Chemistry: A Molecular Approach, 2/e 2 Copyright  2011 Pearson Education, Inc.
First Law of Thermodynamics
• Conservation of Energy
• For an exothermic reaction, “lost” heat from the
system goes into the surroundings
• Two ways energy is “lost” from a system
converted to heat, q
used to do work, w
• Energy conservation requires that the energy
change in the system equal the heat released +
work done
 DE = q + w
 DE = DH + PDV
• DE is a state function
internal energy change independent of how done
The Energy Tax
• You can’t break even!
• To recharge a battery with 100 kJ of
useful energy will require more than
100 kJ
 because of the Second Law of
Thermodynamics
• Every energy transition results in a
“loss” of energy
 an “Energy Tax” demanded by nature
 and conversion of energy to heat which
is “lost” by heating up the surroundings
Heat Tax
fewer steps
generally results
in a lower total
heat tax
Thermodynamics and Spontaneity
• Thermodynamics predicts whether a process will
occur under the given conditions
processes that will occur are called spontaneous
nonspontaneous processes require energy input to go
• Spontaneity is determined by comparing the
chemical potential energy of the system before
the reaction with the free energy of the system after
the reaction
if the system after reaction has less potential energy
than before the reaction, the reaction is
thermodynamically favorable.
• Spontaneity ≠ fast or slow
Comparing Potential Energy
The direction of
spontaneity can
be determined
by comparing
the potential
energy of the
system at the
start and the
end
Reversibility of Process
• Any spontaneous process is irreversible because
there is a net release of energy when it proceeds
in that direction
 it will proceed in only one direction
• A reversible process will proceed back and forth
between the two end conditions
 any reversible process is at equilibrium
 results in no change in free energy
• If a process is spontaneous in one direction, it
must be nonspontaneous in the opposite direction
Thermodynamics vs. Kinetics
Diamond → Graphite
Graphite is more stable than diamond, so the conversion

of diamond into graphite is spontaneous – but don’t worry,
it’s so slow that your ring won’t turn into pencil lead in
your lifetime (or through many of your generations)
Spontaneous Processes
• Spontaneous processes occur because they
release energy from the system
• Most spontaneous processes proceed from a
system of higher potential energy to a system at
lower potential energy
 exothermic
• But there are some spontaneous processes that
proceed from a system of lower potential energy to
a system at higher potential energy
 endothermic
• How can something absorb potential energy, yet
have a net release of energy?
Melting Ice
Melting is an
When a solid process,
Endothermic melts, the
particles have more
yet ice will
freedom of movement.
spontaneously melt
above 0 °C.
More freedom of motion
increases the
randomness of the
system. When systems
become more random,
energy is released. We
call this energy,
entropy
Factors Affecting Whether a
Reaction Is Spontaneous
• There are two factors that determine whether a
reaction is spontaneous. They are the
enthalpy change and the entropy change of
the system
• The enthalpy change, DH, is the difference in
the sum of the internal energy and PV work
energy of the reactants to the products
• The entropy change, DS, is the difference in
randomness of the reactants compared to the
products
Enthalpy Change
 DH generally measured in kJ/mol
• Stronger bonds = more stable molecules
• A reaction is generally exothermic if the bonds in the
products are stronger than the bonds in the
reactants
 exothermic = energy released, DH is negative
• A reaction is generally endothermic if the bonds in
the products are weaker than the bonds in the
reactants
 endothermic = energy absorbed, DH is positive
• The enthalpy change is favorable for exothermic
reactions and unfavorable for endothermic reactions
Entropy
• Entropy is a thermodynamic function
that increases as the number of
energetically equivalent ways of
arranging the components increases, S
 S generally J/mol
• S = k ln W
k = Boltzmann Constant = 1.38 x 10−23 J/K
W is the number of energetically equivalent
ways a system can exist
 unitless
• Random systems require less energy
than ordered systems
W
These are energetically
equivalent states for the
expansion of a gas.
It doesn’t matter, in terms
of potential energy,
whether the molecules
are all in one flask, or
evenly distributed
But one of these states is
more probable than the
other two
Macrostates → Microstates
These
microstates all
have the same
macrostate
Thisare
So there macrostate
six can be achieved through
several
different different arrangements of the particles
particle
arrangements
that result in the
same macrostate
Macrostates and Probability
There is only one possible
arrangement that gives State
A and one that gives State B
There are six possible

arrangements that give State C
The macrostate
Therefore Statewith the
C has
highest entropy
higher also than
entropy has the
greatest dispersal
either State A orofState
energy
B
There is six times the
probability of having the
State C macrostate than
either State A or State B
Changes in Entropy, DS
 DS = Sfinal − Sinitial
• Entropy change is favorable when the result is a
more random system
 DS is positive
• Some changes that increase the entropy are
reactions whose products are in a more random
state
solid more ordered than liquid more ordered than gas
reactions that have larger numbers of product
molecules than reactant molecules
increase in temperature
solids dissociating into ions upon dissolving
Increases in Entropy
DS
• For a process where the final condition is more
random than the initial condition, DSsystem is
positive and the entropy change is favorable
for the process to be spontaneous
• For a process where the final condition is more
orderly than the initial condition, DSsystem is
negative and the entropy change is
unfavorable for the process to be
spontaneous
 DSsystem = DSreaction = Sn(S°products) − Sn(S°reactants)
Entropy Change in State Change
• When materials change state, the number of
macrostates it can have changes as well
the more degrees of freedom the molecules have,
the more macrostates are possible
solids have fewer macrostates than liquids, which
have fewer macrostates than gases
Entropy Change and State Change
Practice – Predict whether DSsystem is + or −
for each of the following
• A hot beaker burning your fingers DS is +

• Water vapor condensing DS is −
• Separation of oil and vinegar salad dressing DS is −
• Dissolving sugar in tea DS is +
• 2 PbO2(s)  2 PbO(s) + O2(g) DS is +
• 2 NH3(g)  N2(g) + 3 H2(g) DS is +
• Ag+(aq) + Cl−(aq)  AgCl(s) DS is −
The 2nd Law of Thermodynamics
• The 2nd Law of Thermodynamics says that the
total entropy change of the universe must be
positive for a process to be spontaneous
for reversible process DSuniv = 0
for irreversible (spontaneous) process DSuniv > 0
• DSuniverse = DSsystem + DSsurroundings
• If the entropy of the system decreases, then the
entropy of the surroundings must increase by a
larger amount
when DSsystem is negative, DSsurroundings must be
positive and big for a spontaneous process
Heat Flow, Entropy, and the 2nd Law
When ice is placed in
water, heat flows from
the water into the ice
According to the 2nd Law,
heat must flow from
water to ice because it
results in more dispersal
of heat. The entropy of
the universe increases.
Heat Transfer and Changes in
Entropy of the Surroundings
• The 2nd Law demands that the entropy of the
universe increase for a spontaneous process
• Yet processes like water vapor condensing are
spontaneous, even though the water vapor is more
random than the liquid water
• If a process is spontaneous, yet the entropy change
of the process is unfavorable, there must have
been a large increase in the entropy of the
surroundings
• The entropy increase must come from heat released
by the system – the process must be exothermic!
Entropy Change in the System and
Surroundings
When the entropy
change in system is
unfavorable (negative),
the entropy change in
the surroundings must
be favorable (positive),
and large to allow the
process to be
spontaneous
Heat Exchange and DSsurroundings
• When a system process is exothermic, it adds heat to
the surroundings, increasing the entropy of the
surroundings
• When a system process is endothermic, it takes heat
from the surroundings, decreasing the entropy of the
surroundings
• The amount the entropy of the surroundings
changes depends on its
original temperature
 the higher the original
temperature, the less
effect addition or
removal of heat has
Temperature Dependence of DSsurroundings
• When heat is added to surroundings that are

cool it has more of an effect on the entropy than
it would have if the surroundings were already
hot
• Water freezes spontaneously below 0 °C
because the heat released on freezing
increases the entropy of the surroundings
enough to make DS positive
above 0 °C the increase in entropy of the
surroundings is insufficient to make DS positive
Quantifying Entropy Changes in
Surroundings
• The entropy change in the surroundings is
proportional to the amount of heat gained or lost
qsurroundings = −qsystem
• The entropy change in the surroundings is also
inversely proportional to its temperature
• At constant pressure and temperature, the
overall relationship is
Example 17.2a: Calculate the entropy change of the
surroundings at 25ºC for the reaction below
C3H8(g) + 5 O2(g)  3 CO2(g) + 4 H2O(g) DHrxn = −2044 kJ
Given: DHsystem = −2044 kJ, T = 25 ºC = 298 K
Find: DSsurroundings, J/K
Conceptual
Plan: T, DH DS
Relationships:
Solution:
Check: combustion is largely exothermic, so the entropy of

the surroundings should increase significantly
Practice – The reaction below has DHrxn = +66.4 kJ at
25 °C. (a) Determine the Dssurroundings, (b) the sign of
DSsystem, and (c) whether the process is spontaneous
2 O2(g) + N2(g)  2 NO2(g)
Practice – The reaction 2 O2(g) + N2(g)  2 NO2(g) has DHrxn
= +66.4 kJ at 25 °C. Calculate the entropy change of the
surroundings. Determine the sign of the entropy change in
the system and whether the reaction is spontaneous.
Given: DHsys = +66.4 kJ, T = 25 ºC = 298 K
Find: DSsurr, J/K, DSreact + or −, DSuniverse + or −
Conceptual
Plan: T, DH DS
Relationships:
Solution: the major difference is that there are
fewer product molecules than
reactant molecules, so the DSreaction
is unfavorable and (−)
both DSsurroundings and DSreaction are (−),

because DSsurroundings is DSuniverse is (−) and the process is
nonspontaneous
(−) it is unfavorable
Gibbs Free Energy and Spontaneity
• It can be shown that −TDSuniv = DHsys−TDSsys
• The Gibbs Free Energy, G, is the maximum
amount of work energy that can be released to the
surroundings by a system
 for a constant temperature and pressure system
 the Gibbs Free Energy is often called the Chemical
Potential because it is analogous to the storing of energy
in a mechanical system
 DGsys = DHsys−TDSsys
• Because DSuniv determines if a process is
spontaneous, DG also determines spontaneity
 DSuniv is + when spontaneous, so DG is −
Gibbs Free Energy, DG
• A process will be spontaneous when DG is
negative
 DG will be negative when
 DH is negative and DS is positive
exothermic and more random
 DH is negative and large and DS is negative but small
 DH is positive but small and DS is positive and large
or high temperature
• DG will be positive when DH is + and DS is −
never spontaneous at any temperature
• When DG = 0 the reaction is at equilibrium
DG, DH, and DS
Free Energy Change and Spontaneity
Example 17.3a: The reaction CCl4(g)  C(s, graphite) + 2 Cl2(g) has
DH = +95.7 kJ and DS = +142.2 J/K at 25 °C.
Calculate DG and determine if it is spontaneous.
Given: DH = +95.7 kJ, DS = 142.2 J/K, T = 298 K
Find: DG, kJ
Conceptual
Plan: T, DH, DS DG
Relationships:
Solution:
Answer: Because DG is +, the reaction is not spontaneous

at this temperature. To make it spontaneous, we
need to increase the temperature.
Practice – The reaction Al(s) + Fe2O3(s)  Fe(s) + Al2O3(s) has
DH = −847.6 kJ and DS = −41.3 J/K at 25 °C.
DH = −847.6 kJ and DS = −41.3 J/K at 25 °C.
Given: DH = −847.6 kJ and DS = −41.3 J/K, T = 298 K
Find: DG, kJ
Conceptual
Plan: T, DH, DS DG
Relationships:
Solution:
Answer: Because DG is −, the reaction is spontaneous at

this temperature. To make it nonspontaneous, we
need to increase the temperature.
Example 17.3b: The reaction CCl4(g)  C(s, graphite) + 2 Cl2(g) has
DH = +95.7 kJ and DS = +142.2 J/K.
Calculate the minimum temperature it will be spontaneous.
Given: DH = +95.7 kJ, DS = +142.2 J/K, DG < 0
Find: T, K
Conceptual
Plan: DG, DH, DS T
Relationships:
Solution:
Answer: the temperature must be higher than 673K for

the reaction to be spontaneous
DH = −847.6 kJ and DS = −41.3 J/K.
Calculate the maximum temperature it will be spontaneous.
DH = −847.6 kJ and DS = −41.3 J/K at 25 °C.
Determine the maximum temperature it is spontaneous.
Given: DH = −847.6 kJ and DS = −41.3 J/K, DG > 0
Find: T, C
Conceptual
Plan: DG, DH, DS T
Relationships:
Solution:
2048 − 273 = 1775 C
Answer: any temperature above 1775 C will make the

reaction nonspontaneous
Standard Conditions
• The standard state is the state of a
material at a defined set of conditions
• Gas = pure gas at exactly 1 atm pressure
• Solid or Liquid = pure solid or liquid in its
most stable form at exactly 1 atm pressure
and temperature of interest
usually 25 °C
• Solution = substance in a solution with
concentration 1 M
The 3rd Law of Thermodynamics:
Absolute Entropy
• The absolute entropy of a
substance is the amount of
energy it has due to dispersion of
energy through its particles
• The 3rd Law states that for a
perfect crystal at absolute zero,
the absolute entropy = 0 J/mol∙K
 therefore, every substance that is not
a perfect crystal at absolute zero has
some energy from entropy
 therefore, the absolute entropy of
substances is always +
Standard Absolute Entropies
• S°
• Extensive
• Entropies for 1 mole of a substance at 298 K
for a particular state, a particular allotrope,
particular molecular complexity, a particular
molar mass, and a particular degree of
dissolution
Standard Absolute Entropies
Relative Standard Entropies:
States
• The gas state has a larger entropy than the
liquid state at a particular temperature
• The liquid state has a larger entropy than the
solid state at a particular temperature
S°,
Substance
(J/mol∙K)
H2O (l) 70.0
H2O (g) 188.8
Molar Mass
• The larger the molar
mass, the larger the
entropy
• Available energy states
more closely spaced,
allowing more dispersal
of energy through the
states
Allotropes
• The less constrained
the structure of an
allotrope is, the
larger its entropy
• The fact that the
layers in graphite
are not bonded
together makes it
less constrained
Molecular Complexity
• Larger, more complex Molar S°,
Substance
molecules generally Mass (J/mol∙K)
have larger entropy CO
Ar (g)
(g) 39.948
28.01 154.8
197.7
• More available energy CNO
2H4(g)
(g) 30.006
28.05 210.8
219.3
states, allowing more
dispersal of energy
through the states
Relative Standard Entropies
Dissolution
• Dissolved solids S°,

Substance
generally have larger (J/mol∙K)
entropy KClO3(s) 143.1
• Distributing particles KClO3(aq) 265.7
throughout the mixture
The Standard Entropy Change, DS
• The standard entropy change is the difference

in absolute entropy between the reactants and
products under standard conditions
DSºreaction = (∑npSºproducts) − (∑nrSºreactants)
remember: though the standard enthalpy of
formation, DHf°, of an element is 0 kJ/mol, the
absolute entropy at 25 °C, S°, is always positive
Substance S, J/molK
Example 17.4: Calculate DS for the NH3(g) 192.8
reaction O2(g) 205.2
4 NH3(g) + 5 O2(g)  4 NO(g) + 6 H2O(g) NO(g) 210.8
H2O(g) 188.8
Given: standard entropies from Appendix IIB
Find: DS, J/K
Conceptual
Plan: SNH3, SO2, SNO, SH2O DS
Relationships:
Sol’n:
Check:
DS is +, as you would expect for a reaction with more gas
product molecules than reactant molecules
Practice – Calculate the DS for the reaction
2 H2(g) + O2(g)  2 H2O(g)

H2(g) 130.7
O2(g) 205.2
H2O(g) 188.8
Example 17.4: Calculate DS for the
H2(g) 130.6
reaction
2 H2(g) + O2(g)  2 H2O(g) O2(g) 205.2
H2O(g) 188.8
Given: standard entropies from Appendix IIB
Find: DS, J/K
Conceptual
Plan: SH2, SO2, SH2O DS
Relationships:
Solution:
Check:
DS is −, as you would expect for a reaction with more
gas reactant molecules than product molecules
Calculating DG
• At 25 C
DGoreaction = SnDGof(products) - SnDGof(reactants)
• At temperatures other than 25 C
 assuming the change in DHoreaction and DSoreaction is
negligible
DGreaction = DHreaction – TDSreaction
• or
DGtotal = DGreaction 1 + DGreaction 2 + ...
Example 17.6: The reaction SO2(g) + ½ O2(g)  SO3(g) has
DH = −98.9 kJ and DS = −94.0 J/K at 25 °C.
Calculate DG at 125 C and determine if it is more or less
spontaneous than at 25 °C with DG° = −70.9 kJ/mol SO3.
Given: DH = −98.9 kJ, DS = −94.0 J/K, T = 398 K
Find: DG, kJ
Conceptual
Plan: T, DH, DS DG
Relationships:
Solution:
Answer: because DG is −, the reaction is spontaneous at

this temperature, though less so than at 25 C
Practice – Determine the free energy change in the
following reaction at 298 K
2 H2O(g) + O2(g)  2 H2O2(g)
Substance DH, kJ/mol S, J/mol
H2O2(g) −136.3 232.7
O2(g) 0 205.2
H2O(g) −241.8 188.8
2 H2O(g) + O2(g)  2 H2O2(g)
Given: standard energies
DH = 211.0 from
kJ, DS Appendix
= −117.4 J/K,IIB,
T =T298
= 298
K K
Find: DG,
DG, kJ
kJ
Conceptual DH ° Sº of prod & react DH, DSº DG
f
Plan:
Relationships:
Solution:
Standard Free Energies of Formation
• The free energy of formation (DGf°) is the change
in free energy when 1 mol of a compound forms
from its constituent elements in their standard
states
• The free energy
of formation of
pure elements in
their standard
states is zero
Substance DGf°, kJ/mol
Example 17.7: Calculate DG at 25 C CH4(g) −50.5
O2(g) 0.0
for the reaction
CO2(g) −394.4
CH4(g) + 8 O2(g)  CO2(g) + 2 H2O(g) + 4 O3(g)
H2O(g) −228.6
O3(g) +163.2
Given: standard free energies of formation from Appendix IIB
Find: DG, kJ
Conceptual DGf° of prod & react DG
Plan:
Relationships:
Solution:
2 H2O(g) + O2(g)  2 H2O2(g)
Substance DG, kJ/mol
H2O2(g) −105.6
O2(g) 0
H2O(g) −228.6
2 H2O(g) + O2(g)  2 H2O2(g)

Find: DG, kJ
Conceptual DGf° of prod & react DG
Plan:
Relationships:
Solution:
DG Relationships
• If a reaction can be expressed as a series of
reactions, the sum of the DG values of the
individual reaction is the DG of the total reaction
 DG is a state function
• If a reaction is reversed, the sign of its DG value
reverses
• If the amount of materials is multiplied by a factor,
the value of the DG is multiplied by the same
factor
 the value of DG of a reaction is extensive
Example 17.8: Find DGºrxn for the following reaction
using the given equations
3 C(s) + 4 H2(g)  C3H8(g)
Given: C3H8(g) + 5 O2(g)  3 CO2(g) + 4 H2O(g) DGº = −2074 kJ
C(s) + O2(g)  CO2(g) DGº = −394.4 kJ
2 H2(g) + O2(g)  2 H2O(g) DGº = −457.1 kJ
Find: DGº of 3 C(s) + 4 H2(g)  C3H8(g)
Rel: Manipulate the given reactions so they add up to the
reaction you wish to find. The sum of the DGº’s is the
DGº of the reaction you want to find.
Solution: 3 CO2(g) + 4 H2O(g)  C3H8(g) + 5 O2(g) DGº = +2074 kJ
3 xC(s)
[C(s)
+ 3+ O 2(g) 
O2(g)  3CO
CO 2(g)]
2(g) DGº
DGº==3(−394.4
−1183.2 kJ
kJ)
2H
4 x 2(g)
[2 H+2(g)
2O +2(g) 
O2(g) 4H22HO2(g)O(g)] DGº
DGº==
2(−457.1
−914.2 kJ
kJ)
3 C(s) + 4 H2(g)  C3H8(g) DGº = −23 kJ
2 H2O(g) + O2(g)  2 H2O2(g)
Substance DG, kJ/mol
H2 (g) + O2(g)  H2O2(g) −105.6
2 H2 (g) + O2(g)  2 H2O(g) −457.2
2 H2O(g) + O2(g)  2 H2O2(g)
Given: H2(g) + O2(g)  H2O2(g) DGº = −105.6 kJ
2 H2(g) + O2(g)  2 H2O(g) DGº = −457.2 kJ
Find: DGº of 2 H2O(g) + O2(g)  2 H2O2(g)
Rel: Manipulate the given reactions so they add up to the
reaction you wish to find. The sum of the DGº’s is the
DGº of the reaction you want to find.
Solution: 2 H2(s) + 2 O2(g)  2 H2O2(g) DGº = −211.2 kJ
2 H2O(g)  2 H2(g) + O2(g) DGº = +457.2 kJ
2 H2O(g) + O2(g)  2 H2O2(g) DGº = +246.0 kJ
What’s “Free” About Free Energy?
• The free energy is the maximum amount of

energy released from a system that is available
to do work on the surroundings
• For many exothermic reactions, some of the
heat released due to the enthalpy change goes
into increasing the entropy of the surroundings,
so it is not available to do work
• And even some of this free energy is generally
lost to heating up the surroundings
Free Energy of an Exothermic Reaction
• C(s, graphite) + 2 H2(g) → CH4(g)
• DH°rxn = −74.6 kJ = exothermic
• DS°rxn = −80.8 J/K = unfavorable
• DG°rxn = −50.5 kJ = spontaneous
DG° is less than DH°

because some of the
released heat energy
is lost to increase the
entropy of the
surroundings
Free Energy and Reversible Reactions
• The change in free energy is a theoretical limit
as to the amount of work that can be done
• If the reaction achieves its theoretical limit, it is a
reversible reaction
Real Reactions
• In a real reaction, some of the free energy is
“lost” as heat
if not most
• Therefore, real reactions are irreversible
DG under Nonstandard Conditions
 DG = DG only when the reactants and products
are in their standard states
 their normal state at that temperature
 partial pressure of gas = 1 atm
 concentration = 1 M
 Under nonstandard conditions, DG = DG + RTlnQ
 Q is the reaction quotient
 At equilibrium DG = 0
 DG = −RTlnK
Example 17.9: Calculate DG at 298 K for Substance P, atm
the reaction under the given conditions NO(g) 0.100
2 NO(g) + O2(g)  2 NO2(g) DGº = −71.2 kJ O2(g) 0.100
NO2(g) 2.00
Given: non-standard conditions, DGº, T

Find: DG, kJ
Conceptual DG, PNO, PO2, PNO2 DG
Plan:
Relationships:
Solution:
Practice – Calculate DGrxn for the given
reaction at 700 K under the given conditions
N2(g) + 3 H2(g)  2 NH3(g) DGº = +46.4 kJ
Substance P, atm
N2(g) 33
H2(g) 99
NH3(g) 2.0
Substance P, atm
Practice – Calculate DGrxn for the given
reaction at 700 K under the given N2(g) 33
conditions H2(g) 99
N2(g) + 3 H2(g)  2 NH3(g) DGº = +46.4 kJ NH3(g) 2.0
Given: non-standard conditions, DGº, T

Find: DG, kJ
Conceptual DG, PNO, PO2, PNO2 DG
Plan:
Relationships:
Solution:
DGº and K
• Because DGrxn = 0 at equilibrium, then
DGº = −RTln(K)
• When K < 1, DGº is + and the reaction is
spontaneous in the reverse direction under
standard conditions
 nothing will happen if there are no products yet!
• When K > 1, DGº is − and the reaction is
spontaneous in the forward direction under
standard conditions
• When K = 1, DGº is 0 and the reaction is at
equilibrium under standard conditions
Example 17.10: Calculate K at 298 K Substance DGf°, kJ/mol
for the reaction N2O4(g) +99.8
N2O4(g)  2 NO2(g) NO2(g) +51.3

Find: K
Conceptual
DGf of prod & react DG K
Plan:
Relationships: DGº = −RTln(K)
Solution:
Practice – Estimate the equilibrium constant
for the given reaction at 700 K
N2(g) + 3 H2(g)  2 NH3(g) DGº = +46.4 kJ
Practice – Estimate the Equilibrium Constant
for the given reaction at 700 K
N2(g) + 3 H2(g)  2 NH3(g) DGº = +46.4 kJ
Given: DGº
Find: K
Conceptual
DG K
Plan:
Relationships: DGº = −RTln(K)
Solution:
Why Is the Equilibrium Constant
Temperature Dependent?
• Combining these two equations
DG° = DH° − TDS°
DG° = −RTln(K)
• It can be shown that
• This equation is in the form y = mx + b

• The graph of ln(K) versus inverse T is a
straight line with slope and y-intercept

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Chemistry: A Molecular Approach, 2nd Ed.

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There are six possible

• A hot beaker burning your fingers DS is +

• When heat is added to surroundings that are

Check: combustion is largely exothermic, so the entropy of

both DSsurroundings and DSreaction are (−),

Answer: Because DG is +, the reaction is not spontaneous

Answer: Because DG is −, the reaction is spontaneous at

Answer: the temperature must be higher than 673K for

2048 − 273 = 1775 C

Answer: any temperature above 1775 C will make the

• Dissolved solids S°,

• The standard entropy change is the difference

Substance S, J/molK

Answer: because DG is −, the reaction is spontaneous at

Given: standard free energies of formation from Appendix IIB

• The free energy is the maximum amount of

DG° is less than DH°

Given: non-standard conditions, DGº, T

Given: non-standard conditions, DGº, T

Given: standard free energies of formation from Appendix IIB

• This equation is in the form y = mx + b

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