Chemical Thermodynamics

Chapter 18

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Section 18.1
Entropy and Spontaneity
• State the second law of thermodynamics.
• Define entropy.
• Identify the sign of ∆S from chemical equations or changes of state.
• Demonstrate a qualitative understanding of the relationship between entropy and
probability.

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Introduction to Chemical Thermodynamics
• Chemical thermodynamics is the study of how heat and work are
involved in chemical reactions and in physical changes, such as
changes of state
• The focus of this chapter is distinguishing spontaneous from
nonspontaneous processes
• Spontaneous processes happen under the indicated conditions;
they may occur quickly or slowly, but the process occurs
• Nonspontaneous processes do not occur under the indicated
conditions
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First Law of Thermodynamics
• The first law of thermodynamics states that the total energy of the
universe is constant
• Energy is neither created nor destroyed, but it can be transformed
from one form to another

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Review of Terms from Thermochemistry
• The process under study is the system, and everything else is the
surroundings

• Together the system + surroundings make up the universe

• In a reversible process, the enthalpy change of the forward process

is equal in magnitude but has the opposite sign of the enthalpy
change of the reverse process

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Enthalpy and Spontaneous Processes
• For example, the melting of ice, H2O(s) → H2O(l), is endothermic
and spontaneous at temperatures above the melting point
• However, the freezing of water is exothermic and spontaneous at
temperatures below the melting point
• Other processes are spontaneous only in one direction. You can
combust gasoline by providing a spark to produce carbon dioxide
and water
• The reverse reaction of gasoline combustion is never spontaneous

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Second Law of Thermodynamics
• The second law of thermodynamics states that spontaneous
processes always result in an overall increase in entropy, S, of the
universe
• Entropy is a measure of the degree of disorder or randomness in a
system
• Another way to think of entropy is that it describes how spread out
a system’s energy is

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Factors Affecting Entropy
• State of matter: Solids are highly organized, liquids less so, and gas
particles move randomly
• Temperature: An increase in temperature increases the kinetic energy,
which increases the motion of particles and the entropy, in all states of
matter

• Gases: An increase in the kinetic energy and motion of gases allows the
energy to be more randomly dispersed throughout the sample
• An increase in the number of particles provides more ways for the
system’s energy to be distributed

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Summary of Increases in Entropy, +ΔS
• A positive value for ΔS of the process (an increase in entropy)
results when there is
• a phase change from solid to liquid,
• a phase change from solid or liquid to gas,
• the dissolution of a solid into an aqueous solution,
• an increase in temperature within a phase, or
• an increase in the number of gas particles
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Online Resource: Figure 18.1 - Molecular View of the Phases - Animation

Figure 18.1
Phase Changes and Entropy

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Example 18.1
Determine the sign of ΔS for the following processes:
a. 2 KClO3(s) → 2 KCl(s) + 3 O2(g)

b. CO2(g) → CO2(s)
c.

d. condensation appearing on bathroom mirror after a shower

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Example 18.1 Solution (1 of 2)
Determine the sign of ΔS for the following processes:
a. 2 KClO3(s) → 2 KCl(s) + 3 O2(g)
∆𝑆 = +
The number of particles increases and a gas is formed.

b. CO2(g) → CO2(s)
∆𝑆 = −
A gas becomes a solid.

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Example 18.1 Solution (2 of 2)
Determine the sign of ΔS for the following processes:
c.
∆𝑆 = +
A solid becomes a gas.

d. condensation appearing on bathroom mirror after a shower

∆𝑆 = −
A gas becomes a liquid.

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Section 18.2
Entropy Changes:
Both Chemical and Physical
• State the third law of thermodynamics.
• Determine ∆S for both chemical reactions and changes of state using
standard molar entropies.

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Third Law of Thermodynamics
• You can predict the sign of ΔS based on the guidelines presented
earlier
• ΔS can be calculated based on the third law of thermodynamics,
which states that the entropy of a pure, perfectly ordered,
crystalline substance at absolute zero is zero: S (0 K) = 0

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Using Standard Molar Entropies
• Tabulated entropy values based on the third law are standard molar
J
entropies, 𝑆 °, and have units of
mol∙K

• Standard thermodynamic conditions are:

298 K, 1 atm gas pressure, and 1 M solute concentration

• Changes in entropy, ∆𝑆 °, can be calculated from 𝑆 °values.

°
∆𝑆rxn = ∑𝑚 𝑆 ° products − ∑𝑛 𝑆 ° reactants

• In this equation, m and n are the coefficients of the products and

reactants from the balanced chemical equation

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Table 18.1
Standard Entropies at 298 K of Selected Substances
Compound Compound
(state) (state)
CO2(g) 213.8 HCl(g) 186.9
CaO(s) 38.1 Hg(l) 75.9
CaCO3(s) 91.7 Hg(g) 175.0
H2(g) 130.7 I2(s) 116.1
H2O(l) 70.0
I2(g) 260.7
H2O(g) 188.8
O2(g) 205.2
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Example 18.3 °
∆𝑆rxn = ∑𝑚 𝑆 ° products − ∑𝑛 𝑆 ° reactants

Predict the sign of ΔS and calculate the standard entropy change

associated with the reaction of gaseous hydrogen and gaseous
oxygen to form water vapor.
2 H2(g) + O2(g) → 2 H2O(g)

Compound °
𝐉
𝑺
(state) 𝐦𝐨𝐥 · 𝐊
H2(g) 130.7
O2(g) 205.2
H2O(g) 188.8
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Example 18.3 Solution (1 of 3)
Predict the sign of ΔS and calculate the standard entropy change associated
with the reaction of gaseous hydrogen and gaseous oxygen to form water vapor.

Start by writing the balanced chemical equation.

2 H2(g) + O2(g) → 2 H2O(g)
Prediction: The number of moles of gases decreases in the reaction,
so ΔS will be negative (–).

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Example 18.3 Solution (2 of 3)
Predict the sign of ΔS and calculate the standard entropy change associated
with the reaction of gaseous hydrogen and gaseous oxygen to form water vapor.

2 H2(g) + O2(g) → 2 H2O(g)

°
Rewrite the equation for calculating ∆𝑆rxn in terms of this chemical
reaction.

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Example 18.3 Solution (3 of 3)
Predict the sign of ΔS and calculate the standard entropy change associated
with the reaction of gaseous hydrogen and gaseous oxygen to form water vapor.

Insert the tabulated 𝑆 ° values, taking care to match the states of

matter, and complete the calculation.
°
∆𝑆rxn

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Example 18.4
Predict the sign of ΔS and calculate the change in entropy
when 72.85 g of liquid mercury is vaporized.
Compound 𝐉
Hg(l) → Hg(g)
°
𝑺
(state) 𝐦𝐨𝐥 · 𝐊
Hg(l) 75.9
Hg(g) 175.0

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Example 18.4 Solution (1 of 3)
Predict the sign of ΔS and calculate the change in entropy when 72.85 g of
liquid mercury is vaporized.

Start by writing the chemical equation for the process.

Hg(l) → Hg(g)
Prediction: ΔS will be positive (+) because this is a phase change
from liquid to gas.

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Example 18.4 Solution (2 of 3)
Predict the sign of ΔS and calculate the change in entropy when 72.85 g of
liquid mercury is vaporized.

Hg(l) → Hg(g)
Entropy changes for physical changes are calculated the same as for
chemical changes; simply use one mole of the substance.

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Example 18.4 Solution (3 of 3)
Predict the sign of ΔS and calculate the change in entropy when 72.85 g of
liquid mercury is vaporized.

Insert the tabulated 𝑆f° values, taking care to match the states of matter,
and complete the calculation.

Finally, multiply by the number of moles present in the sample.

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Section 18.3
Entropy and Temperature
• Compare and contrast ∆Suniv, ∆Ssys, and ∆Ssurr .
• Calculate ∆Ssurr from ∆Hsys and temperature data for chemical and physical
changes.

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Entropy of the System, the Surroundings
and the Universe
• An overall change in entropy is equal to the change in entropy of the
system plus the change in entropy of the surroundings:

Δ𝑆univ = Δ𝑆sys + Δ𝑆surr

• For a process to be spontaneous, Δ𝑆univ must be positive, which occurs

if:
• both Δ𝑆sys and Δ𝑆surr are positive;

• Δ𝑆sys is negative, but Δ𝑆surr is positive and Δ𝑆surr > Δ𝑆sys; or

• Δ𝑆surr is negative, but Δ𝑆sys is positive and Δ𝑆sys > Δ𝑆surr

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Isothermal Processes
• In chemistry, the reaction being studied (the system) is typically
very small compared to the surroundings

• Thus, enthalpy changes in the system, ΔHsys, have a very minimal

effect on the temperature of the surroundings

• Systems that cause no temperature change on the surroundings

are known as isothermal processes

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ΔSsurr and Isothermal Processes
• For an isothermal process, the entropy change of the surroundings
is related to the thermal energy change of the system

• Because many chemical reactions occur at constant

pressure, qsys is simply the enthalpy change for the reaction

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• The entropy change of the surroundings is inversely proportional
to the temperature

• Low T—The surroundings have lower kinetic energy (KE) and the
release of heat energy by the system increases that KE. This causes
the particles in the surroundings to become more dispersed

• High T—The surroundings have higher KE and the release of heat

energy by the system increases that KE by a much smaller
percentage, dispersing the particles to a lesser degree

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Example 18.5
Calculate ΔSsurr and ΔSuniv for the reaction of gaseous hydrogen and
gaseous oxygen to form 2 mol of water vapor at 298 K.

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Example 18.5 Solution (1 of 3)
Calculate ΔSsurr and ΔSuniv for the reaction of gaseous hydrogen and gaseous
oxygen to form 2 mol of water vapor at 298 K.

Start by writing the balanced chemical equation,

2 H2(g) + O2(g) → 2 H2O(g),
° from ∆𝐻° data found here.
and calculating ∆𝐻rxn f

°
∆𝐻rxn = −483.6 kJ
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Example 18.5 Solution (2 of 3)
Calculate ΔSsurr and ΔSuniv for the reaction of gaseous hydrogen and gaseous
oxygen to form 2 mol of water vapor at 298 K.

Now calculate ΔSsurr using this equation:

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Example 18.5 Solution (3 of 3)
Calculate ΔSsurr and ΔSuniv for the reaction of gaseous hydrogen and gaseous
oxygen to form 2 mol of water vapor at 298 K.

Recall that ΔSsys was calculated for this reaction in Example 18.3.

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Section 18.4
Gibbs Free Energy
• Define Gibbs free energy.
• Describe how the signs of ∆H and ∆S affect the sign of ∆G.
• Calculate ∆𝐺 ° for chemical and physical processes using ∆𝐻f° ,∆𝑆 ° , and ∆𝐺f°
data and interpret the results.

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Free Energy, Enthalpy, and Entropy
• In the 1870s, J. Willard Gibbs defined a new state function, now
called Gibbs free energy, G, capable of predicting if a process is
spontaneous at a given temperature
• Recall that a state function is a property of a system that depends
only on the current state of the system and not on any changes
that have occurred previously
• Gibbs free energy is related to both the enthalpy change and the
entropy change of the system under study

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Deriving Gibbs Free Energy, G
• Start with the equation for total change in entropy
∆𝑆univ = ∆𝑆sys + ∆𝑆surr

• Substitute for ∆Ssurr

• Multiply by –T
– 𝑇∆𝑆univ = ∆𝐻sys − 𝑇∆𝑆𝑠𝑦𝑠

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G Is Defined as
• According to the second law of thermodynamics, ∆𝑆univ must be
positive for a spontaneous process

• Thus, −𝑇∆𝑆univ must be negative for a spontaneous process

• In the formal definition of Gibbs free energy below, H is enthalpy, S

is entropy and T is the absolute temperature

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Forms of the Free-Energy Equation
• For most chemical reactions, the process occurs at constant
temperature and pressure. Changes in free energy of these
systems is given by
∆𝐺 = ∆𝐻 − 𝑇∆𝑆
• For a process occurring under standard conditions, the Gibbs free-
energy change is
∆𝐺 ° = ∆𝐻° − 𝑇∆𝑆 °

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Interpreting Values
• A decrease in Gibbs free energy, ΔG < 0, corresponds to a
spontaneous process, i.e., spontaneous in the forward direction

• An increase in Gibbs free energy, ΔG > 0, indicates a

nonspontaneous process, i.e., spontaneous in the reverse direction

• When ΔG = 0, the system is at equilibrium

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Example 18.6
Determine ΔG° for the reaction of hydrogen and oxygen to
form water.
2 H2(g) + O2(g) → 2 H2O(g)

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Example 18.6 Solution
Determine ΔG° for the reaction of hydrogen and oxygen to form water.
2 H2(g) + O2(g) → 2 H2O(g)
Refer to Example 18.3 and Example 18.5 to obtain the previously
calculated values for ∆𝑆 ° and ∆𝐻° . Use these, and the standard
temperature (𝑇 = 298 K) in the Gibbs free-energy equation.

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Spontaneous, but Not Necessarily Fast
• The reaction of hydrogen and oxygen has a very large negative ΔG°
value of −457.1 kJ

• However, hydrogen and oxygen explosions do not happen at room

temperature (unless a spark is provided) due to the very high
activation energy

• Thermodynamics tells you if a process is spontaneous—it does not

provide any information about the rate of that process

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Free Energy of Formation,
• The standard free energy of formation, ∆𝐺f°, is the free-energy
change associated with the formation of a substance from its
component elements, in their standard states

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Example 18.7
°
Calculate Δ𝐺rxn for the combustion of propane.
C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O(l)

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Example 18.7 Solution (1 of 2)
°
Calculate Δ𝐺rxn for the combustion of propane.
C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O(l)
°
Start with the equation for calculating Δ𝐺rxn from tabulated Δ𝐺f°
data,
°
Δ𝐺rxn = Σ𝑚 Δ𝐺f° products − Σ𝑛 Δ𝐺f° reactants

and rewrite it for the combustion of propane.

°
Δ𝐺rxn = 3Δ𝐺f° CO2 g + 4Δ𝐺f° H2 O g − Δ𝐺f° C3H8 g + 5Δ𝐺f° O2 g

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Example 18.7 Solution (2 of 2)
°
Calculate Δ𝐺rxn for the combustion of propane.
C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O(l)
Insert the appropriate Δ𝐺f° values and calculate.

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Free Energy of Solution
• Free energy and entropy are also relevant to the formation of
solutions

• For example, the dissolution of ammonium nitrate, NH4NO3, in

water is highly endothermic and is used in instant cold packs

• A positive value of ΔHsoln indicates that the total energy needed to

separate the particles is greater than the energy released by
solvation

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Free Energy of Solution
• Why would this process occur spontaneously?

• The particles in the solid ionic compound are highly ordered, but
in solution, these particles become dispersed

• This increase in entropy is sufficient to overcome the positive

enthalpy changes associated with the dissolution of many solutes

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 Figure 18.6 - Endothermic Dissolution - Video

Figure 18.6
Endothermic Dissolution

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Section 18.5
Free-Energy Changes and Temperature
• Calculate ΔG at nonstandard temperatures.
• Determine the equilibrium temperature of a reaction and interpret the
results.

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Free-Energy Changes and Temperature
• Negative ΔH and positive ΔS are favored and drive the spontaneity of a
process
• When both quantities are favorable, the reaction is spontaneous as
written at all temperatures (nonspontaneous in reverse)
• When neither quantity is favorable, the reaction is nonspontaneous as
written (spontaneous in reverse)
• When one quantity is favorable but the other is not, the reaction is
enthalpy-driven in one direction but entropy-driven in the other. The
direction of spontaneity depends on the temperature

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Table 18.2
Signs of ΔH, ΔS, and ΔG
ΔH ΔS − TΔS ΔG = ΔH− TΔS Reaction Characteristics
− + − − Spontaneous at all temperatures

+ − + + Nonspontaneous at all temperatures

Spontaneous at low temperatures

− − + + or − Nonspontaneous at high temperatures

Spontaneous at high temperatures

+ + − + or − Nonspontaneous at low temperatures

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Calculating ΔG at Different Temperatures
ΔG = ΔH – TΔS

• The tabulated data are specific for values measured at 298 K

• However, ΔH and ΔS vary only slightly with temperature, so these

data can be used at temperatures other than 298 K

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Example 18.9
Calculate ΔG for the vaporization of TiCl4 at (a) 298 K and (b)
775 K.
TiCl4(l) → TiCl4(g)

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Example 18.9a Solution (1 of 3)
Calculate ΔG for the vaporization of TiCl4 at (a) 298 K and (b) 775 K.
TiCl4(l) → TiCl4(g)
Determine ΔH° and ΔS° to calculate ΔG at both temperatures.

°
Use tabulated data to calculate Δ𝐻rxn .

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Example 18.9a Solution (2 of 3)
Calculate ΔG for the vaporization of TiCl4 at (a) 298 K and (b) 775 K.
TiCl4(l) → TiCl4(g)
° .
Use tabulated data to calculate Δ𝑆rxn

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Example 18.9a Solution (3 of 3)
Calculate ΔG for the vaporization of TiCl4 at (a) 298 K and (b) 775 K.
TiCl4(l) → TiCl4(g)
Calculate ΔG at 298 K, ΔG°.

The positive value of ∆𝐺° indicates that vaporization of TiCl 4 is not

spontaneous at 298 K.

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Example 18.9b Solution
Calculate ΔG for the vaporization of TiCl4 at (a) 298 K and (b) 775 K.
TiCl4(l) → TiCl4(g)
Calculate ΔG at 775 K.

The negative value of ∆𝐺° indicates that the vaporization of TiCl4 is

spontaneous at 775 K.

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Determining the Temperature at which a
Process Becomes Spontaneous
• Consider again the vaporization of TiCl4. At what temperature
does the process become spontaneous?
• When the forward rate of a process equals the reverse rate, at
equilibrium, there is no net reaction and no free-energy change,
ΔG =0
∆𝐺 = ∆𝐻 − 𝑇∆𝑆 = 0
∆𝐻 = 𝑇∆𝑆

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Figure 18.7
Spontaneity and Temperature

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Example 18.10
Determine the minimum temperature for the spontaneous vaporization
of liquid mercury using data from Example 18.4 and Appendix A.2.
Hg(l) → Hg(g)
° J
From Example 18.4, Δ𝑆 = 99.1 and from the appendix, ∆𝐻° =
K
° kJ ° kJ
Δ𝐻f Hg g = 61.4 because Δ𝐻f Hg l = 0 .
mol mol

The vaporization of mercury becomes spontaneous at temperatures

above 620 K.

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Section 18.6
Gibbs Free Energy and Equilibrium
• Calculate ΔG° at nonstandard concentrations.
• Apply the relationship between ΔG° and the equilibrium constant, K.

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 at Nonstandard Conditions
• Standard conditions: 298 K, 1 M solutes, and gases at 1 atm

• For ∆𝐺 at nonstandard temperatures, use ∆𝐺 = ∆𝐻° − 𝑇∆𝑆°

• For ∆𝐺 under other nonstandard conditions, use

Δ𝐺 = Δ𝐺° + 𝑅𝑇 ln 𝑄

• ΔG° is the standard free-energy change, R is the gas constant

J
8.3145 , Q is the reaction quotient, and T is the absolute
mol⋅K
temperature

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 at Nonstandard Conditions
Δ𝐺 = Δ𝐺° + 𝑅𝑇 ln 𝑄
• In this equation, Q means Qc for aqueous reactions, but Qp for gaseous
reactions
• Q includes a concentration term for each aqueous species and a
pressure term for each gaseous species. So for heterogeneous systems,
Q may contain both concentrations and pressures
• The Haber process: N2(g) + 3 H2(g) ⇌ 2 NH3(g)

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Example 18.11
Calculate ΔG for the Haber process at 365 K for a mixture of 1.5 atm
N2, 4.5 atm H2, and 0.75 atm NH3.
N2(g) + 3 H2(g) ⇌ 2 NH3(g)

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Example 18.11 Solution (1 of 3)
Calculate ΔG for the Haber process at 365 K for a mixture of 1.5 atm N2, 4.5 atm
H2, and 0.75 atm NH3.
N2(g) + 3 H2(g) ⇌ 2 NH3(g)

Use the equation for ΔG and nonstandard conditions.

Start by calculating ΔG° from Δ𝐺f° values found in Appendix A.2.

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Example 18.11 Solution (2 of 3)
Calculate ΔG for the Haber process at 365 K for a mixture of 1.5 atm N2, 4.5 atm
H2, and 0.75 atm NH3.
N2(g) + 3 H2(g) ⇌ 2 NH3(g)

Calculate Q next.

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Example 18.11 Solution (3 of 3)
Calculate ΔG for the Haber process at 365 K for a mixture of 1.5 atm N2, 4.5 atm
H2, and 0.75 atm NH3.
N2(g) + 3 H2(g) ⇌ 2 NH3(g)

Plug your calculated values for Δ𝐺°and 𝑄 into the equation.

∆𝐺 = −49.5 kJ/mol

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Interpreting the Results
• In the previous example, the reaction has a greater free-energy
change under the stated nonstandard conditions than it does
under standard conditions. What does this mean?
• The negative sign of Δ𝐺° indicates that the reaction is not at
equilibrium under standard conditions and that Q < K. This favors
the forward direction
• The larger negative value of ∆𝐺 indicates that the reaction is even
farther from equilibrium and favors the forward reaction more
strongly

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Free Energy at Equilibrium
• When a reaction is at equilibrium, ΔG = 0 and Q = K

• When these are used in the ∆𝐺 equation, a bit of rearranging

results in an equation relating ∆𝐺 ° and K

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Table 18.3
The Relationship of and K
Δ𝐺° = −𝑅𝑇 ln 𝐾

𝚫𝑮° K

<0 >1

=0 =1

>0 <1

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Systems Proceed Spontaneously Toward
Equilibrium
• ΔG < 0
• The equilibrium position lies closer to the lower-energy
products and K > 1
• Starting from standard conditions (Q = 1), the forward process
is spontaneous
• ΔG = 0
• At equilibrium. Q = K
• No net change in the forward or reverse direction

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Systems Proceed Spontaneously Toward
Equilibrium
• ΔG > 0
• The equilibrium position lies closer to the lower-energy
reactants and K < 1
• Starting from standard conditions (Q = 1), the reverse process
is spontaneous

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Figure 18.9
Free Energy and the Approach to Equilibrium

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Calculating K from
Rearrange the equation below to isolate the equilibrium constant

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Example 18.12
Calculate the equilibrium constant for the Haber process at
298 K.

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Example 18.12 Solution (1 of 2)
Calculate the equilibrium constant for the Haber process at 298 K.

In Example 18.11, you calculated the ∆𝐺 ° for the Haber process from
Δ𝐺f° data. Use that value to solve for K.

Start by calculating the exponent.

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Example 18.12 Solution (2 of 2)
Calculate the equilibrium constant for the Haber process at 298 K.

Now solve for 𝐾.

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Interactive General Chemistry, © 2019 Macmillan Learning