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CHEM 015
CHEMISTRY FOR ENGINEERS
Lecture 4
CHEMICAL THERMODYNAMICS
and
HEAT ENGINES
HANDOUT VERSION
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Chemical Thermodynamics
• Spontaneity
• Entropy and its physical concept
• The Second and Third Law of
Outline Thermodynamics
• Entropy changes in chemical Reactions
• Gibbs Free Energy, temperature and
the equilibrium constant
Introduction to heat engines

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The Second Law

of
Thermodynamics
• Heat will not flow
spontaneously from a colder
body to a warmer body AND
heat energy cannot be
transformed completely into
mechanical work.
• The bottom line:
1. Heat always flows from a hot
body to a cold body
2. Nothing is 100% efficient

Statistical Thermodynamics

• κB - Boltzmann constant
• Ω - number of microstates for a given energy

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Correlations

Third Law of Thermodynamics

• The entropy of a perfect crystal of any pure substance approaches
zero as the temperature approaches absolute zero
• Implication is that it is impossible to attain a temperature of absolute
zero
• Though it is possible to evaluate the entropy of one mole of any given
chemical substance under standard conditions, by determining the
change in entropy from 0 K to 298 K at a pressure of 1 atm. This value
is called standard molar entropy, S°

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Gibbs free energy, G

• a thermodynamic potential that can

be used to calculate the maximum
amount of work that may be
performed by a thermodynamically
closed system at constant
temperature and pressure.
• The Gibbs free energy of a system at
any moment in time is defined as
the enthalpy of the system minus
the product of the temperature
times the entropy of the system.
• If the data are collected under
standard-state conditions, the result
is the standard-state free energy of
reaction (ΔG°)

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Free Energy and Spontaneous Change

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Free Energy and Chemical Reactions

• The free energy change under these conditions is the standard Gibbs
free energy change, ΔG°.
• We define a standard state as 1 atmosphere of pressure and
concentrations of solutions of 1 M.

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ΔGf° is the standard free energy of formation of a compound, that is, the free-
energy change that occurs when 1 mole of compound is synthesized from its
element in their standard states.

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Phase Transition Entropy

• At the temperature at which a phase transition occurs (the melting
point or boiling point) the system is at equilibrium (ΔG = 0).

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Free Energy and Chemical Equilibrium

• At equilibrium, by definition, ΔG = 0 and Q = K, where K is the
equilibrium constant. Thus,

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Carnot Engine

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Some useful diagrams

a thermodynamic process in which the a process in which no heat transfer takes

temperature of a system remains constant. place

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Expression Derivation for Reversible

Isothermal Process

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Expression Derivation for Reversible Adiabatic

Process

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References

• Brown, L., & Holme, T. (2005). Chemistry for Engineering Students. Cengage Learning.
• Brown, T., LeMay, H., Bursten, B., Murphy, C., Woodward, P., & Stoltzfus, M. (2017). Chemistry:
The Central Science (MasteringChemistry) (14th ed.). Pearson.
• Chang, R. (2002). Chemistry. McGraw-Hill Education.
• Gibbs Free Energy. (n.d.). https://chemed.chem.purdue.edu/genchem/topicreview/bp/ch21/gibbs.php

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