Chemistry 180-213B

Introductory Physical
Chemistry

David Ronis

© 2002
McGill University
 -2-
All rights reserved. In accordance with Canadian Copyright Law, reproduction of this material, in whole or
in part, without the prior written consent the author is strictly prohibitied.
All truths are easy to understand once they are discovered; the point is to discover
them.

Philosophy is written in this grand book-I mean the universe-which stands contin-
ually open to our gaze, but it cannot be understood unless one first learns to com-
prehend the language and interpret the characters in which it is written. It is writ-
ten in the language of mathematics, and its characters are triangles, circles, and
other geometrical figures, without which it is humanly impossible to understand a
single word of it.
Opere Il Saggiatore
Galileo Galilei (1564 - 1642)
 -2-

The Founders of Thermodynamics

Joule

Clausius

Maxwell

Carnot

Kelvin

Gibbs
 -3-

Table of Contents

1. General Information . . . . . . . . . . . . . . . . . . . . . . 5
2. Kubo’s Divertissements . . . . . . . . . . . . . . . . . . . . . 8
2.1. Divertissement 1: Founders of the first law of thermodynamics . . . . . . . . 8
2.2. Divertissement 2: Why do we have winter heating? . . . . . . . . . . . 8
2.3. Divertissement 3: Nicolas Leonard Sadi Carnot . . . . . . . . . . . . . 10
2.4. Divertissement 4: Absolute Temperature . . . . . . . . . . . . . . . 10
2.5. Divertissement 8: On the names of thermodynamic functions . . . . . . . . 11
3. Probability and Statistics . . . . . . . . . . . . . . . . . . . . 13
4. Maxwell-Boltzmann Distribution . . . . . . . . . . . . . . . . . . 16
5. Collision Rates, Mean Free Path, and Diffusion . . . . . . . . . . . . . 22
6. Collision Theory of the Rate Constant . . . . . . . . . . . . . . . . 27
7. Notes on the First Law of Thermodynamics . . . . . . . . . . . . . . . 29
7.1. Zeroth Law of Thermodynamics . . . . . . . . . . . . . . . . . 29
7.2. Some Definitions . . . . . . . . . . . . . . . . . . . . . . 29
7.3. Euler’s Theorem, Partial Molar Quantities, . . . . . . . . . . . . . . 31
7.4. Work and Heat in Thermodynamics . . . . . . . . . . . . . . . . 32
7.5. Energy in Classical Mechanics . . . . . . . . . . . . . . . . . . 35
7.6. The First Law of Thermodynamics: . . . . . . . . . . . . . . . . 36
8. Thermochemistry . . . . . . . . . . . . . . . . . . . . . . . 38
8.1. Enthalpy Calculations: Chemical Reactions and Hess’ Law . . . . . . . . . 38
8.2. Measuring ∆H 0f . . . . . . . . . . . . . . . . . . . . . . . 39
8.3. Reactions at Different Temperatures: Kirchoff’s Law . . . . . . . . . . . 40
8.4. Bond Energies . . . . . . . . . . . . . . . . . . . . . . . 41
8.5. Some Manipulations Involving Thermodynamic Functions . . . . . . . . . 43
8.5.1. The relationship between C P and CV . . . . . . . . . . . . . . . 43
8.5.2. The Joule-Thompson Experiment . . . . . . . . . . . . . . . . . 44
9. The Second Law of Thermodynamics . . . . . . . . . . . . . . . . 46
10. Carnot Engines, Efficiency, and The Second Law . . . . . . . . . . . . 49
11. Efficiency Of A Real Carnot Engine . . . . . . . . . . . . . . . . . 54
12. The Clausius Inequality and the Mathematical Statement of the Second Law . . . . 57
13. Systems With Variable Composition: The Chemical Potential . . . . . . . . 59
14. Exact Differentials and Maxwell Relations . . . . . . . . . . . . . . 61
15. Thermodynamic Stability: Free Energy and Chemical Equilibrium . . . . . . . 67
15.4.1. Free Energy and Entropy of Mixing . . . . . . . . . . . . . . . 75
15.4.2. Determination of Free Energies of Formation . . . . . . . . . . . . 76
15.4.3. Determination of the Extent of a Reaction . . . . . . . . . . . . . 76
15.5. Coupled Reactions . . . . . . . . . . . . . . . . . . . . . 77
15.6. Temperature Dependence of K p . . . . . . . . . . . . . . . . . 77
16. Eigenvalues and Thermodynamic Stability . . . . . . . . . . . . . . 79
17. Entropy of Mixing: A Statistical View . . . . . . . . . . . . . . . . 81
18. Phase Equilibrium . . . . . . . . . . . . . . . . . . . . . . 84
19. Minimum and Maximum Boiling Azeotropes: The Gibbs-Konovalov Theorem . . . 88
20. Ideal Eutectic Phase Diagrams . . . . . . . . . . . . . . . . . . 91
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21. Capillary Rise and Depression . . . . . . . . . . . . . . . . . . 93

22. Problem Sets . . . . . . . . . . . . . . . . . . . . . . . . 95
22.1. Problem Set 1 . . . . . . . . . . . . . . . . . . . . . . . 95
22.2. Problem Set 2 . . . . . . . . . . . . . . . . . . . . . . . 97
22.3. Problem Set 3 . . . . . . . . . . . . . . . . . . . . . . . 99
22.4. Problem Set 4 . . . . . . . . . . . . . . . . . . . . . . . 100
22.5. Problem Set 5 . . . . . . . . . . . . . . . . . . . . . . . 101
22.6. Problem Set 6 . . . . . . . . . . . . . . . . . . . . . . . 102
22.7. Problem Set 7 . . . . . . . . . . . . . . . . . . . . . . . 103
22.8. Problem Set 8 . . . . . . . . . . . . . . . . . . . . . . . 104
22.9. Problem Set 9 . . . . . . . . . . . . . . . . . . . . . . . 105
22.10. Problem Set 10 . . . . . . . . . . . . . . . . . . . . . . 106
23. Past Exams . . . . . . . . . . . . . . . . . . . . . . . . 107
23.1. Quiz I: 1999 . . . . . . . . . . . . . . . . . . . . . . . 107
23.2. Quiz I: 2000 . . . . . . . . . . . . . . . . . . . . . . . 109
23.3. Quiz I: 2001 . . . . . . . . . . . . . . . . . . . . . . . 112
23.4. Quiz II: 1999 . . . . . . . . . . . . . . . . . . . . . . . 114
23.5. Quiz II: 2000 . . . . . . . . . . . . . . . . . . . . . . . 117
23.6. Quiz II: 2001 . . . . . . . . . . . . . . . . . . . . . . . 120
23.7. Final Exam: 1999 . . . . . . . . . . . . . . . . . . . . . . 122
23.8. Final Exam: 2000 . . . . . . . . . . . . . . . . . . . . . . 125
23.9. Final Exam: 2001 . . . . . . . . . . . . . . . . . . . . . . 128
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CHEMISTRY 213B: Introductory Physical Chemistry I.

1. General Information
Lectures: MWF 9:30 - 10:30
Otto Maass 10
Course Web Site: http://ronispc.chem.mcgill.ca/ronis/chem213/Notes.html
(Username: chem213; Password: Gibbs)

Professor: David Ronis

Office: Otto Maass Room 426
E-mail: [email protected]

Text
G. W. Castellan, Physical Chemistry.
Supplementary Texts
1. P. A. Rock, Chemical Thermodynamics.
2. Gordon M. Barrow, Physical Chemistry.
3. R. Kubo, Thermodynamics (Physics orientation, advanced)
Grades
There will be approximately one problem set per week, two quizes and a final exam.
The quizes will be given at 18:00 on:

Wednesday, February 6, 2002 and Wednesday, March 13, 2002

(in Otto Maass 112)

Completion of the homework is mandatory. Most of the problems will not be graded, although
one or two problems may be chosen at random and graded. Solutions to the problem sets will be
posted on the course web page.
You are strongly encouraged to do the homework. The problems will cover many
details not done in class and will prepare you for the exams. The exams will involve extensive
problem-solving and, in part, will contain problems from the homework! The typical student
will not do well in (or even pass) this course unless the problems are done. The course grading
scheme is:

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General Information -6- Chemistry CHEM 213W

Grade Distribution
Problems 10%
1st Quiz 25%
2nd Quiz 25%
Final 40%

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CHEMISTRY 213B: TENTATIVE OUTLINE

Date Topic Text Chapter

Lecture 1. Introduction: Thermodynamics, an overview 2

Lecture 2. Empirical properties of gases 2
Lecture 3. Empirical properties of liquids and solids 5

Lecture 4. Molecular basis: Kinetic theory of gases 4

Lecture 5. Collision rates, effusion, and diffusion 30
Lecture 6. Viscosity 30

Lecture 7. Temperature: the zeroth law of thermodynamics 6

Lecture 8. Mechanics, Work, and Heat 7
Lecture 9. Reversible and irreversible changes 7

Lecture 10. The First Law of Thermodynamics: Energy 7

Lecture 11. Enthalpy, Hess’s Law 7
Lecture 12. Heat Capacities, Kirchoff’s Law 7

Lecture 13. Estimating Enthalpy Changes: Bond Enthalpies 7

Wednesday, February 6, 2002: First Quiz

Lecture 14. The Carnot Engine/Refrigerator 8

Lecture 15. The Second Law of Thermodynamics: Entropy 8

Lecture 16. Entropy Calculations 8

Lecture 17. The Third Law of Thermodynamics: Absolute Entropies 9
Lecture 18. Conditions for Stable Equilibrium: Free Energies 10

Lecture 19. Equilibrium Conditions (continued) 10

Lecture 20. Maxwell Relations and applications 9.4
Lecture 21. Chemical equilibrium 11

February 25 - March 1: STUDY BREAK

Lecture 22. Chemical equilibrium calculations 11

Lecture 23. Heterogeneous Equilibrium: The phase rule 12
Lecture 24. Phase diagrams of Simple systems: Clapeyron and Clau- 12
sius-Clapeyron equations

Lecture 25. Ideal Solutions 13

Lecture 26. Colligative properties 13

Wednesday, March 13, 2002: Second Quiz

Lecture 27. Colligative properties (continued) 13

Lecture 28. Solutions of volatile components 14

Lecture 29. Lever-principle and fractional distillation 14
Lecture 30. Henry’s Law and solubility. 14

Lecture 31. Solubility calculations 14

Lecture 32. Electrolyte solutions 17
Lecture 33. Electrochemistry: Electrochemical cells 17

Lecture 34. Redox reactions and half-cell potentials 17

Lecture 35. Nernst equation and applications1 17
Lecture 36. Summary
General Information -8- Chemistry CHEM 213W

2. Kubo’s Divertissements

From Thermodynamics
(North Holland, 1976)

Ryogo Kubo
University of Tokyo

2.1. Divertissement 1: Founders of the first law of thermodynamics

If a tomb of the Unknown Scientists had been built in the 1850’s, the most appropri-
ate inscription would have been "In memory of the grief and sacrifice of those who fought to
realize a perpetuum mobile". But the law of conservation of energy, or the first law of thermody-
namics, is associated primarily with three great names, Mayer, Helmholtz and Joule.
Julius Robert Mayer (1814-1878) was really a genius who was born in this world
only with the errand to make this great declaration. Hermann Ludwig Ferdinand von Helmholtz
(1821-1894) gave this law the name "Erhaltung der Kraft" or "the conservation of energy". Like
Mayer, he started his career as a medical doctor but lived a glorious life as the greatest physiolo-
gist and physicist of the day. James Prescott Joule (1818-1889) worked over forty years to estab-
lish the experimental verification of the equivalence of work and heat.
Among the three, Mayer was the first who arrived at this law and the last whose
work was recognized. His life was most dramatic. A lightening stroke of genius overtook him, a
German doctor of the age of twenty six, one day on the sea near Java when he noticed that
venous blood of a patient under surgical operation appeared an unusually fresh red. He consid-
ered that this might be connected with Lavoisier’s theory of oxidation in animals, which process
becomes slower in tropical zones because the rate of heat loss by animals will be slower there. A
great generalization of this observation lead him to the idea of the equivalence of heat and
mechanical work. For three years after his voyage, while he was working as a medical doctor at
home, he devoted himself to complete the first work on the conservation of energy "Bemerkun-
gen uber die Krafte der unbelebten Natur" which was sent to the Poggendorf Annalen and was
never published by it. In 1842 Liebig published this paper in his journal (Annalen der Chemie
und Pharmacie) but it was ignored for many years.
Mayer wrote four papers before 1851. During these years of unusual activity he
cared for nothing other than his theory. In 1852 he became mentally deranged and was hospital-
ized. He recovered after two years but never returned to science.

2.2. Divertissement 2: Why do we have winter heating?

The layman will answer: "To make the room warmer." The student of thermody-
namics will perhaps so express it: "To import the lacking (inner, thermal) energy." If so, then the
layman’s answer is right, the scientist’s is wrong.
We suppose, to correspond to the actual state of affairs, that the pressure of the air in
the room always equals that of the external air. In the usual notation, the (inner, thermal) energy
is, per unit mass,*

u = cvT .
Divertissement 2 -9- Chemistry CHEM 213W

(An additive constant may be neglected.) Then the energy content is, per unit of volume,

u = cv ρ T ,

or, taking into account the equation of state, we have

P
= RT ,
ρ

we have

u = c v P/R.

For air at atmospheric pressure,

u = 0. 0604cal/cm 3 .

The energy content of the room is thus independent of the temperature, solely determined by the
state of the barometer. The whole of the energy imported by the heating escapes through the
pores of the walls of the room to the outside air.
I fetch a bottle of claret from the cold cellar and put it to be tempered in the warm
room. It becomes warmer, but the increased energy content is not borrowed from the air of the
room but is brought in from outside. Then why do we have heating? For the same reason that
life on the earth needs the radiation of the sun. But this does not exist on the incident energy, for
the latter apart from a negligible amount is re-radiated, just as a man, in spite of continual
absorption of nourishment, maintains a constant body-weight. Our conditions of existence
require a determinate degree of temperature, and for the maintenance of this there is needed not
addition of energy but addition of entropy.
As a student, I read with advantage a small book by F. Wald entitled "The Mistress
of the World and her Shadow". These meant energy and entropy. In the course of advancing
knowledge the two seem to me to have exchanged places. In the huge manufactory of natural
processes, the principle of entropy occupies the position of manager, for it dictates the manner
and method of the whole business, whilst the principle of energy merely does the bookkeeping,
balancing credits and debits.

R. EMDEN

Kempterstrasse 5,
Zurich.
The above is a note published in Nature 141 (l938) 908. A. Sommerfeld found it so
interesting that he cited it in his book Thermodynamic und Statistik (Vorlesungen uber theoretis-
che Physik, Bd. 5, Dietrich’sche Verlag, Wiesbaden; English translation by F. Kestin, Academic
*
The author has assumed that the specific heat of the gas is independent of temperature;
a reasonable approximation for the oxygen and nitrogen around room temperature.

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Divertissement 2 -10- Chemistry CHEM 213W

Press Tic., New York, 1956). R. Emden is known by his work in astrophysics and meteorology as
represented by an article in der Enzyklopadie der mathematischen Wissenschafte Thermody-
namik der Himmelskorper (Teubuer, Leipzig-Berlin, 1926).

2.3. Divertissement 3: Nicolas Leonard Sadi Carnot

In the first half of the last century, the steam engine, completed by introduction of
the condenser (the low-temperature heat reservoir), due to James Watt (1765) had come to pro-
duce more and more revolutionary effects on developments in industry and transportation. Many
eminent physicists like Laplace and Poisson set about to study the Motive Power of Fire. Sadi
Carnot (1796-1832) was a son of Lazare Carnot, Organizer of Victory in the French Revolution,
and was born and died in Paris. He probably learned the caloric theory of heat, in which heat was
assumed to be a substance capable either of flowing from body to body (heat conduction) or of
making chemical compound with atoms (latent heat). He wrote a short but very important book,
Reflexions sur la puissance motrice du feu et sur les machines propres a developper cette puis-
sance (Paris, 1824), which was reprinted by his brother (1878) together with some of Carnot’s
posthumous manuscripts.
Carnot directed his attention to the point that, in the heat engine, work was done not
at the expense of heat but in connection with the transfer of heat from a hot body to a cold body,
and thus heat could not be used without a cold body, in analogy of water falling from a high
reservoir to a low reservoir. In his book he assumed the law of conversation of heat, namely that
the quantity of heat was a state function, although he later abandoned this law and arrived at the
law of equivalence of heat and work: he actually proposed many methods to estimate the
mechanical equivalent of heat. He introduced what came to be known as Carnot’s cycle, and
established Carnot’s principle.
Carnot’s book had been overlooked until B. P. E. Clapeyron (1834) gave Carnot’s
theory an analytical and graphical expression by making use of the indicator diagram devised by
Watt. The law of conservation of heat assumed by Carnot was corrected by R. Clausius (1850),
based on the work of J. R. von Mayer (1841) and J. P. Joule (1843-49), into the form that not
only a change in the distribution of heat but also a consumption of heat proportional to the work
done is necessary to do work, and vice versa. Clausius named this modification the First Law of
Thermodynamics. H. L. F. van Helmholtz (1847) and Clausius generalized this law to the princi-
ple of the conservation of energy. W. Thomson (Lord Kelvin), who introduced Kelvin’s scale of
temperature (1848) based on Carnot’s work, also recognized the law of equivalence of heat and
work. The Second Law of Thermodynamics was formulated by Thomson (1851) and Clausius
(1867).
A sketch of the history of early thermodynamics is given by E. Mendoza, Physics
Today 14 (1961) No. 2, p. 32. See also E. Mach: Principien der Warmelehre (vierte Aufl. 1923,
Verlag von Johann Ambrosius Barth, Leipzig).

2.4. Divertissement 4: Absolute Temperature

The absolute temperature scale means that temperature scale which is determined by
a thermodynamic method so that it does not depend on the choice of thermometric substance, the

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Divertissement 4 -11- Chemistry CHEM 213W

zero of the scale being defined as the lowest temperature which is possible thermodynamically.
Absolute temperature, which is now used in thermal physics, was introduced by Lord Kelvin
(William Thomson) in 1848 and is also called the Kelvin temperature.
For the complete definition of the scale, we have two choices; one is to use two fixed
points above zero and assign their temperature difference and the other is to use one fixed point
and assign its numerical value. Until recently the calibration of the Kelvin temperature scale was
performed using two fixed points: the ice point T 0 o K and the boiling point T 0 + 100o K of pure
water under 1 standard atm (= 101325 Pa). We can measure T 0 by a gas thermometric method.
At low pressures, the equation of state of a real gas can be written in the form

pV = α + κ p.

We measure the values of pV, α and κ at the above two fixed points.Considering that α is equal
to nRT , we have

100α 0
T0 =
α 100 − α 0

If we put T 0 = 0, we get the thermodynamic Celsius temperature scale. Hence, −T 0 o C means

absolute zero as measured by this scale.
The precise gas thermometric investigations of the Frenchman P. Chap- puis from
1887 to 1917 gave the value of T 0 between 273.048 and 273.123. Inspired by this work, more
than one hundred determinations of T 0 were performed until 1942. Among them, the results of
W. Heuse and J. Otto of Germany, W. H. Keesom et al. of the Netherlands, J. A. Beattie et al. of
the U.S.A. and M. Kinoshita and J. Oishi of Japan are noted for their high precision. Their values
are found to lie between 273.149 and 273.174.
Considering these results and the fact that the triple point of pure water is very near
to 0.0100o C, the 10th General Conference on Weights and Measures in 1954 decided to use the
triple point of the water as the fixed point and to assign the value 273.16 as its temperature. It
also redefined the thermodynamic Celsius temperature to C as t = T-273.15, where T is the value
of the absolute temperature determined from the above decision. The zero of the new thermody-
namic Celsius temperature differs by about 0.0001o from the ice point.
For ordinary purposes, the differences in these new and old scales are quite negligi-
ble. However, for cases where a precision of 1O−4 degree in the absolute value is required, we
must take the differences into consideration.

2.5. Divertissement 8: On the names of thermodynamic functions

The word "energy εν ε ργ εια " can be seen in the works of Aristotle but "internal
energy" is due to W. Thomson (1852) and R. J. E. Clausius (1876). The portion "en" means
inhalt=capacity and "orgy", like the unit "erg", derives from ε ργ oν =work. "Entropy" is also at-
tributed to Clausius (1865) who took it from {εν τ ρε π ειν =verwandeln and means verwand-
lungsinhalt=change quantity. "Enthalpy" was introduced by H. Kamerlingh Onnes (1909) from
{εν θ α λπ ειν =sich erwarmen which means warmeinhalt. J.W. Gibbs called it the heat function

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Divertissement 8 -12- Chemistry CHEM 213W

(for constant pressure). "Free energy" is due to H. van Helmholtz (1882), and means that part of
the internal energy that can be converted into work, as seen in the equation dF=d’A for an
isothermal quasi-static process. It was customary to call the remaining part, TS, of the internal
energy, U = F + TS, the gebundene energie (bound energy), but this is not so common now. The
Gibbs free energy (for constant pressure) was introduced by Gibbs, but German scientists used to
call it die freie enthalpie. Thus the thermodynamic functions often have different names in Ger-
man and in English.
Further, on the equation of state: Kamerlingh Onnes gave the names, thermische zus-
tandsgleichung to p = p(T , V ) and the name kalorische zustandsgleichung to E = E(S, V ). M.
Planck (1908) called the latter kanonische zustandsgleichung.

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Probability -13- Chemistry CHEM 213W

3. Probability and Statistics

As we have stressed in class, when dealing with a macroscopic sample of a material
it is practically impossible to measure or calculate all the microscopic properties of the ∼ 1023
atoms or molecules in the system. Fortunately, many kinds of phenomena do not depend on the
precise behavior of any single particle, and only average properties of the constituent particles
are important. In order to quantify these averages, we must consider some simple ideas in proba-
bility and statistics.
We all encounter probabilistic concepts in daily life. Results of opinion polls, life
expectancy tables, and grade distributions are but a few examples. Shown below, are two grade
distributions for two classes taking an hourly exam in some course.

How would you use this information?

Perhaps the simplest quantity to compute is the average grade; i.e.,
100 N (i)
AVERAGE GRADE = Σ
i=0 N total
i,

where N (i) is the number of students with grade i and N total is the total number of students in
each class. Notice that even though the two distributions are very different, they have the same
roughly the same average grade.
How much information is contained in the average grade and how relevant is the
average to any individual in the class? In the hypothetical distribution the average tells the whole
story. The distribution is extremely narrow, and thus practically everyone got the average grade.
The same is not true in the real distribution; there is a significant spread in the scores. This
spread can be quantified by defining the probability, P(i), of finding any student with grade i. For
this example,

N (i)
P(i) ≡
N total

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Probability -14- Chemistry CHEM 213W

which is simply the faction of students with grade i. Notice that probabilities are "normalized" in
the sense that

Σi P(i) = 1.
This is just a complicated way of stating the fact that every student taking the exam receives
some grade.
A measure of the width of the distribution can be obtained by computing the stan-
dard deviation. If we denote the average grade by <i>, then the standard deviation, σ , is defined
as:

σ2 ≡ Σi P(i) [ i − < i > ]2

(Note, σ is the Greek letter sigma).
When we consider atomic and molecular systems the situation becomes somewhat
more complicated, although the basic ideas are the same as those introduced in the grade exam-
ple discussed above. You have already used probability when you learned about atomic and
molecular orbitals. In the kinetic theory of gasses, a different sort of question is being asked;
namely, how do the molecules move?
To be specific, suppose we want the distribution of velocities in the x direction for a
sample of gas containing 1023 molecules. Even if we ignore the experimental impossibility of
measuring the velocities of all of the molecules, what would we do with this huge amount of
information? It would be useful to make the kind of histogram used in discussing grade distribu-
tions; however there is an additional complication. For the exam discussed above, no fractional
grades were assigned, and thus there is a natural bin width of 1 grade point. On the other hand,
nature does not assign discrete values to the x components of the molecular velocities. Hence, if
we were to make our bins too small in constructing our histogram, most of them would contain
only 0 or 1 particles, even for a sample containing 1023 particles.
In order to get around this difficulty, we must include some information about the
size of the "bin" in our introduction of probability. This is done by defining probability density,
F(v x ):

F(v x ) ∆v x ≡ The probability that a molecule has

velocity between v x and v x + ∆v x .

Notice that the bin size is explicitly contained in our definition. Also note that in general proba-
bility densities have units (in this example the units are inverse velocity).
Once we know the probability density, averages can be computed just as in the grade
example considered above. For example,

< v nx > = Σ v nx F(v x ) ∆v x . (1)

vx

Throughout this part of the course, we will denote average quantities by surrounding them with

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Probability -15- Chemistry CHEM 213W

"< >". What should this average be for n=0 or 1? What is the physical significance of the aver-
age for n=2?
Of course, typical samples of the gas contain a large number of particles, and thus,
the bins can be taken to be very small. What does the sum in eq. (1) become in this limit? We
know that this is an integral, and we therefore rewrite eq. (1) as
∞
< v nx > = ∫ v nx F(v x ) dv x .
∞
−

Finally, one more aspect of probability must be considered. In the molecular veloc-
ity example, we discussed only the x component. However, velocity is a vector and there are
also the y and z components. How would we describe the probability that any molecule is travel-
ing in some specific direction? Clearly, for molecules in a gas, the probability that the x compo-
nent of the velocity lies in some interval should be independent of what the other two compo-
nents are doing. For such situations, the probability that a molecule has velocity with compo-
nents in the intervals v x to v x + ∆v x , v y to v y + ∆v y , and v z to v z + ∆v z is

F(v x , v y , v z )∆v x ∆v y ∆v z = F(v x )F(v y )F(v z )∆v x ∆v y ∆v z .

If you are having trouble believing this, consider the probability that three coins come up heads
or tails in any set of three of tosses. This is a model the velocity probability distribution in a uni-
verse were all the magnitudes of the velocity components in the three directions are equal.
Further aspects of probability densities in gas kinetics will be discussed in class, but
this material should get you started.

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Boltzmann Distribution -16- Chemistry CHEM 213W

4. The Maxwell-Boltzmann Distribution

The molecular description of the bulk properties of a gas depends upon our knowing
the mathematical form of the velocity distribution; That is, the probability,
F(v x , v y , v z )∆v x ∆v y ∆v z , of finding a molecule with velocity components in the range v x to
v x + ∆v x , v y to v y + ∆v y , and v z to v z + ∆v z (see the last handout). This can be found by making
two very simple assumptions:
1. The three components of the velocity are independent of each other. This implies
that the velocity probability density can be written as:

F(v x , v y , v x ) = f (v x ) f (v y ) f (v z ) (1)

2. All directions are equivalent (space is isotropic). This implies that the probability of
finding a molecule moving with a certain velocity cannot depend on the direction; it
is equally probable to find a molecule with any speed v moving in any direction.
Mathematically, this implies that the probability density can only depend on the
magnitude of the velocity, or the molecular speed. Hence,

F(v x , v y , v x ) = F([v 2x + v 2y + v 2z ]1/2 ). (2)

By comparing Eqs. (1) and (2), we have

f (v x ) f (v y ) f (v z ) = F([v 2x + v 2y + v 2z ]1/2 ). (3)

Very few functions can satisfy Eq. (3); in fact, the only one is:

f (v i ) = A e−bvi , i = x, y, z
2
(4)

where A and b are, as yet, arbitrary constants. Verify that f given by Eq. (4) satisfies Eq. (3). To
show that Eq. (4) is the only possible function, requires some mathematics which might be
beyond the level of Chemistry 213; however, the proof is contained in the appendix for those of
you who have this extra background.
How do we determine the values of the constants A and b? The function f, is a prob-
ability density and every molecule must have some velocity. From the previous section, we
know that this means

∞ ∞
1= Σ
v x =−∞
f (v x )∆v x → ∫ f (v x )dv x , (5)
−∞

where the integral is obtained when we make ∆v x very small. By going to a table of integrals we
find that
∞
π 1/2

∫ A e−bv dv = A   ,
2
(6)
b
−∞

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Boltzmann Distribution -17- Chemistry CHEM 213W

which when used in Eq. (5) gives

1/2
b
A=  . (7)
π 

The parameter b is found as follows: We will compute the pressure that a dilute gas
exerts on the walls of its container and then compare the result with experiment (i.e., the ideal
gas equation of state). What is the pressure and how do we get it from the velocity distribution?
The pressure is the force exerted by the gas per unit area. Moreover, the force is the rate of
change of momentum per unit time due to collisions with the wall.
Imagine the molecules which comprise our gas as billiard balls and assume that the
walls are perfectly smooth. What happens when a molecule collides with the wall? Actually rel-
atively little; the normal component of the velocity changes sign (see Fig. 1).
1111
0000
0000
1111
0000
1111 |vx dt|
0000
1111
0000
1111
0000
1111
0000
1111
0000
1111
0000
1111
0000
1111
0000
1111 x
0000
1111
0000
1111
0000
1111
0000
1111
0000
1111
0000
1111
Figure 1
If the wall is taken to be the y-z plane, the momentum change is

∆ p = − 2mv x , (8)

where m is the mass of the molecule. A typical velocity is 105 cm/sec; what is a typical momen-
tum change for argon? How many molecules with velocity v x will collide with the wall per unit
area in time ∆t? From Fig. 1, it should be clear that any molecule within a distance v x ∆t will hit
the wall. The number per unit area is therefore:

n(v x )v x ∆t, (9)

where n(v) is the number of molecules per unit volume with x component of velocity in the
range v x to v x + ∆v x . This is related to the molecular velocity distribution by

n(v x ) = n0 f (v x )∆v x , (10)

where n0 is the number of molecules per unit volume. By multiplying Eqs. (8) and (9), dividing
by ∆t and by using Eq. (10), we arrive at the pressure exerted by those molecules with x velocity
component in the range v x to v x + ∆v x :

2 m n0 v 2x f (v x )∆v x . (11)

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Boltzmann Distribution -18- Chemistry CHEM 213W

All that remains is to include the contributions from all velocities corresponding to molecules
moving towards the wall. The pressure, P, thus equals:

∞ ∞
P= Σ 2 m n0 v x 2 f (v x )dv x = ∫0 2 m n0 v x f (v x )dv x
2
v x ≥0

∞  
1/2
b
∫0 2 m e−bv x dv x ,
2
= n0 v 2x   (12)
π 

where the last equality comes from using the explicit form of the probability density, [see Eqs.
(4) and (7)]. The value of the integral is:
∞
1  π 1/2
∫0 v 2x e−bv x dv x =
2
.
4b  b 

If we use this result in Eq. (12), we find that

m n0
P= . (13)
2b

Next we write the ideal gas equation of state in terms of the number density:

P = n0 k B T ,

where k B is Boltzmann’s constant:

R
kB ≡ = 1. 38 × 10−16 erg/deg.
6. 0225 × 10 23

By comparing this with Eq. (13) we see that

m
b= .
2k B T

The velocity probability density for the x component can now be written as
1/2
 m  −
mv 2x
f (v x ) =   e 2k B T (14)
 2π k B T 
or for the full velocity as
3/2
 m  −
E
F(v x , v y , v x ) =   e k BT , (15)
 2π k B T 

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Boltzmann Distribution -19- Chemistry CHEM 213W

where E = m(v 2x + v 2y + v 2z )/2 is the energy of the molecule. This is referred to as the Maxwell-
Boltzmann distribution function and is illustrated in the following figure:

Notice that increasing the temperature makes it more probable to find molecules
with higher velocities and that the probability of observing any given velocity will decrease as
the energy associated with that velocity increases. This last comment is not limited to our simple
billiard ball model of the molecules.
For many applications, the Maxwell-Boltzmann velocity distribution gives too much
detail. In particular, remember that it is a probability density for the vector velocity. Suppose we
are interested in some property which depends only on the speed of the molecules and not their
direction. What is the probability density which describes the distribution of molecular speeds?
The speed distribution function, F(c) dc, is the probability of observing a molecule
with a speed in the interval c to c + dc irrespective of its direction. It can be obtained from Eq.
(15) as follows: Eq. (15) describes the distribution of velocities. If we are not interested in the
direction of the velocity, all we need do is to average it out; i.e.,

F(c)dc = Σ F(v x , v y , v z )∆v x ∆v y ∆v z = F(v x , v y , v z ) Σ ∆v x ∆v y ∆v z . (16)

→
c≤|v|≤c+dc |v|=c →
c≤|v|≤c+dc

The sums in these last equations are over all velocities such that the speed is between c and
c + dc. The second equality comes from noting that F only depends on the magnitude of the
velocity (see Eq. (15)). What is this last sum? ∆v x ∆v y ∆v z is a volume element in a coordinate
system whose axes are the components of velocity. The sum represents the volume between two
concentric spheres of radius c and c+dc, respectively. Thus

4π 
Σ ∆v x ∆v y ∆v z = (c + dc)3 − c 3  ≈ 4π c 2 dc, (17)
→
c≤|v|≤c+dc 3  

where the last expression was obtained by expanding the products and dropping nonlinear terms
in dc (remember that we will consider infinitesimally small dc). If we use Eq. (17) in (16), we

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Boltzmann Distribution -20- Chemistry CHEM 213W

find that
3/2
 m  −
mc 2
F(c) = 4π c F(v x , v y , v z )
2
= 4π c 2   e 2k B T . (18)
|v|=c  2π k B T 
This is the speed distribution and is shown below. Notice that it vanishes when c=0; why?

4.1. Appendix: Proof of Eq. (4)

You will not be responsible for this proof. Differentiate both sides of Eq. (3) with
respect to v x and divide by v x . You get:

df (v x ) dF([v 2x + v 2y + v 2z ]1/2 )
f (v y ) f (v z )
dv x dv x
= .
vx [v x + v 2y + v 2z ]1/2
2

By repeating this for v y , equating the results and carrying out a little algebra, we find that:

df (v x ) df (v y )
dv y dv y
=
v x f (v x ) v y f (v y )

The right hand side of the equation depends only on v y and the left hand side depends only on
v x . Since these two components of velocity can be chosen independently, the only way that this
last equation can be satisfied is if both sides are equal to the same constant. Hence,

df (v x ) 1
= − bv x f (v x ).
dv x 2

This is a first order differential equation. It has a general solution which will depend on a single

Winter Term 2001-2002

Boltzmann Distribution -21- Chemistry CHEM 213W

multiplicative constant. This solution is given by Eq. (4).

Winter Term 2001-2002

Collision Rates and Diffusion -22- Chemistry CHEM 213W

5. Collision Rates, Mean Free Path, and Diffusion

In the previous section, we found the parameter b by computing the average force
exerted on the walls of the container. Suppose, instead, that the rate of collisions (i.e., the num-
ber of collisions per unit area per unit time) was desired. This is important for a number of prac-
tical considerations; e.g., if a chemical reaction takes place every time a molecule hits the sur-
face, then the rate of the reaction will just be the collision rate.
We obtain the collision rate by repeating the analysis which determined the force on
the wall in the previous section. Thus the number of molecules with velocity v x which collide in
time interval ∆t is

n(v x )v x ∆t, (1)

where we are using the same notation as in the preceding section. The total number of collisions
thus becomes:
0
Z wall ∆t ≡ ∫ n(v x )|v x |∆tdv x ,
−∞

0 1/2
 m  −mv2x /(2k B T )
= ∫
−∞
dv x n0
 2π k B T 
e |v x |∆t

1/2
 k BT 
= n0 ∆t (2)
 2π m 

Hence the wall collision rate, Z wall , is given by

1/2
 k BT 
Z wall = n0 (3)
 2π m 

Aside from the previously mentioned example of chemical reaction on a surface, another applica-
tion of this expression is in effusion though a pinhole. If there is a hole of area A in the surface,
the rate that molecules escape the system is just Z wall A. Notice that heavier molecules or iso-
topes will escape more slowly (with a 1/√ 
mass dependence); hence, effusion through a pinhole is
a simple way in which to separate different mass species.

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Collision Rates and Diffusion -23- Chemistry CHEM 213W

RA + R B

|v| ∆ t

Fig. 1
Next consider the number of collisions which a molecule of type A makes with
those of type B in a gas. We will model the two molecules as hard spheres of radii R A and R B ,
respectively. Moreover, in order to simplify the calculation, we will assume that the B molecules
are stationary (this is a good approximation if m B >> m A ). An A molecule moving with velocity
→
v for time ∆t will collide with any B molecule in a cylinder of radius R A + R B (cf. Fig. 1) and
→
length |v|∆t. Hence, volume swept out will just be

|v|∆t π (R A + R B )2 , (4)

and the actual number of collisions will n B × volume swept out The average A-B collision rate, is
→
obtained by multiplying by the probability density for A molecules with velocity v and averag-
ing. Moreover, since only the speed of the molecule is important, we may use the molecular
speed distribution function obtained in the preceding section to average over the speed of A.
Thus, we get
∞ 3/2
 m A  −m a c2 /(2k B T )
Z A ∆t ≡ ∫0 4π c 2
 2π k B T 
e n B c∆t π (R A + R B )2 dc (5)

which, when the integral is performed, gives:

Z A = π (R A + R B )2 c A n B , (6)

where c A is the average molecular speed of A; i.e.,

1/2
 8k B T 
cA ≡ . (7)
 π mA 

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Collision Rates and Diffusion -24- Chemistry CHEM 213W

This is the number of collisions one A suffers in time ∆t. The number of collisions
with B’s that all the A molecules in a unit volume suffer per unit time, Z A,B , is

Z A,B = π (R A + R B )2 c A n A n B (8)

As was mentioned at the outset, our expression is correct if the B’s are not moving.
It turns out that the correction for the motion of B is rather simple (and involves going to what is
called the center-of-mass frame, which is not); specifically, we replace the m A in the definition of
the mean speed by µ A,B , the reduced mass for the A,B pair. The reduced mass is defined as:
m AmB
µ A,B ≡ . (9)
m A + mB

With this correction, our expression becomes

Z A,B = π (R A + R B )2 c A,B n A n B , (10)

where
1/2
 8k B T 
c A,B ≡ (11)
 π µ A,B 

is the mean speed of A relative to B. A special case of this expression it the rate of collision of A
molecules with themselves. In this case, Eq. (10) becomes

1
Z A, A = π σ A2 c A 21/2 n2A , (12)
2
where σ A is the molecular diameter of A and where we have divided by 2 in order to not count
each A-A collision twice.
Next, we will consider how far a molecule can move before it suffers a collision.
For simplicity, we will only consider a one component gas. According to Eq. (6), the mean time
between collisions is

1
τ collision ≈ .
21/2 π σ A2 c A n A

Hence, the typical distance traveled by a molecule between collisions, λ is approximately

τ collision c A or

1
λ= .
21/2 π σ A2 n A

This distance is called the mean free path. Note that it only depends on the density of the gas
and the size of the molecules.

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Collision Rates and Diffusion -25- Chemistry CHEM 213W

We can use these results to obtain an approximate expression for the way in which
concentration differences equilibrate in a dilute gas. Consider a gas containing two kinds of mol-
ecules in which there is a concentration gradient; i.e., the density of molecules per unit volume,
ni (z) depends on position. One way in which the concentration becomes uniform is via diffu-
sion.
To quantify diffusion, we want to find the net number of molecules of a given type
that cross a plane in the gas per unit area per unit time; this is known as the diffusion flux. To see
how the diffusion flux depends on molecular parameters, consider the following figure.

z+λ

z− λ

Fig. 2

We want the net flux through the plane at z. From our preceding discussion of mean free paths,
clearly any molecule that starts roughly from a mean free path above or below z, moving towards
z, will not suffer any collisions and will cross. The number that cross the planes at z ± λ per unit
area, per unit time is the same as the wall collision rates we calculated above, that is
1/2
 k BT  1
n(z ± λ ) = cn(z ± λ ),
 2π m  4

where we have rewritten Eq. (3) in terms of the average molecular speed, Eq. (7). Since all the
molecules that wont collide and will thus cross the plane at z, the net flux (upward) is just

1 1
J= cn(z − λ ) − cn(z + λ )
4 4

1
=− c[n(z + λ ) − n(z − λ )].
4
Since, for most experiments the density barely changes on over a distance comparable to the
mean free path, we use the Taylor expansion to write

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Collision Rates and Diffusion -26- Chemistry CHEM 213W

dn(z) 1 d 2 n(z) 2 ...

n(z ± λ ) ≈ n(z) + λ+ λ + ,
dz 2 dz 2
which gives Fick’s Law of diffusion,

dn(z)
J = −D ,
dz
where

1
D≡ λc
2
is known as the diffusion constant and has units of length2 /time. (Actually the factor of 1/2 in
our expression for D is not quite right, but the other factors are).
Next consider the total number of molecules inside of some region bounded by
planes at z and z + L. The length L is small compared to the scales that characterize the concen-
tration nonuniformity, but large compared with the mean free path. Clearly the only way for the
total number of molecules in our region, n(z, t)L, to change is by fluxes at the surfaces at z and
z + L. Thus,

∂n(z, t)L ∂J(z, t)

= −J(z + L, t) + J(z, t) ≈ −L ,
∂t ∂z
where we have again used a Taylor expansion, now for the flux itself. Finally, by using our result
for the diffusion flux and canceling the factors of L, we see that

∂n(z, t) ∂2 n(z, t)
=D ,
∂t ∂z 2
which is a kinetic equation for the relaxation of the concentration and is known as the diffusion
equation. Although value of the diffusion constant is quite different, the diffusion equation actu-
ally is more general than our derivation might suggest and holds in liquids and solids as well.
Finally, note that we have only considered systems where the concentration is only nonuniform
in one spatial direction. Should this not be the case, then some simple modifications of our
expressions must be introduced, but these will not be considered here.
There are standard ways in which to solve diffusion equations. However, there is one
general feature of systems relaxing diffusively. Imagine introducing a small droplet of an impu-
rity into a system. Clearly the droplet will spread in time, and you might naively think that the
average droplet size would grow like ct. Of course, this ignores collisions and is incorrect.
From the diffusion equation dimensional analysis correctly suggests that

1 D
≈ 2
t R
or R ≈ √
Dt, which is much slower than the linear behavior that would arise in the absence of col-
lisions. This is what is observed.

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Collision Rates and Diffusion -27- Chemistry CHEM 213W

6. Collision Theory of the Rate Constant

The simplest collisional model for the rate constants in bimolecular elementary reac-
tions, e.g.,

A + B → Products,

is to assume that reaction occurs every time an A and B molecule collide. Thus the rate
becomes:

RATE = Z A,B (1)

where Z A,B is the number of AB collisions occurring per unit time, per unit volume of the sys-
tem. The kinetic theory of gases gives

Z A,B = π (R A + R B )2 c AB n A n B , (2)

where R A and R B are the van der Waals radii of A and B, respectively, n A and n B are their num-
ber densities, and c AB is the mean relative speed of A with respect to B; i.e.,
1/2
 8k B T 
c AB ≡ . (3)
 π µ AB 

In Eq. (3), k B is Boltzmann’s constant and µ AB ≡ m A m B /(m A + m B ) is the AB reduced mass

(m A,B denotes the mass of A or B).
Equation (2) is obtained by considering how many B molecules will lie in the cylin-
der swept out by an A molecule in time dt. The radius of the cylinder is the maximum distance
and A and B can be in order to collide, i.e., R A + R B . Thus the volume of the cylinder for mole-
cules moving with relative speed v is

V (v) ≡ π (R A + R B )2 vdt. (4)

The number of B molecules in the cylinder with relative speed v to v + dv is V (v)n B f (v)dv,
where

3/2 µ AB v 2
2µ AB  −
f (v) = 4π v e 2k B T (5)
 2π k B T 

is the Maxwell-Boltzmann speed distribution function governing the relative motion of B with
respect to A. Finally, our expression for the rate is obtained by adding (integrating) the contribu-
tions for the different relative velocities, multiplying by the number of A molecules per unit vol-
ume and dividing out the factor of dt; i.e,
∞
RATE = n A n B π (R A + R B )2 ∫0 dv f (v)v, (6)

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Collision Rate Constants -28- Chemistry CHEM 213W

which gives the expression presented above.

As was mentioned in class, Eqs. (1) - (3) in general do not correctly describe the
temperature dependence of rate constants since the activation energy does not appear. In order to
correct for this, we will modify our initial hypothesis; specifically, now assume that only those
molecules whose relative speed is greater than v min can react. In this case, Eq. (6) becomes:
∞
RATE = n A n B π (R A + R B )2
v
∫ dv f (v)v, (7)
min

which upon evaluating the integral gives

 E 
RATE = π (R A + R B )2 c AB e−E A /k B T 1 + A n A n B , (8)
 k BT 

where E A ≡ µ AB v 2min /2 is the activation energy. This expression has the correct Arrhenius form
except for the extra nonexponential factors containing temperature. However, compared with the
exponential factor, these usually do not change very rapidly in temperature and can approxi-
mately be treated as constant. Thus we have derived an approximate expression for the bimolec-
ular rate constant which has at least some of the qualitative features of those found in gas reac-
tions.

Winter Term 2001-2002

Notes on the First Law -29- Chemistry CHEM 213W

7. Notes on the First Law of Thermodynamics

7.1. Zeroth Law of Thermodynamics

If two bodies at equilibrium are brought into thermal (i.e., no mechani-
cal, electrical, magnetic, gravitational, etc., work is performed) and
nothing happens, then they are at the same temperature.
Given this, we can always measure the temperature of any system by bringing it into
thermal contact with some standard thermometer. As we shall see, a very convenient choice is
the ideal-gas thermometer. Here a manometer is used to measure the pressure of a fixed amount
of gas in a fixed volume and the relation

NRT
V =
P
is used to calculate the temperature. Needless to say, other temperature standards can (and are)
used.

7.2. Some Definitions

Intensive Doesn’t depend on the size of the system; e.g., P, T, partial molar quan-
tities.
Extensive The opposite of intensive; e.g., mass, volume, energy (but not energy
per unit volume or mass), heat capacities (but not specific heats).
System The part of the universe under investigation. Systems can be:
a) Isolated: no interaction of any kind with surroundings.
Note that real systems cannot be truly isolated, but can be
approximately so on the time-scale of relevance.
b) Closed: energy can be exchanged with surroundings, but
matter cannot.
c) Open: matter and energy can be exchanged.
Surroundings The part of the universe not under investigation.
Boundary What divides the system from the surroundings (and controls whether
the system is open, closed, or isolated).
State A systems state is specified when all measurable properties have defi-
nite values to the accuracy of the experiment.
State Variables A set of measurable quantities, which when known, completely specify
the state of the system. In classical or quantum mechanics there are on
the order of 1023 state variables; however, in thermodynamics, experi-
ence tells us that the macroscopic state of the system is specified after a
small set of measurements are made (e.g., T, P, V, x 1 , ..., x r ).

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Notes on the First Law -30- Chemistry CHEM 213W

Process Something whereby the state of a system is changed. A process has two
parts:
a) Initial and final states (i.e., where the system starts and
ends).
and a
b) Path. The path describes how the change was effected. In
order to specify the path, intermediate changes in the sys-
tem, surroundings and boundary must be specified. This is
clearly something which we would like to avoid in many
cases.
Reversible A process is said to be reversible if it is possible to return both the sys-
tem and the surroundings to their original state. If not, it is irreversible
(even if the system can be returned to the original state).
State Function A property of the system which only depends on the current state of the
system. Hence, changes in state functions do not depend on the path
taken. State functions play a key role in thermodynamics and allow
macroscopic properties of matter to be studied in a rigorous, systematic
manner. Examples of state functions are: energy, entropy (to be intro-
duced later), P, V, T, etc. A one-component ideal gas has a pressure,
P(T,N,V), given by PV=NRT no matter what--how the T, V, or N
attained their current values is irrelevant.

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Notes on the First Law -31- Chemistry CHEM 213W

7.3. Euler’s Theorem, Partial Molar Quantities, and the Gibbs-Duhem Relations
Next consider any extensive quantity in a mixture containing r components; i.e.,
...
A(T , P, N 1 , , N r ). Real examples could be the energy, volume, mass, heat capacity, etc.. Con-
sider the small change in A associated with changes in its arguments, namely

 ∂A  ∂A
dA = dT + dP
 ∂T  P,N 1 ,...,N r  ∂P T ,N 1 ,...,N r

 ∂A   ∂A 
+ dN 1 + ... + dN , (1)
 ∂N 1 T ,P,N 2 ,...,N r  ∂N r T ,P,N 1 ,...,N r−1 r

Now, by assumption, A is extensive; hence,

A(T , P, λ N 1 , ..., λ N r ) = λ A(T , P, N 1 , ..., N r ). (2)

If we differentiate both sides of this equation with respect to λ and evaluate the answer at λ = 1 it
follows that

 ∂A   ∂A 
A(T , P, N 1 , ..., N r ) = N 1 + ... + N (3)
 ∂N 1 T ,P,N 2 ,...,N r  ∂N r T ,P,N 1 ,...,N r−1 r

r
≡ Σ Ai N i ,
i=1
(4)

where

 ∂A 
Ai ≡ (5)
 ∂N i T ,P,N j≠i

is called a partial molar quantity. Note that the partial molar quantities are intensive. In obtain-
ing Eq. (3) you may use Eq. (1) for dT = dP = 0 and d(λ N i ) = N i d λ for i = 1, ..., r). Also note
that Eq. (3) is a special case of Euler’s theorem for homogeneous functions in calculus.
Equations (3) or (4) allow us to explicitly express the nontrivial features of an exten-
sive quantity in terms of intensive ones, thereby reducing the number of dependencies we must
worry about. It also turns out that the partial molar quantities (or more specifically changes in
them) are not all independent. To see this, we calculate dA from Eq. (4):
r
dA = Σ Ai dN i + N i d Ai ,
i=1
(6)

where we have used the calculus result d(xy) = xdy + ydx. Of course, dA could have been com-
puted from Eq. (1); i.e.,

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Notes on the First Law -32- Chemistry CHEM 213W

 ∂A  ∂A r
dA = dT + dP + Σ Ai dN i , (7)
 ∂T  P,N 1 ,...,N r  ∂P T ,N 1 ,...,N r i=1

where we have rewritten the derivatives with respect to the numbers of moles in terms of the par-
tial molar quantities, cf. Eq. (5). By equating the right hand sides of Eqs. (6) and (7) it follows
that

 ∂A  ∂A r
dT + dP − Σ N i d Ai = 0 (8)
 ∂T  P,N 1 ,...,N r  ∂P T ,N 1 ,...,N r i=1

and hence, the changes in the partial molar quantities and other derivatives are not all indepen-
dent. Equation (8) is known as a Gibbs-Duhem relation and can be used to relate seemingly dis-
parate thermodynamic derivatives.
As an exercise, what are the partial molar volumes for an ideal gas mixture obeying
Dalton’s law of partial pressures? Do they obey the Gibbs-Duhem relation?

7.4. Work and Heat in Thermodynamics

Two central concepts in thermodynamics are work and heat. You probably have
seen examples of the former in your freshman physics class, and the latter is something you
experience in daily life. In thermodynamics, both have very precise definitions.
Work: anything which crosses the boundary of the system and is completely convertible
into the lifting of a weight in the surroundings.
Note that work only appears at the boundary of a system, during a change of state, is
extensive, and is manifested by an effect in the surroundings. From mechanics, we know that

dW = Fdx = mgdx,

where dW is the incremental work done by the system, F is the force, and dx is the distance tra-
versed. The second equality is for moving a mass m a distance dx in a gravitational field (g is the
gravitational acceleration constant). Consider the following apparatus:

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The inside of the piston is filled with some gas at pressure P

M (mass) and is maintained at constant temperature T. Instead of
characterizing the work done in terms of the mass, it is
more convenient to introduce the pressure exerted on the
top of the piston (i.e., force per unit area, A)

F mg
P op ≡ = .
A (area) A A
dx

Note that P op need not equal P.

Thus

d− W = P op Adx = P op dV

where dV is the incremental change in the volume of the system. The work involved in these
sorts of processes is known as pressure-volume work.
Note that the work done is not a state function--it depends on the pressure exerted
on the piston (the path) and is not simply a function of the state of the gas in the piston. To stress
this fact, the notation d− will be used for infinitesimal changes in quantities which depend on the
path.
For an process whereby the gas is expanded against some pressure, dV > 0, and
hence, d− W > 0. Conversely, in a compression process, d− W < 0, i.e., negative work is done by
the system. The surroundings do positive work on the system.
This diagram shows a process for the isothermal
expansion of a gas (in this case an ideal gas). The solid
curve gives the pressure of the gas (i.e., its equation of
state). The dotted curve gives the opposing pressure actu-
ally used in the expansion. Note that the latter lies com-
pletely below the former. If at any point this were not the
case, then the expansion would not proceed spontaneously
(i.e., the opposing pressure would be too large and the gas
would contract).

The total work done by the system is just the area

under the dotted curve:

V final V final

W = ∫
V initial
P op (V )dV ≤ ∫
V initial
P(V )dV ≡ W rev .

If the gas inside the piston is ideal, then the ideal-gas equation of state is valid and

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Notes on the First Law -34- Chemistry CHEM 213W

V final
NRT
W rev = ∫
V initial
V
dV = NRT ln(V final /V initial ).

Note that the maximum work you can get out of a spontaneous expansion is
obtained when the opposing pressure is infinitesimally less than the pressure being exerted by the
gas in the piston. In this case, W = W R . Unfortunately, the rate of such an expansion would be
zero, as would be the power delivered by the system. On the other hand, it is easy to show that
the path given by P op = P is the only reversible one for the isothermal expansion of an ideal gas.
Consider the following apparatus (from L. K. Nash, Elements of Chemical Thermo-
dynamics, Addison-Wesley, 1970):

The spring is assumed to obey Hooke’s law (i.e, the force is proportional to the elongation). A
series of experiments are performed whereby weights are moved to pan from platforms at various
heights in the surroundings. In doing so, the system (the spring and pan) move from state I to II.
How much work is performed in each of the cases (a)−(c) (assume that there is a total 1cm elon-
gation of the spring and ignore the mass of the pan and spring)?
In order to reverse the process (i.e., the expansion of the spring) the weights are
moved back to the adjacent platforms. However, it is easy to see that while the spring will be
fully compressed at the end of the experiment, the surroundings will not be restored to their ini-
tial state; specifically, in the best case, the topmost weight will be transferred to the lowest plat-
form, no matter how many platforms are used. Clearly the biggest change in the surroundings
will happen in case (a) and the smallest in (c). Moreover, the smaller the individual weights we
use, the more reversible the process becomes (i.e., the change to the surroundings decreases).
The process is reversible in the limit where the applied force (the weight) is only infinitesimally
more than the force exerted by the spring.
This argument can easily be extended to our discussion of pressure-volume work or
to other kinds of work. Hence, the maximum work in a P-V expansion is obtained for a
reversible path.

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Another key quantity in thermodynamics is heat.

Heat: Anything which flows across the boundary of a system by virtue of a temperature
difference between the system and the surroundings.
Heat is quantified by measuring the temperature rise (or fall) in a standard material
(e.g., a calorie corresponds to the amount of heat required to raise the temperature of 1 g of water
1 oC). Like work, heat appears only at the boundary of a system, during a change of state, is
extensive, and is manifested by an effect in the surroundings. It is also not a state function since
it depends on the nature of the thermal contact allowed at the boundary of the system.
In a classic set of experiments in the 19’th century, J. P. Joule showed that the same
changes in the state of a system could be achieved by either adding work or heat to the system.
One of his devices is shown below.

As the weight falls, the paddles turn and

heat up the liquid in the container by friction
(viscous heating). The same temperature
rise can be achieved by directly heating the
container using a known amount of heat.

The amounts of heat and work were

definite and Joule concluded that work and
heat were simply two different ways in
which energy could be added to a system.
Specifically, Joule showed that

1 calorie = 4. 184 kg m 2 /sec 2 .

We are now ready to state the first law of thermodynamics. Before doing so, it is
illustrative to consider energy in classical mechanics.

7.5. Energy in Classical Mechanics

You probably have heard the statement that "energy is conserved." What does this
mean exactly? Consider a system comprised of N point particles of mass m, at positions
r 1 , ..., r N , and moving with velocities v 1 , ...v N . The system is not subjected to any external
→ → → →

forces. In addition, assume that Newton’s laws of motion are valid and that the particles interact
via pairwise additive forces which are derivable from a potential; i.e., the force particle i exerts
→
on j, F i, j is given by

→ ∂ui, j
F i, j ≡ − → .
∂r i

Consider the energy function, E, defined as

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N m →2 1 N N
E≡ Σ
i=1
v + Σ Σ ui, j .
2 i 2 i=1 j=1
i≠ j

How does E change as the particles move around under the action of Newton’s Laws?

dE N → 1 N N →
= Σ m v i ⋅ F i − Σ Σ F i, j ⋅ (v i − v j ),
→ → →

dt i=1 2 i=1 j=1

i≠ j

→ → →
where F i ≡ Σ
j≠i
F i, j is the total force acting on the i’th particle. Using this definition of F i in our
expression for the rate of change of E gives:

dE 1 N N →
= Σ Σ F i, j ⋅ (v i + v j )
→ →

dt 2 i=1 j=1
i≠ j

1 N N → →
Σ Σ
→
= ( F i, j + F j,i ) ⋅ v i
2 i=1 j=1
i≠ j

→
where the dummy summation indices, i and j, were exchanged for the terms in v j in obtaining
→ →
the last equality. Newton’s third law states that F i, j = − F j,i ; i.e., the force i exerts on j is equal
and opposite to that j exerts on i. Using this in our last expression immediately shows that

dE
= 0.
dt
In other words, the energy of our classical system of particles doesn’t change in time or is con-
served. The same is true under the laws of quantum mechanics. What happens if, in addition to
the forces acting between the particles, the particles are subjected to an external forces?
The first law of thermodynamics also has something to say about changes in energy,
although not in precisely the same way as in classical or quantum mechanics

7.6. The First Law of Thermodynamics:

In any cyclic process (i.e., one where the system returns to its initial
state) the net heat absorbed by the system is equal to the work pro-
duced by the system.
Suppose this were not the case. Then you could presumably find a process which
produced more work than it absorbed heat. This extra work could be used to run a generator,
which in turn could be used to produce more heat, which could run more of process, producing
even more excess work, and so on. The energy crisis, electric bills, etc. would be things of the
past. Unfortunately, no such device has ever been built and the first law still stands.

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In mathematical terms, the first law implies that there is a state function, called the
internal energy of the system, defined up to an arbitrary additive constant through its differential

dE ≡ d− Q − d− W ,

where d− W is the work done by the system (the negative of the work done on the system). For a
finite change of state, the change in the internal energy, ∆E, is given by
final state
∆E = ∫
initial state
d− Q − d− W .

The first law states that

∫odE = ∫od− Q − ∫od− W = 0.

The first law implies that the energy change computed along different paths must
give the same answer. If not, two such paths could be used to to build the energy-creating device
discussed above (i.e., by reversing one of the paths).

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8. THERMOCHEMISTRY

8.1. Enthalpy Calculations: Chemical Reactions and Hess’ Law

The enthalpy change for a process, ∆H, is equal to the heat absorbed by the system
if that process is done under constant pressure conditions (and assuming that only P-V work is
possible). Since the enthalpy of a system, H = E + PV, is a state function, we can systematize
enthalpy calculations by considering a path whereby the compounds first turn into their con-
stituent elements in their standard states (by convention at 25 oC and 1 atm pressure) and then
recombine to form the products. The enthalpy change in the latter step is just the enthalpy of for-
mation of the products and the former is the enthalpy of destruction (i.e., the negative of the
enthalpy of formation) of the reactants. Hence,

∆H = Σ ∆H 0f ( products) − ∆H 0f (reactants). (1)

 

Since we are interested in calculating a difference, the absolute enthalpy of the ele-
ments in their standard states is unimportant [it cancels out of Eq. (1)], and we adopt the conven-
tion that the enthalpy of formation of an element in its standard state is zero.
Consider the following example (reduction of iron oxide):
25 o C, 1 atm
Fe2 O3 (s) + 3H 2 (g) → 2Fe(s) + 3H 2 O(l).

A table of thermochemical data gives:

Enthalpies of Formation at 1 atm and 25 C

Compound ∆H 0f (kJ/mole)

Fe2 O3 (s) -824.2

H 2 (g) 0.0
Fe(s) 0.0
H 2 O(l) -285.830

By using these in Eq. (1), we find that

∆H = [3(−285. 830) − (−824. 2)]kJ/mole

= −33. 29kJ/mole.

Note that the calculated enthalpy change depends on how the reaction was written. For example,
if we wrote

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Thermochemistry -39- Chemistry CHEM 213W

1 3 25 o C, 1 atm 3
Fe2 O3 (s) + H 2 (g) → Fe(s) + H 2 O(l),
2 2 2
then ∆H = −16. 65 kJ/mole.

8.2. Measuring ∆H 0f
There are a number of ways in which to measure the enthalpy of formation of a
compound; here are two. The most obvious is to simply carry out the formation reaction from
the constituent elements in their standard states in a constant pressure calorimeter (recall that
∆H = Q p ).
For example, consider the combustion of graphite to form carbon dioxide
25 o C, 1 atm
C(graphite) + O2 (g) → CO2 (g).

The heat released in this reaction is −∆H 0f (CO2 ), since the standard enthalpy of formation of the
reactants is zero.
For this method to work, two conditions must be met: 1) the reaction goes to com-
pletion and 2) only one product is formed. Thus, the reaction
25 o C, 1 atm
C(graphite) + 2H 2 (g) → CH 4 (g)

is not suitable for this method since it doesn’t readily go to completion and we get a complicated
mixture of hydrocarbons.
In order to get around this, note that it is often possible to burn something to com-
pletion (and measure ∆H combustion , the heat released). Thus consider
25 o C, 1 atm
CH 4 (g) + 2O2 → CO2 (g) + 2H 2 O(l).

Equation (1) gives

∆H combustion = ∆H 0f (CO2 (g)) + 2∆H 0f (H 2 O(l)) − ∆H 0f (CH 4 (g)).

The standard enthalpies of formation of carbon dioxide and water can be measured using the first
method; hence, once we measure the heat of combustion, the only unknown is the standard
enthalpy of formation of methane (CH4) and a little algebra gives:

∆H 0f (CH 4 (g)) = ∆H 0f (CO2 (g)) + 2∆H 0f (H 2 O(l)) − ∆H combustion .

= [−398. 51 + 2(−285. 83) − (−890. 36)]kJ/mole

= −74. 81kJ/mole.

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In general, in order to measure the enthalpy of formation, all you need to to is find
any reaction where all but one of the standard enthalpies of formation are known and where the
reaction goes to completion. These sorts of manipulations are valid because the enthalpy is a
state function, and are referred to as Hess’s law. Also note that the same arguments could be
made for the energy changes (under constant volume conditions).

8.3. Reactions at Different Temperatures: Kirchoff ’s Law

What happens if the temperature at which you perform the reaction (either at con-
stant P or V) is different than that of your table of enthalpies of formation. Since the enthalpy is
a state function, an alternate path can be found whereby the enthalpy change, calculated using
the temperature of your table, can be used. Consider the constant pressure case depicted below
Reactants Products (T )
1

I II

Reactants Products (T )
0

The enthalpy change for the reaction at T 1 is equal to the enthalpy change at T 0 plus the enthalpy
change for paths 1 and 2. However, on 1 or 2, only the constant pressure heating or cooling of
the reactants or products is performed (i.e., no chemical reaction takes place). Since the constant
pressure heat capacity, C P was defined as

 ∂H 
CP ≡ ,
 ∂T  P,N

the incremental heat absorbed by the system on 1 or 2 is C P dT . Integrating gives:

T0 T1
∆H 1 = ∫T C P (reactants)dT = − T∫ C P (reactants)dT
1 0

and
T1
∆H 2 = ∫T C P ( products)dT .
0

Adding the contributions together gives

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T1
∆H(T 1 ) = ∆H(T 0 ) + ∫T C P ( products) − C P (reactants).
0

This is known as Kirchoff’s law. What changes must be made for the energy?
Consider our example of the reduction of Fe2 O3 . What is the enthalpy change at
358K? We will assume that the heat capacities are constant over the temperature range 298 - 358
K.

Constant Pressure Heat Capacities at 1 atm and 25 C

Compound C P (J/mole/K)

Fe2 O3 (s) 103.8

H 2 (g) 28.8
Fe(s) 25.1
H 2 O(l) 75.3

Note that elements in their standard states do not have zero heat capacities. Using the data in the
table, and the result of our earlier calculation gives

[2(25. 1) + 3(75. 3) − 103. 8 − 3(28. 8)][358 − 298]

∆H rxn (358K ) = −33. 29 +
1000

= −28. 1kJ/mole.

Note that no change in phase occurred when we cooled (heated) the reactants (prod-
ucts). What changes would have to be made if the reaction was carried out at 400 K?

8.4. Bond Energies

A useful, albeit very approximate, way to calculate enthalpy changes in chemical
reactions is through the concept of bond energies. Consider the following reaction

CH 4 → CH 3 + H;

i.e., one C-H bond is broken. Experimentally, ∆H for this reaction is 102 kcal/mole. Similarly,
∆H = 96 kcal/mole for

C 2 H 6 → C 2 H 5 + H.

A survey of such reactions will show that the heat required to break a single C-H bond is in the
range 96-102 kcal/mole. We can thus assign 98 kcal/mole as an average bond energy for the C-H
bond. Similar tends are observed in the bond strength of other types of bonds, and the results are
summarized in the following table

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Average Bond Energies

Energy Energy
Bond Bond
(kcal/mole) (kcal/mole)
H-H 103 C-H 98
C-C 80 N-H 92
C=C 145 O-H 109
C ≡C 198 Cl-H 102
N-N 37 Br-H 87
N≡N 225 I-H 71
O-O 34 C-Cl 78
O=O 117 C-N 66
Cl-Cl 57 C≡N 210
Br-Br 45 C-O 79
I-I 35 C=O 173

How can this be used? Consider the hydrogenation of ethlyene:

H 2 C = CH 2 + H − H → H 3 C − CH 3 .

At the molecular level, we break one H-H and one C=C bond, and form one C-C and two C-H
bonds. The energy change is just the net energy left in the molecule in such a process. From the
table, the bond breaking steps take 145+103=248 kcal/mole. The bond formation will give off
80+2(98)=276 kcal/mole. Hence the net energy change in the system is 248-276 = -28
kcal/mole. To get the enthalpy change, note that at constant pressure,

∆H = ∆E + P∆V .

For this reaction, all reactants and products are gases. If we assume that the gases are ideal, we
can compute ∆V ; i.e.,

RT
∆V = ∆N .
P
Here ∆N = −1 and thus

∆H = −28 − 1. 9872 × 10−3 kcal/mole/K × 298K

= −28. 6 kcal/mole.

(Note that here the difference between ∆H and ∆E is relatively small). The correct answer is
-32.7 kcal/mole. Thus while, the bond energy method is not exact it gives a reasonable estimate.
The reason for the discrepancy is the assumption that the bond energy doesn’t depend on what
other bonds are present in the molecule--in general this is not true.

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8.5. Some Manipulations Involving Thermodynamic Functions

8.5.1. The relationship between C P and CV

We know that

 ∂E 
CV =
 ∂T  N ,V

and that

 ∂H 
CP = .
 ∂T  N ,P

How these two quantities are related is a good exercise in manipulating thermodynamic func-
tions. Since H=E+PV,

 ∂E   ∂V 
CP = +P ,
 ∂T  N ,P  ∂T  N ,P

where the last derivative should be recognized as V α , where α is the thermal expansion coeffi-
cient,

1  ∂V 
α ≡ .
V  ∂T  N ,P

If we view the energy as a function of N,V,T,

 ∂E   ∂E   ∂E   ∂V 
= +
 ∂T  N ,P  ∂T  N ,V  ∂V  N ,T  ∂T  N ,P

 ∂E 
= CV + α V .
 ∂V  N ,T

Hence,

  ∂E  
C P − CV =  P + αV
 ∂V  N ,T 
 

VT α 2
= ,
β

where

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Thermochemistry -44- Chemistry CHEM 213W

1  ∂V 
β ≡−
V  ∂P T ,N

is the isothermal compressibility, and where the last equality will be proven later. The compres-
sitility must be positive (i.e., things get smaller when squeezed) and this implies that C P ≥ CV .
For an ideal gas, Joule showed that the internal energy per mole did not depend on the volume.
In this case,

C P − CV = α PV = R.

8.5.2. The Joule-Thompson Experiment

Consider the following adiabatic (i.e, Q=0) process, whereby a gas is squeezed
through a porous, rigid plug
P P
1 2

T1 P1 V1 T2 P 2 V2

Porous Plug

Fig. 1. The Joule-Thompson Experiment

Since, by assumption, Q=0,

∆E = E(P 2 , V 2 ) − E(P 1 , V 1 ) = −W = P 1V 1 − P 2V 2 .

By rearranging this expression we show that

E(P 1 , V 1 ) + P 1V 1 = E(P 2 , V 2 ) + P 2V 2 ;

i.e., the enthalpy, H is constant in the Joule-Thompson expansion.

In practice, large temperature changes can be obtained in this type of expansion
(which can be used in designing a refrigerator). The key parameter is the so-called Joule-
Thompson coefficient

 ∂T 
µ JT ≡ . (2)
 ∂P  H,N

In order to express µ JT in terms of more readily measurable quantities, note that

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∂ f 
 ∂y   ∂x  y
=− ,
 ∂x  f ∂ f 
 ∂y  x

which is sometimes known as the "cyclic rule" or "implicit function differentiation." It is proved
by noting that

∂ f  ∂ f 
df = dx + dy,
 ∂x  y  ∂y  x

setting df=0, and by solving for the ratio dy/dx.

By using the cyclic rule on Eq. (2), we find that

 ∂H 
 ∂P T ,N
µ JT =−
 ∂H 
 ∂T  P,N

1  ∂H 
=−
C P  ∂P  N ,T

V    ∂E  
=− 1 − β  P +   
CP   ∂V N ,T 

V  β V
=− 1− (C P − CV ) = − [1 − α T ],
CP  αV  Cp

where the second to last equality follows when the definition of the enthalpy in terms of the
energy is used and the manipulations used in calculating C P − CV are repeated. β is the isother-
mal compressibility. Note that the Joule-Thompson coefficient vanishes for an ideal-gas.

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9. The Second Law of Thermodynamics

The second law of thermodynamics gives information concerning the direction of
spontaneous change. If the second law says that a certain process is impossible, you will not be
able to get the process to go. On the other hand, note that if the second law says that a process is
possible, you still have to worry about kinetics--you have to find a way in which to carry out the
process in a reasonable amount of time.
There are a number of equivalent physical statements of the second law of thermo-
dynamics. According to Kubo (Thermodynamics, North Holland Publishing Co., 1976) they are:
1. Clausius principle: A process which involves no change other than the transfer of
heat from a hotter body to a cooler body is irreversible; or, it is impossible for heat
to transfer spontaneously from a colder to a hotter body without causing other
changes.
2. Thompson’s (or Kelvin’s) principle: A process in which work is transformed into
heat without any other changes is irreversible; or, it is impossible to convert all the
heat taken from a body of uniform temperature into work without causing other
changes.
3. Impossibility of perpetual motion of the second kind: (due to Max Planck) It is
impossible to devise an engine operating in a cycle which does work by taking heat
from a single heat reservoir without producing any other change.
4. Caratheodory’s principle: For a given thermal equilibrium state of a thermally
uniform system, there exists another state which is arbitrarily close to it, but which
can never be reached from it by an adiabatic change.
Any of these physical statements can be used to prove the others, and to finally
prove the mathematical statement of the second law of thermodynamics:
5. There exists a state function, the entropy (denoted by the letter S) which for any
spontaneous process satisfies the Clausius inequality:

d/Q
∆S ≥ ∫ T
where the equality holds when the process is reversible.
Before showing how 1.-4. imply 5., let’s first consider how the different physical
statements imply one another. For example, how does one show that Clausius’ principle implies
Thompson’s? Suppose it didn’t; i.e., Clausius’s principle is correct, but Thompson’s is not. This
means that you can build an engine which produces work, and which is connected to a single
heat reservoir. If so, consider the following device:

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TH

Q =Q +W
H L

W
E R

QE =W
Q’
L

TL
where, E is the Thompson violator, and R is a Carnot refrigerator.
If we adjust the sizes of E and R such that all the work is used to run the Carnot
refrigerator, and view the combined E-R apparatus as the system, we have succeeded in creating
a device, which spontaneously pumps heat from cold to hot without any work input from the sur-
roundings. This violates Clausius’ principle and thus we have proved Thompson’s principle by
contradiction.
Similarly, we can use Thompson’s principle to prove Clausius’. Again, the proof is
by contradiction. If Clausius’s principle is untrue, then you can find a device which sponta-
neously (i.e., without any work input) transfers heat from a colder body to a hotter one. Consider
the following apparatus:
TH

Q1 + Q2

Clausius C W= Q2
Q1
Violator

Q1

TC

where C is a Carnot engine and where the sizes of the Carnot engine and our Clausius violator
are adjusted such that the heats transferred are as indicated.

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Thermochemistry -48- Chemistry CHEM 213W

What is the net result after one cycle? Work has been produced in the surroundings,
but there is no net change in the heat content in the cooler reservoir. Hence, it is as if the system
were operating in contact with a single reservoir and producing work in the surroundings, in con-
tradiction to Thompson’s principle.
These kind of arguments can be used to prove the equivalence of the other physical
formulations of the second law.

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Second Law of Thermodynamics -49- Chemistry CHEM 213W

10. Carnot Engines, Efficiency, and The Second Law

Fig. 1. The Carnot Cycle

The Carnot engine is a useful construction for relating the mathematical (∆S ≥ 0 for
a spontaneous process in an isolated system) and the physical statements of the Second Law of
Thermodynamics (heat spontaneously flows from hot to cold). This handout goes through the
analysis of the amounts of work and heat produced in the isothermal and adiabatic parts of the
Carnot cycle for an ideal gas.

10.1. Energy in an Ideal Gas: Joule’s Experiment

In his study of the thermal properties of gases, Joule considerer the isothermal
expansion of dilute gases using the apparatus depicted below:

Thermometer

000000000
111111111
111111111
000000000
000000000
111111111
000000000
111111111
000000000
111111111
000000000
111111111
000000000
1111111110000
1111
000000000
111111111
0000000001111
1111111110000
0000
1111
000000000
111111111
P=0
/ 0000
1111 P=0
000000000
111111111
000000000
111111111
000000000
111111111
000000000
111111111
000000000
111111111
000000000
111111111
000000000
111111111
000000000
111111111

Fig. 2. Joule’s Experiment

The bulb on the right was evacuated initially and heat was allowed to exchange with the heat
bath, whose temperature was measured. For sufficiently dilute gases, Joule found that the tem-
perature of the bath didn’t change. This has some important consequences.

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Second Law of Thermodynamics -50- Chemistry CHEM 213W

For this process, P op = 0, and hence, W = 0. Moreover, since the temperature of the
bath remained constant, no heat was absorbed by the system, and thus ∆E = 0. What does this
say about the functional form of the energy of an ideal gas?
We know that we can write the energy of a one-component system as

E(N , V , T ) = N E(T , N /V ),

where density was chosen instead of pressure as an independent variable (as can always be done
if the equation of state is known). In Joule’s experiment T and N were held fixed but V, and
hence N/V, changed. Nonetheless, E didn’t change. Therefore, for an ideal gas,

E(N , V , T ) = N E(T );

i.e., the energy per mole of an ideal gas depends only on the temperature of the gas. Similarly,
the heat capacity will only be a function of temperature (as it turns out, the heat capacity of an
ideal gas is usually only weakly dependent on temperature).

10.2. Reversible, Adiabatic Expansion or Compression of an Ideal Gas

When an ideal gas is reversibly expanded (compressed) adiabatically, its temperature
falls (rises). In order to relate the temperature and volume changes, we note that the energy of a
ideal gas depends only on the temperature; hence,

dV
dE = CV dT = d− Q − d− W = d− Q − NRT , (1)
V
where CV is the heat capacity at constant volume and where the last equality is obtained by using
the ideal gas equation of state. For an adiabatic process, d− Q = 0. After a little algebra, Eq. (1)
can be rearranged to give:

CV dT dV
=− .
NR T V
If we assume that CV is independent of temperature (this a good approximation for gases of sim-
ple molecules such as Ar, CO2 etc.), this equality can be summed (or integrated) over the entire
adiabatic expansion; that is,
T final V
CV dT CV  T final  final
dV  V final 
NR ∫
T initial
T
= ln 
NR  T initial 
=−
V initial
V ∫
= − ln  ,
 V initial 
(2)

where the integrals have been evaluated and "ln" is the natural logarithm function. Finally, both
sides of Eq. (2) are exponentiated, and we find that
CV /NR
 V initial   T final 
 =  . (3)
 V final   T initial 

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Second Law of Thermodynamics -51- Chemistry CHEM 213W

This shows how volume and temperature changes are related along an adiabatic path. (No viola-
tion of Charles’ law is implied; why?) Notice, if V initial < V final , then the gas is cooler after the
expansion. This is to be expected since the expansion removes energy from the system, energy
which is not replaced by the addition of heat from a heat reservoir.
Finally, for an adiabatic change in an ideal gas,
T final

∆E = −W = +∆U mechanical =
T
∫ CV (T )dT ≈ CV ∆T
initial

whether or not the path is reversible!

10.3. Reversible, Isothermal Expansion or Compression of an Ideal Gas

Since the energy of an ideal gas depends only on the temperature T, it remains con-
stant during any isothermal process (i.e., dE = 0). From the first law, this implies that

dV
d− Q = dW = P dV = NRT . (4)
V
If the dQ’s given by Eq. (4) are summed over the entire expansion (i.e., between the initial vol-
ume, V initial and the final volume, V final ) we find that
V final
dV  V final 
W = Qisothermal = NRT
V
∫ V
= NRT ln 
 V initial
,

(5)
initial

10.4. Entropy Changes in the Carnot Cycle

Next we use Eq. (5) for the isothermal portions of the Carnot cycle (see Fig. 1, part 1
and 3); it is easy to show that

Q H QC V ′ V ′ 
+ = NR ln  2 1 . (6)
TH TC  V 1V 2 
However, if we use Eq. (3) on part 2 of the cycle, it follows that
CV /NR
V 2′  T C 
=  .
V2  T H 

Similarly, for the adiabatic compression,

CV /NR
V 1′  T H 
=  .
V 1  TC 

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Second Law of Thermodynamics -52- Chemistry CHEM 213W

Thus, if we use these two expressions in Eq. (6) the argument of the logarithm becomes equal to
1, and

Q H QC
+ = 0. (7)
TH TC

This is an explicit demonstration of the Second Law of Thermodynamics (i.e., that the entropy is
a state function).
Note that the efficiency, (denoted by the Greek letter eta, η ), of the Carnot cycle (i.e.,
how much work is produced per unit heat absorbed) is easily obtained using Eq. (7):

W Q + QC T
η≡ = H =1− C ,
QH QH TH

where the second equality follows form the first law and where the last equality follows from Eq.
(7). As is shown on the following pages of the handout, this efficiency formula must hold no
matter what the working fluid in the Carnot engine, and hence, Eq. (7) must hold for materials
other than ideal gases.

10.5. Entropy Changes in Arbitrary Cycles

What if we have a process which occurs in a cycle other than the Carnot cycle, e.g.,
the cycle depicted in Fig. 3.

Figure 2
Fig. 3. An arbitrary cycle.
If entropy is a state function,

∫
cycle
dS = 0

no matter what the nature of the cycle. In order to see that this is true, break up the cycle into

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Second Law of Thermodynamics -53- Chemistry CHEM 213W

sub-cycles, each of which is a Carnot cycle, as shown in Fig. 3. If we apply Eq. (7) to each
piece, and add the results, we get zero for the sum.
In summary, we have shown that the entropy

dQ reversible
S≡ ∫ T
is a state function. Moreover, since d− Q ≤ dQ reversible ,

d− Q
dS ≥ ;
T
the equality holds only for reversible processes.

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Efficiency of Carnot Engines -54- Chemistry CHEM 213W

11. Why the Efficiency of a Carnot Engine is Independent of the Kind of Working Material
Here are two proofs that the efficiency of a reversible Carnot engine depends only on
the temperatures of the heat baths.

11.1. Method I using Thompson’s Principle

TH

Q Q’
H H

W W’
R E

Q
L
Q’
L

TL
where

W′ = the work produced by the engine,

Q′H = the heat absorbed by the engine from the hot reservoir,
Q′L = the heat given off by the engine to the cooler reservoir,
W = the work used to run the Carnot refrigerator,
QH = the heat given off by the refrigerator to the hot reservoir,
QL = the heat absorbed by the refrigerator from the cooler reservoir.

The sizes of the engine and refrigerator are adjusted such that no net heat is taken
from the cool reservoir in one cycle (i.e., Q L = Q L ′). According to Thompson’s principle, no net
positive work can be realized in the surroundings from any device which takes heat from a single
heat source. Thus,

W ′ − W ≤ 0. (1)

However, from the First Law, the net work produced must equal the net heat absorbed by the sys-
tem; i.e.,

W ′ − W = QH ′ − QH . (2)

If we denote the "engine efficiencies" of the refrigerator and engine as η and η ′, respectively, Eq.
(2) can be rewritten as:

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Efficiency of Carnot Engines -55- Chemistry CHEM 213W

1 − η ′ = [1 − η ] Q H (3)
  QH ′

From Eqs. (1) and (2) it follows that

QH
≥ 1;
QH ′

which when used in Eq. (3) gives:

η ≥ η ′. (4)

Note that this is true even if one or both of the engines is not reversible. If both engines are
reversible, then the roles of engine and refrigerator can be interchanged and we conclude that

η′ ≥ η.

In light of Eq. (4) this is possible only if η = η ′. Note that for this case, the net work is zero!.
Finally, if the engine is irreversible, an upper bound to its efficiency can be obtained by using a
reversible refrigerator. In this case, Eq. (4) implies that

TL
η IR ≤ η REV = 1 − .
TH

11.2. Method II using Clausius’ Principle

TH

Q Q’
H H

W
E R

Q
L
Q’
L

TL
where

W = the work produced by the engine

QH = the heat absorbed by the engine from the hot heat bath

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Efficiency of Carnot Engines -56- Chemistry CHEM 213W

QL = the heat released by the engine to the cool heat bath

Q′H = the heat released by the refrigerator to the hot heat bath
Q′L = the heat absorbed by the refrigerator from the cool heat bath

We will assume that the Carnot engine is more efficient than the Carnot refrigerator
and that the size of the engine is adjusted so that the work output of the former equals that
needed to run the latter; i.e.,

W W
ηE = > ηR = . (1)
QH Q′H

By assumption therefore,

Q H < Q′H . (2)

Since the engine and the refrigerator run in a cycle, the first law tells us that (∆E = 0):

W = Q H − Q L = Q′H − Q′L , (3)

which when combined with (2) shows that

Q L − Q L ′ = Q H − Q′H < 0. (4)

What does this mean? The quantity Q H − Q′H is the net heat taken OUT of the hot-
ter heat source. However, cf. Eq. (4), we have just shown that it is negative; i.e., a net amount of
heat (>0) has been transferred INTO the hotter heat source from the cooler one. No net work has
been done by the surroundings (i.e., by us), and thus our initial assumption violates Clausius’
statement of the second law of thermodynamics. Hence, we must conclude that η E ≤ η R . This
reverses the inequality in Eq. (4); i.e., now the net heat taken OUT of the hotter body and going
INTO the colder one is positive, and does not violate Clausius’ statement of the second law.
If both the engine and refrigerator are reversible, then they can both be run in
reverse; hence the engine now acts as a refrigerator and the refrigerator as an engine. All the
signs on work and heat flip and we conclude that η R ≤ η E (where the R and E refer to the origi-
nal devices). The only way out of this contradiction is for the efficiencies of all reversible Carnot
cycles to be equal no matter what the nature of the material in the engine or refrigerator.

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The Clausius Inequality -57- Chemistry CHEM 213W

12. The Clausius Inequality and the Mathematical Statement of the Second Law
Here is a summary of the proof of the Clausius inequality given in class.

To

Carnot Engine dWC

−dQS

System, T dWS
} dW Total

where C is a reversible Carnot engine which takes heat −d− Q s from a part of the system at tem-
perature T, produces work, d− W c , in the surroundings, and gives the remaining heat to a reservoir
at temperature T 0 . While this happens, the system absorbs heat d− Q s and produces work d− W s .
From our definition of efficiency and the fact that the efficiencies of all reversible
Carnot engine are the same (cf. previous handout), we have:

T
d− W c = −η c d− Q s =  o − 1 d− Q s . (1)
T 
From Thompson’s principle and Eq. (1), it follows that

To
W Total = o d− W s + d− W c = o d− W s +  − 1 d− Q s ≤ 0.
∫ ∫ (2)
T 
This inequality must hold if the process is to proceed as written. Now we integrate Eq. (2)
around one cycle of the system (reversible or not) and use the fact that the system’s energy is
conserved; i.e.,

∫od− W s = ∫od− Q s .
After a little algebra, this gives:

d− Q s
∫
o
T
≤ 0, (3)

where the constant, positive multiplicative factor, T 0 , has been dropped. This is the Clausius
inequality.

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The Clausius Inequality -58- Chemistry CHEM 213W

Equation (3) holds for any spontaneous process which can occur in the system;
although, all irreversible processes will require a net work input in order to run in the configura-
tion depicted above. The inequality in Thompson’s principle, cf. the last handout, becomes an
equality only for reversible processes (no matter what the path) and thus Eq. (3) becomes:

d− Q rev
0= o∫ T
≡ odS ∫ (4)

where the entropy is defined along any reversible path (Eq. (4) is a proof that it is a state func-
tion) through

d− Q rev
dS ≡ (5)
T

d− Q
Proof that dS ≥
T

Consider some process whereby the system changes from state A to B along path I;
it may be irreversible. After the process is finished, the system is restored to its initial state (A)
along a reversible path II. If we apply the Clausius inequality to this cycle, we have

d− Q I d− Q rev
B A

∫
A, pathI
T
+ ∫
B, pathII
T
≤ 0. (1)

Since path II is reversible, the process can be carried out in reverse (This is not necessarily true
for path I) and thus:

d− Q rev d− Q rev
A B

∫
B, pathII
T
=− ∫
A, pathII
T
= −∆S A→B (2)

By using Eq. (2) in Eq. (1) we conclude that

d− Q I
B
∆S A→B ≥ ∫
A
T
,

or for infinitesimal changes

d− Q
dS ≥ .
T
Note that the equality holds only for reversible processes.

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Chemical Potential -59- Chemistry CHEM 213W

13. Systems With Variable Composition: The Chemical Potential

Up to now, we have not seriously considered the consequences of changing the com-
position of a thermodynamic system. In practice, this can happen in two ways: 1) by externally
adding or removing material or 2) by changing the composition through chemical reaction.
Nonetheless, as far as state functions are concerned, the same results must be considered.
There is an energy change associated with changing the composition of the system.
For example, you may add compounds with different types of bonds and this will change the
energy available to carry out other processes (e.g., via combustion).
In order to account for the energy change associated with adding material to the sys-
tem we introduce a new kind of work done by the system:

d− W i ≡ − µ i,op dN i , (1)

where dN i is the change in the amount of the i’th component (i.e., mass, number of moles, etc.)
and where µ i,op is called the opposing chemical potential (and is analogous to the opposing pres-
sure). For reversible processes, the opposing chemical potential equals the chemical potential,
µ i , of component i in the system. In general, the chemical potential for component i in a system
is intensive and is a function of T,P, composition and phase. Moreover, like the equation of state,
it must be measured or calculated from a microscopic theory, and we will consider some specific
examples later.
The energy change of the system can now be written as:

dE = d− Q − P op dV + Σ µ i,op dN i (2)
i

or for reversible paths as

dE = TdS − PdV + Σ µ i dN i . (3)

i

Henceforth, we will restrict ourselves to processes where the addition of matter is reversible and
thus drop the subscript "op" on µ .
Equation (2) has an interesting consequence. If we view the energy of a system as a
function of S, V, and the N i (all of which are extensive), then Euler’s theorem implies that

 ∂E   ∂E   ∂E 
E(S, V , N i ) = S+ V +Σ Ni .
 ∂S V ,N i  ∂V  S,N i i  ∂N i  S,V ,N j≠i

The partial derivatives immediately follow from Eq. (4), and we find that

E = TS − PV + Σ µ i N i . (4)
i

We also obtain the Gibbs-Duhem equation

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Chemical Potential -60- Chemistry CHEM 213W

0 = SdT − VdP + Σ N i d µ i . (5)

i

By using Eq. (4) and H ≡ E + PV , it follows that

H = TS + Σ µ i N i . (6)
i

As we will now see, the chemical potentials play a key role in any quantitative anal-
ysis of chemical equilibria.

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Maxwell Relations -61- Chemistry CHEM 213W

14. Exact Differentials and Maxwell Relations

14.1. A Theorem From Calculus

Consider the differential form:

df ≡ M(x, y)dx + N (x, y)dy. (1)

If can we define a single-valued, differentiable function f(x,y) which satisfies Eq. (1), then
M(x, y)dx + N (x, y)dy is said to be an exact differential. Of course, we can always define f(x,y)
by integrating the right hand side of Eq. (1) along some path; however, we require that the func-
tion be single-valued (i.e., that it be a state function), hence different paths must give the same
answer.
THEOREM:
If M and N have continuous first partial derivatives at all points of some open rectan-
gle, the differential form, (1), is exact at each point of the rectangle if and only if the condition

 ∂M   ∂N 
= (2)
 ∂y  x  ∂x  y

is satisfied throughout the rectangle. When this holds, the function f(x,y) is given by the line
integral

f (x, y) = ∫C M(s, t)ds + N (s, t)dt (3)

along the path from (a,b) to (x,y) shown in Fig. 1.

t

C’ (x,y)

C
(a,b)

s
Figure 1

Proof:

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Maxwell Relations -62- Chemistry CHEM 213W

The necessity of the condition is shown by noting that if f is exact, then

∂ f 
= M(x, y)
 ∂x  y

and

∂ f 
= N (x, y).
 ∂y  x

However, if the second partial derivatives of a function are continuous then the order of differen-
tiation is immaterial and

∂2 f (x, y) ∂2 f (x, y)
= ,
∂x∂y ∂y∂x

which when expressed in terms of derivatives of M and N gives Eq. (2).

To show that the condition is sufficient is slightly more complicated. First, consider
a point infinitesimally close to (a,b); i.e., (a+dx,b+dy). In this case, we can make linear approxi-
mations for the behaviors of M and N and the function defined on C, f C becomes

dx dy
fC = ∫0 M(a + s, b)ds + ∫0 N (a + dx, b + t)dt

 
dy
dx
 ∂M    ∂N   ∂N  
≈ ∫0  M(a, b) + 

s ds +
∂x  x=a;y=b  ∫0  N (a, b) + 
 ∂x  x=a;y=b
dx +
 ∂y  x=a;y=b
t  dt


 ∂M  dx 2   ∂N    ∂N  dy 2
= M(a, b)dx + +  N (a, b) + dx  dy + (4)
 ∂x  x=a;y=b 2  ∂x  x=a;y=b  ∂y  x=a;y=b 2
 
which is valid up to terms of third order in dx and/or dy. Next we repeat the preceding argument
on the path C’ shown in Fig. 1. This gives

 ∂N  dy 2   ∂M    ∂M  dx 2
≈ N (a, b)dy + +  M(a, b) + dy dx +
 ∂y  x=a;y=b 
f C′ . (5)
 ∂y  x=a;y=b 2  ∂x  x=a;y=b 2
 
If f is single-valued, f C = f C′ . By equating the right hand sides of Eqs. (4) and (5) we see that

 ∂N ∂M 
f C − f C′ ≈ dxdy  −  (6)
 ∂x ∂y 

which vanishes if Eq. (2) holds. Incidentally, note that the left hand side of Eq. (6) is just a line

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Maxwell Relations -63- Chemistry CHEM 213W

integral around a closed path and the quantity on the right hand side is an approximate surface
integral.
Of course, Eq. (6) is valid only for (x,y) infinitesimally close to (a,b). For arbitrary
paths, and (x,y) we break up the interior of the path into small rectangles as shown in Fig. 2.

Figure 2
If the rectangles are small enough, then Eq. (6) can be used on each one and the results added
together. This leads to cancellations of all the line integrals on the edges of adjacent rectangles
inside the path (because of the directions of the integrations) and finally gives

 ∂N ∂M 
∫
o M(x, y)dx + N (x, y)dy = ∫∫ dxdy 
 ∂x
− .
∂y 

In calculus, this result is called Green’s theorem in the plane. Finally, Since we’ve assumed that
(2) holds,

∫o M(x, y)dx + N (x, y)dy = 0

which is just what we need to show that f defined by Eq. (3) is single-valued (i.e., it is a state
function).

14.2. Applications to Thermodynamics: Maxwell Relations

We have been able to combine the first and second laws of thermodynamics to write

dE = TdS − PdV .

Since E is a state function, Eq. (2) must hold and thus

 ∂T   ∂P 
=− .
 ∂V  S  ∂S V

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Maxwell Relations -64- Chemistry CHEM 213W

This is called a Maxwell relation and is a powerful tool for relating different quantities thermo-
dynamics.
Another Maxwell relation can be obtained from the enthalpy for which

dH = TdS + VdP. (7)

Hence, Eq. (2) gives

 ∂T   ∂V 
=
 ∂P  S  ∂S  P

Clearly every state function will generate one or more Maxwell relations. The trick is to know
which ones to use in any given application.

14.3. A Complicated Example

Suppose we want to express the change in the entropy as a function of T and P. To
begin, note that

 ∂S   ∂S 
dS = dT + dP + SdN ,
 ∂T  P,N  ∂P T ,N

where S is the partial molar entropy (remember that entropy is extensive and Euler’s theorem
must hold). The term in dT is easy to reexpress. When the pressure is constant, the change in
the entropy is

d− Q P C P
dS = = dT
T T
and thus

CP  ∂S 
dS = dT + dP + SdN .
T  ∂P T ,N

A new entropy derivative still remains to be reexpressed in terms of something more

conventional. To do so we will use a Maxwell relation. We know that

∂2 H ∂2 H
= ; (8)
∂T ∂P ∂P∂T
however, from Eq. (7)

∂   ∂S  
LHS = T   + V
∂T  ∂P T ,N 

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Maxwell Relations -65- Chemistry CHEM 213W

 ∂S  ∂2 S
= +T + Vα ,
 ∂P T ,N ∂T ∂P

where recall that α ≡ V −1 (∂V /∂T ) P,N . Similarly,

∂   ∂S  
RHS = T 
∂P   ∂T  N ,P 

∂2 S
=T .
∂P∂T
Since the entropy is a state function, its mixed second derivatives must be equal; hence, equating
the LHS and RHS of Eq. (8) and carrying out some algebra gives:

 ∂S   ∂V 
=− = −V α . (9)
 ∂P T ,N  ∂T  P,N

Thus, we have succeeded in expressing the change in the entropy in terms of readily measurable
quantities; namely

CP
dS = dT − V α dP + SdN . (10)
T
(Actually, there is a much simpler route to Eq. (9) using the Maxwell relation for the Gibb’s Free
energy, see below). For for finite changes in state, Eq. (10) gives
(T ,P)
CP
S(T , P) = S(T 0 , P 0 ) + ∫
(T ,P )
T
dT − V α dP,
0 0

where the choice of path is unimportant. Note that no change in phase must occur along the
path. If not, corrections for the enthalpy change associated with the transition (i.e., the heat)
must be included.
With Eq. (10), we can finish our discussion of the difference between the heat capac-
ities. In Sec. 5.1 of the Thermochemistry handout we showed that

  ∂E  
C P − CV = α V  P +
 ∂V  N ,T 
. (11)
 
But, dE = TdS − PdV ; hence,

 ∂E   ∂S 
=T −P
 ∂V  N ,T  ∂V  N ,T

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 ∂S   ∂P 
=T − P,
 ∂P  N ,T  ∂V  N ,T

where the second equality follows from the chain rule. Equation (10) gives the entropy deriva-
tive, and the pressure derivative is equal to −V / β , where β is the isothermal compressibility.
Thus,

 ∂E  TV α
= −P
 ∂V  N ,T β

and

VT α 2
C P − CV = .
β

Note that C P ≥ CV for all materials! Express the Joule-Thompson coefficient in terms of α , β ,
and C P /V .

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15. Thermodynamic Stability: Free Energy and Chemical Equilibrium

All the criteria for thermodynamic stability stem from the Clausius inequality; i.e.,
for any possible change in nature,

d− Q
dS ≥ . (1)
T
Conversely, if

d− Q
dS < (2)
T
for every allowed change in state, then the system cannot spontaneously leave the current state
NO MATTER WHAT; hence the system is in what is called stable equilibrium.
The stability criterion becomes particularly simple if the system is adiabatically
insulated from the surroundings. In this case, if all allowed variations lead to a decrease in
entropy, then nothing will happen. The system will remain where it is. Said another way, the
entropy of an adiabatically insulated stable equilibrium system is a maximum. Notice that the
term allowed plays an important role. For example, if the system is in a constant volume con-
tainer, changes in state or variations which lead to a change in the volume need not be considered
even if they lead to an increase in the entropy.
What if the system is not adiabatically insulated from the surroundings? Is there a
more convenient test than Eq. (2)? The answer is yes. To see how it comes about, note we can
rewrite the criterion for stable equilibrium that using the first law as

d− Q = dE + P op dV − µ dN > TdS, (3)

which implies that

dE + P op dV − µ dN − TdS > 0 (4)

for all allowed variations if the system is in equilibrium. Equation (4) is the key stability result.
As discussed above, if E, V, and N are held fixed d− Q = 0 and the stability condition becomes
dS < 0 as before.
What if S,V,N is held constant? From Eq. (4), the system will be stable if dE > 0;
i.e., the energy is a minimum. This has a nice mechanical analogy. Consider a ball rolling on a
frictionless parabolic surface in a gravitational field. Clearly, if we place the ball at rest at the
lowest point then it will stay there forever. This is the point which minimizes the energy.
Of course, it is not always easy to see how to hold the entropy constant in real exper-
iments. (When is the entropy constant?) A more common situation is when the temperature of
the system is held fixed. What is the stability criterion? The problem and its solution are similar
to those which led to the introduction of the enthalpy. If (N,T,V) are held fixed, Eq. (4) becomes

(dE) N ,T ,V − T (dS) N ,T ,V > 0, (5a)

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or since T is constant,

d(E − TS) N ,T ,V > 0. (5b)

Thus, we see that a new state function, A ≡ E − TS, is a minimum for a stable equilibrium where
(N,T,V) are not allowed to vary. This new state function, is defined via a Legendre transforma-
tion on the energy and is called the Helmholtz free energy.
From the definition of A, for a general change in state (i.e., not necessarily with
dT = 0, etc.)

dA = dE − SdT − TdS

= (d− Q − TdS) − d− W − SdT + µ dN . (6)

The Clausius inequality implies that the quantity in the parenthesis is negative (or zero for a
reversible process) for any spontaneous change in the state of the system. Moreover, if we con-
sider systems where T and N are held fixed

dA ≤ −d− W

or

W ≤ −∆ A. (7)

This means the −∆ A is the maximum work you can get out of a process run under constant T and
N conditions (hence the name "free energy"). In addition, since A is a state function, you can get
the bound without knowing anything about the path (or device)--just by knowing the initial and
final states and how to carry out a calculation similar to those we did in thermochemistry.
Since A is a state function, we can always compute changes along reversible paths.
In this case,

dA = −SdT − PdV + µ dN . (8)

In addition, we pick up some new Maxwell relations, e.g.,

 ∂S   ∂P 
= . (9)
 ∂V T ,N  ∂T V ,N

Clearly, there are many different choices of which state variables can be held con-
stant. We will only consider two more. First suppose (S,P,N) is held fixed. This is analogous to
what we encountered with the enthalpy. In this case, Eq. (4) becomes

d(E + PV )S,P,N = (dH)S,P,N > 0 (10)

for stable equilibrium; i.e., the enthalpy is a minimum.

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Finally, and perhaps most importantly, suppose T, P, and N are held fixed. This is
the most commonly encountered case. Now Eq. (4) becomes

d(E + PV − TS)T ,P,N > 0. (11)

Thus a new state function, G ≡ E + PV − TS = H − TS, is a minimum for a stable equilibrium

with fixed temperature, pressure, and mass. This state function is called the Gibbs free energy.
As was the case with the Helmholtz free energy, ∆G has a direct physical interpreta-
tion. From its definition, for a constant (T,P,N) processes,

dG = dE − TdS + PdV (12a)

= (d− Q − TdS) − (d− W − PdV ) ≤ −(d− W − PdV ), (12b)

where the last inequality follows from the Clausius inequality. For finite changes in state, we
find

W− ∫ PdV ≤ −∆G. (13)

What does this mean? Up to now, we have mainly considered PV work. Of course, there are
other kinds (magnetic, electrical but to name two). Hence, −∆G provides an upper bound to the
non-PV work that can be obtained from a constant T,P,N process. If you are manufacturing elec-
tric batteries you probably don’t care about the amount of PV work which is wasted if the battery
expands or contracts--all you want is the electrical work.
As in the case of the Helmholtz free energy, we can consider arbitrary changes in the
Gibbs free energy along reversible paths. From its definition

dG = −SdT + VdP + µ dN . (14)

As before, this gives additional Maxwell relations, for example

 ∂S   ∂V 
=− = −V α , (15)
 ∂P T ,N  ∂T  P,N

which we obtained in a very complicated way in the last handout.

One final point, note that the partial molar Gibbs free energy is

 ∂G 
G= = µ, (16)
 ∂N T ,P

where Eq. (14) was used. Hence, in a one component system, the Gibbs free energy per mole is
just the chemical potential. More generally, G i , the partial molar quantity for the i’th component
is µ i , and hence, from Euler’s theorem

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G = Σ Ni µ i . (17)
i

As we discussed earlier, in order that Eqs. (17) and (14) be consistent, a Gibbs-Duhem relation
must hold; i.e.,

0 = SdT − VdP + Σ N i d µ i , (18)

i

which shows that the changes in temperature, pressure and chemical potentials are not all inde-
pendent.
The various stability results are summarized in the following table.

Criteria for Stable Equilibrium

State Stable Equilibrium
Held Fixed Definition Differential
Function Criterion

dQ rev
E,V,N S - dS = maximum
T
S,V,N E - dE = TdS − PdV + µ dN minimum

S,P,N H H ≡ E + PV dH = TdS + VdP + µ dN minimum

T,V,N A A ≡ E − TS dA = −SdT − PdV + µ dN minimum

T,P,N G G ≡ H − TS dG = −SdT + VdP + µ dN minimum

15.1. Examples of free energy calculations

Free energy calculations are carried out in much the same as enthalpy calculations.
There are tables of standard free energies of formation of compounds. Elements in their stan-
dard states are assigned zero as their Gibbs free energy of formation.
Consider the following chemical reaction:

H 2 (g) + Cl 2 (g) → 2HCl(g).

Will the reaction proceed as written under constant T and P conditions? The free energy change
is simply

Σ ∆G 0f ( products) − ∆G 0f (reactants) (19)

which for the case at hand is just 2∆G 0f (HCl, g) or -184.62 kJ/mole (from Barrow). Hence, a
mixture of hydrogen and and chlorine can lower its free energy (by a substantial amount) by
reacting to form HCl.

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This is an interesting example for another reason; if you mix stoichiometric amounts
of H 2 and Cl 2 , you will not see any perceptible reaction--the rate of reaction (no matter what the
thermodynamics says) is in this case extremely slow. On the other hand, a small amount of light
at the right frequency will catalyze the reaction which then proceeds explosively!
Next consider the reaction between graphite and diamond,

C(graphite, s) → C(diamond, s).

Now ∆G = 2.90 kJ/mole. The reaction does not proceed as written (too bad). What is perhaps
more troubling is that the reverse reaction should proceed spontaneously at STP. (So why invest
in diamonds?)
What happens at other temperatures or pressures. To answer this note that from Eq.
(14), for any compound,
(T ,P)
∆G f (T , P) = ∆G 0f + ∫
(298K, 1 atm)
−S(T , P)dT + V (T , P)dP,

where any convenient path can be chosen.

Thus if we raise the pressure,
(298K ,P)
∆G rxn (T , P) = ∆G rxn + ∫ ∆V rxn dP.
0
(20)
(298K, 1 atm)

At STP, ∆V rxn = -1.9 cm 3 /mole. Hence, increasing the pressure decreases the Gibbs free energy
change. If we assume that the molar densities of carbon are roughly independent of pressure, we
can calculate the pressure at which the reaction will proceed as written. In this approximation,

∆G rxn (T , P) ≈ 2. 90 − 1. 9 × 10−9 ∆P (kJ/mole)

Hence, the reaction begins to be possible when P ≈ 1. 530 × 109 Pa or about 15,000 atm.

15.2. Chemical Equilibrium

A very important example of thermodynamic equilibrium is that of chemical equilib-
rium at constant pressure and temperature. Consider the following general chemical reaction:

2 A + B ←→ 3C + D.

The chemical equation imposes a strong constraint on the changes in the numbers of moles of
each component; for the forward reaction, each time a mole of B reacts, 2 of A are used up and 3
of C and one of D are produced. Mathematically,

dN A dN B dN C dN A
= = = ≡ dξ ,
−2 −1 3 1

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where the extent of the reaction is characterized by the quantity ξ (the Greek letter, pronounced
kse) called the progress variable. For an arbitrary chemical reaction involving r chemical com-
ponents, the last expression generalizes to

dN 1 dN r
= ... = ≡ dξ , (22)
ν1 νr

where ν i is the stoichiometric coefficient for the i’th component in the reaction (by convention, it
is negative for reactants).
For constant temperature and pressure and total mass (for each element) conditions,
the reaction can proceed until the Gibbs free energy is a minimum with respect to all allowed
variations in the state of the system. For fixed total mass, temperature, and pressure, the only
variations which can be considered are those which change ξ . That is the reaction moves either
to the right or left until G(ξ ) is a minimum.
G can be a minimum with respect to changes in the progress variable only if

 ∂G 
=0 (23)
 ∂ξ T ,P,N total

and

∂ G
2
> 0. (24)
 ∂ξ 2 T ,P,N total

By using the differential form for the change in the free energy together with Eq. (22) we find
that
r
dG = −SdT + VdP + Σ ν i µ i d ξ , (25)
i=1

which when used in Eq. (23) gives

r
Σ ν i µi = 0
i=1
(26)

at equilibrium. Since the µ i are the partial molar Gibbs free energies, Eq. (26) is equivalent to
∆G = 0. At equilibrium the free energy change in the reaction per mole vanishes. (Indeed,
this is the principle we applied in the "reaction" between graphite and diamond). From the defi-
nition of the Gibbs free energy (G = H -TS), it follows that

∆H
∆S =
T
at equilibrium.
What happens if we change temperature or pressure by a small amount? Which way
will the equilibrium shift? To answer this note the following Maxwell relations:

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Free Energy -73- Chemistry CHEM 213W

 ∂µi   ∂S 
=− = −S i (27a)
 ∂T  P,N j  ∂N i  P,T ,N j≠i

and

 ∂µi   ∂V 
= = Vi (27b)
 ∂P T ,N j  ∂N i  P,T ,N j≠i

which follow from the Gibbs free energy. Thus the changes in the chemical potential associated
with temperature or pressure are related to the partial molar entropies or volumes, respectively.
Next consider

 ∂µi   ∂µi   ∂(Σ ν i µ i ) 

d(Σ ν i µ i ) = Σ ν i dT + Σ ν i dP + dξ
i i  ∂T  P,N j i  ∂P  P,N j  ∂ξ T ,P,N total

∂∆G
= −∆SdT + ∆V dP + dξ , (28)
∂ξ

where, cf. Eqs. (27), ∆S ≡ Σ ν i S i and ∆V ≡ Σ ν i V i are the entropy and volume changes per mole
or reaction. Equation (28) shows how the free energy change per mole of reaction changes when
we change T, P, or ξ .
What happens if we change, T or P in a system where chemical reaction is possible?
The progress variable will change until Eq. (26) is again valid. Since both the initial and final
states satisfy Eq. (26), the change in ∆G must vanish. From Eq. (28) this implies that

∆SdT − ∆V dP
dξ = . (29)
 ∂∆G 
 ∂ξ T ,P,N total

Moreover, the denominator of the right hand side of the equation is positive, cf. Eq. (24). Equa-
tion (29) can be rewritten by noting [cf. Eq. (26)] that ∆S = ∆H /T ; i.e.,

∆H
dT − ∆V dP
dξ = T . (30)
 ∂∆G 
 ∂ξ T ,P,N total

Equation (30) is a mathematical statement of LeChatellier’s principle. For reac-

tions which lead to an increase in the volume (∆V > 0, increasing (decreasing) the pressure will
shift the equilibrium to the reactant (d ξ < 0) [product (d ξ > 0)] side of the equation. The reverse
is true if the volume change is negative. Similarly, increasing the temperature shifts the equilib-
rium to the reactant side for reactions which are exothermic (∆H < 0) and to the product side for
reactions which are endothermic.

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15.3. Chemical equilibria in dilute gases

For a one-component gas, the pressure dependence of the chemical potential (free
energy per mole) is easily obtained from Eq. (20); i.e.,
P
µ = µ 0 (T ) + ∫1 V (T , P′)d P′.
Where µ 0 (T ) is the standard Gibbs free energy of formation at one atm and temperature T. If the
gas is ideal, then V=RT/P and we find that

µ (T , P) = µ 0 (T ) + RT ln(P), (31)

where P is the pressure in atmospheres.

This result can be generalized to gas mixtures if we recall our discussion of Dalton’s
law of partial pressures. There we considered a gas mixture where one of the components could
diffuse in and out of the system through a selective, porous film into a container containing a
pure sample of that component. At equilibrium, the pressure in the pure sample was P i , the par-
tial pressure of the i’th component in the mixture.
If we view the process as the following "chemical reaction"

Component i in mixture ←→ Component i in pure sample.

The equilibrium condition becomes:

µ i,mixture (T , P, x 1, ..., x r−1 ) = µ i, pure (T , P i ) = µ 0i (T ) + RT ln(P i ). (32)

Hence, the form of the chemical potential in a gas mixture is very similar to that in a pure sam-
ple, with the exception that the pressure is not the total pressure of the gas, but is the partial pres-
sure of the component in question.
Knowing this, we are ready to discuss chemical equilibria in gases. From Eq. (26),
the equilibrium condition becomes:

0 = Σ ν i µ 0i (T ) + RT ln(Pν11 Pν22 ... Pνr r ) (33a)

i

or

Pν11 Pν22 ... Pνr r = K P (T ) ≡ exp − Σ ν i µ 0i (T )/RT  = e−∆G/RT , (33b)

 
where K P (T ) is called the pressure equilibrium constant. Notice that it is only a function of tem-
perature, the stoichiometric coefficients, and properties of the pure (i.e., unmixed) gases.

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15.4. Examples of Chemical Equilibrium Calculations

15.4.1. Free Energy and Entropy of Mixing

Perhaps the simplest process were two samples of different pure gases are isother-
mally mixed as depicted below

A(P,T,V) + B(P,T,V) A+B (P,T,2V)

As you might expect, this process always occurs spontaneously. The total pressure and tempera-
ture remain constant during the process. What is the Gibbs free energy change?
From Eq. (32), it follows that the free energy of the final state is

G final = N 1  µ 01 (T ) + RT ln(P 1 ) + N 2  µ 02 (T ) + RT ln(P 2 ). (34a)

   
Similarly, the Gibbs free energy of either of the pure samples is

G i = N i  µ 0i (T ) + RT ln(P) (34b)
 
and hence, the free energy of mixing per mole of mixture, ∆G mix , is

∆G mix = RTx 1 ln(x 1 ) + RTx 2 ln(x 2 ), (35)

where x i is the mole fraction of i and where Dalton’s law of partial pressures, P i = Px i , was
used. It is easy to generalize this result to arbitrary mixtures of ideal gases

∆G mix = RT Σ x i ln(x i ). (36)

i

Since 0 < x i < 1, the free energy change is negative and the mixing occurs spontaneously.
Equation (36) can be used to calculate the entropy and enthalpy of mixing. By using
Eq. (14) it follows that

 ∂∆G mixing 
∆S mix = − , (37)
 ∂T  P,x i

which when used in Eq. (36) gives

∆S mix = −R Σ x i ln(x i ) > 0. (38)

i

Moreover, since

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∆H mix = ∆G mix + T ∆S mix,

it follows that the heat of mixing associated with the mixing of ideal gases is zero. No heat is
absorbed or released for the mixing of ideal gases. The process is driven entirely by entropy.
As we shall see later, a similar result holds for the mixing of dilute solutions. Finally, note that
there is no volume change for mixing ideal gases (see Eq. (14) and take a pressure derivative). In
a binary mixture, what composition has the most negative free energy of mixing?

15.4.2. Determination of Free Energies of Formation

There are a number of ways in which to measure the standard free energies of for-
mation of a compound. Consider the formation of ammonia,

1 3
N 2 (g) + H 2 (g) ←→ NH 3 (g),
2 2
at STP. The free energy change for the reaction is ∆G 0f (NH 3 , g). If we measure the equilibrium
constant,

P NH 3
= e−∆G f (NH 3 ,g)/RT ,
0

1/2 3/2
P N2 P H2

then we can easily compute the free energy of formation of ammonia.

15.4.3. Determination of the Extent of a Reaction

Reconsider the reaction

N 2 O4 (g) ←→ 2NO2 (g).

The extent of the reaction is easily measured by measuring the apparent deviation from the ideal
gas law. As before, let α be the fraction of N 2 O4 dissociated. If there were N 0 moles of N 2 O4
initially, then there are (1 − α )N 0 and 2α N 0 moles of N 2 O4 and NO2 at equilibrium, respec-
tively. The corresponding partial pressures can be computed from Dalton’s law.
When the result is used in the equilibrium constant condition we find that

P 2NO2 4α 2 N 0 RT 4α 2 P
KP = = = ,
P N 2 O4 1 − α V 1 −α2

where P is the total pressure on the system. This can be solved for the fraction dissociated, with
the result that
1/2
 KP 
α =
 K P + 4P 

Thus, if we calculate the equilibrium constant from a table of free energies, the degree of dissoci-
ation is easily found. Note that the result depends on both T and P.

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15.5. Coupled Reactions

In some cases, the direct formation of a certain compound by direct reaction is ther-
modynamically forbidden. An example is the formation of titanium tetrachloride from common
TiO2 ore; i.e.,

TiO2 (s) + 2Cl 2 → TiCl 4 (l) + O2 (g).

It turns out that ∆G = +152. 3kJ/mole. Nonetheless, we can make the reaction go by coupling it
to one which pulls it along. For example, suppose we use the produced oxygen to burn carbon;
i.e.,

C(s, graphite) + O2 (g) → CO2 (g),

where here ∆G = −394. 36kJ/mole. The free energy change for the coupled processes is -394.36
+ 152.3 = -242.1 kJ/mole, and thus the coupled reaction can proceed. The burning carbon sup-
plies the needed free energy to make the desired reaction work.

15.6. Temperature Dependence of K p

The equilibrium constant, K p , is only a function of the temperature. From its defini-
tion, cf. Eq. (33b),

d ln(K P ) d(∆G/RT )
=−
dT dT

1  d(∆G) 
=− T − ∆G
RT 2  dT 

T ∆S + ∆G
=
RT 2

∆H
= , (39)
RT 2
where the second to last equality follows when Eqs. (27a) and (33b) are used. Thus,

 K p (T 2 ) 
T
∆H
2

ln  =∫
 K p (T 1 )  T 1 RT
2
dT (40)

∆H  1 1
≈ − . (41)
R  T1 T2 

Equation (41) follows if we assume that ∆H is approximately constant. Note that as in our

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discussion of LeChatellier’s principle, the equilibrium will shift to the product side when the
temperature is raised if ∆H > 0

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16. Eigenvalues and Thermodynamic Stability

When considering thermodynamic stability for an isolated system, we had to show
that

1  ∂2 E   ∂ E 
2
1  ∂2 E 
∆E (2) ≡ ∆S 2
+ ∆S∆V + ∆E 2 + ... (1)
2  ∂S 2 V ,N i  ∂S∂V  N i 2  ∂V 2  S,N i

was positive, where terms involving changes of N i have been dropped. Moreover, by using the
expressions for the derivatives of the internal energy, Eq. (1) can be rewritten as:

T  ∂T  1  ∂P 
∆E (2) ≡ ∆S 2 + ∆S∆V − ∆V 2 + ..., (2)
2CV  ∂V  S,N i 2  ∂V  S,N i

or in matrix notation:

 T  ∂T  
† 
1  ∆S  CV  ∂V  S,N i   ∆S 
∆E (2) =   ⋅ ⋅
 ∆V 
. (3)
2 ∆V    ∂T   ∂P 
  ∂V  −
 ∂V  S,N i 
 S,N i 
The matrix in Eq. (3) is symmetric. From linear algebra, we know that symmetric matrix can be
diagonalized; i.e., a basis in the [∆S, ∆V ] space can be found where the matrix elements are zero
except for the diagonal ones which are equal to the eigenvalues (denoted as λ ± ). In this basis,
Eq. (3) becomes

1
∆E (2) = (λ + c 2+ + λ − c 2− ),
2
where c ± are the expansion coefficients of [∆S, ∆V ] in the special basis.
In order that the right hand side of Eq. (3) is greater than zero for all possible varia-
tions of the system, it is necessary that the eigenvalues, λ ± , be positive. The eigenvalues, λ ± , sat-
isfy the characteristic equation, i.e.,

T  ∂P   T  ∂P   ∂T 
2
0= λ 2± − λ ± − − −
 ∂V  S,N i  CV  ∂V  S,N i  ∂V  S,N i
. (4)
 CV 
This quadratic equation is easily solved. It thus follows that in order that the eigenvalues be pos-
itive,

CV > 0, (5)

 ∂P 
− > 0, (6)
 ∂V  S,N i

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and

 ∂T  T  ∂P 
2
<− . (7)
 ∂V  S,N i CV  ∂V  S,N i

The analysis for variations involving the number of moles of a given species follows in exactly
the same manner.

Winter Term 2001-2002

Entropy & Randomness -81- Chemistry CHEM 213W

17. Entropy of Mixing: A Statistical View

As was mentioned in class, it is possible to give a simple quantitative microscopic
derivation of the expression for the entropy of mixing for an ideal solution. To begin, consider
the following simple lattice model for a solution:

1 1 8 1 1 8 1 8
1 2 4 3 8 1 8 4
1 2 8 1 8 8 8 2
1 8 7 5 2 7 3 8
1 6 2 7 4 4 8 2
8 3 8 1 8 8 1 8
Fig. 1
The volume occupied by the solution has been divided into M equivalent cells, and each is ran-
domly occupied by a single molecule of a given type in the solution. Let N i be the number of
molecules of the i’th species (the "solvent" counts as a species).
How many states are available for the solution in this model? Specifically, how
many ways can the molecules occupy the cells? Consider species 1: The first molecule can
choose M cells, the second M-1, etc.. Finally, the last species 1 molecule can choose M-N1-1
different cells to occupy. Thus the number of ways of assigning the species 1 molecules to the
cells is

M!
M(M − 1)...(M − N 1 − 1) ≡ , (1)
(M − N 1 )!

where N ! = N (N − 1)(N − 2)...1 is called the factorial function.

The other species must still be added to the lattice. Consider species 2. Now there
are only M − N 1 cells to choose from; by repeating the preceding argument, it is easy to show
that the number of ways of adding species 2 is

(M − N 1 )!
. (2)
(M − N 1 − N 2 )!

The total number of ways of adding both species 1 and species 2 to the lattice is the product of
the ways of adding each; i.e.,

M!
. (3)
(M − N 1 − N 2 )!

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Entropy & Randomness -82- Chemistry CHEM 213W

Finally, we can repeat the argument until the entire lattice is filled. The total number of ways of
adding the molecules to the solution is

M!. (4)

Does each of these ways correspond to a state of the system? The answer is no, not
because we have made an error in our calculation, but because we have ignored a basic property
of nature; namely, the Heisenberg Uncertainty Principle. Equation (4) would be correct if we
could distinguish the different molecules of each species. The uncertainty principle makes this
impossible, and thus each state of the system cannot depend on which of the equivalent mole-
cules are in the specific cells -- it is impossible to tell.
Thus Eq. (4) overcounts the number of different states available to the system. By
how much? Again consider species 1. After the N 1 cells are chosen one still has the freedom to
permute species 1 molecules between the different chosen cells; there are N 1 ! ways of permuting
the species 1 molecules, and these permutations are included in Eq. (2). However, as we have
just argued, quantum mechanics makes these permutations irrelevant to the calculation of the
number of inequivalent states available to the system, and hence, Eq. (2) should be divided by the
number of ways of rearranging the equivalent molecules on the same set of lattice cells. By
repeating this argument for all species, it follows that the number of inequivalent states of the
solution are:

M!
. (5)
N 1 !N 2 !...

The calculation of the entropy of mixing now follows by using the statistical (Boltz-
mann) expression for the entropy:

S = k B ln(number of states), (6)

where k B is Boltzmann’s constant (k B = R/N A = 1. 38 × 10−23 J K −1 ). By using Eq. (5) in Eq.

(6), we obtain

 
∆S mixing = k B ln(M!) − Σ ln(N i !). (7)
 i 
This still doesn’t look like the expression we obtained in class. Note, however, that the factorials
which appear in Eq. (7) are factorials of huge numbers (≈ 1023 ). There is an accurate approxi-
mation for the natural logarithm of a large factorial known as Sterling’s formula; it is:

ln(N !) ≈ N [ln(N ) − 1] (8)

(try it for N=50). If Eq. (8) is used in Eq. (7) and we remember that M = Σ N i , a little algebra
i
shows that

Winter Term 2001-2002

Entropy & Randomness -83- Chemistry CHEM 213W

 Ni 
S mixing = − k B Σ N i ln . (8)
i M

Since, x i , the mole fraction of species i is

Ni
,
M
Eq. (8) is equivalent to the expression we obtained by examining solutions that obey Raoult’s
Law. (Recall that the gas constant R = k B N A , where N A is Avogadro’s number).

Winter Term 2001-2002

Phase Equilibrium -84- Chemistry CHEM 213W

18. Phase Equilibrium

An important class of equilibria involves the different equilibria established between
different states of matter, e.g., solids, liquids, and gases. As we shall now show, such equilibria
are governed by very simple principles, essentially the same as those we worked out for chemical
equilibria.

N1 N2

Figure 1

Consider a system containing an arbitrary number of non-reacting components

placed in a constant pressure and temperature container (the space enclosed by the heavy lines in
the figure). When equilibrium is attained, each part of the system will have a certain number of
moles in each part. For example, if we divide the system up according to the dashed lines the
figure, there will be N 1 moles of one component in the first part, N 2 in the second, etc.
Since the entire system is at constant T , P, and number of moles of each component,
the Gibbs free energy, G, must be at a minimum at equilibrium. If so, consider what would hap-
pen if we changed the number of moles in the first two compartments by letting N 1 → N 1 + dN
and N 2 → N 2 − dN . Clearly, we have not changed the total number of moles. However,

dG = ( µ Compartment 1 − µ Compartment 2 )dN (1)

which will be nonzero (and hence G cannot be a minimum) unless

µ Compartment 1 = µ Compartment 2 , (2)

or, since the division into compartments was completely arbitrary, unless the chemical potential
of each component is the same in each part of the system. Note, that this is just a special exam-
ple of our criterion for chemical equilibrium for the trivial "chemical" reaction:

N Compartment 1 →
← N Compartment 2 . (3)

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Phase Equilibrium -85- Chemistry CHEM 213W

Since, our preceding discussion only depended on the ability to have matter
exchanged between different parts of the system (but not on transfers to and from the surround-
ings), it will also hold for systems in which phase separation has occured, for example if there
was a liquid-vapor interface in our system, or if there was a precipitate at the bottom of the con-
tainer. Would it hold if there was a semipermiable membrane separating different parts of our
container?
In order to study some of the general consequences of these equilibrium conditions,
consider a system containing C components that have phase separated into P phases. Applying
Eq. (2) to each component we see that

µ1
(1)
= µ1
(2)
= ⋅ = (P)
µ1
⋅ ⋅ ⋅ ⋅ ⋅ ⋅ ⋅
⋅ ⋅ ⋅ ⋅ ⋅ ⋅ ⋅ (4)
⋅ ⋅ ⋅ ⋅ ⋅ ⋅ ⋅
µC
(1)
= µC
(2)
= ⋅ = (P)
µC ,
( j)
where µ i is the chemical potential of component i in phase j. It is easy to see that there are
(P − 1)C conditions. Each chemical potential depends on T and P (the same throughout the sys-
tem, WHY?) and on the composition of the phase in question (e.g., as we saw for dilute gases).
Since, we aren’t currently interested in extensive properties, we can characterize the composition
of each phase by the mole fractions, x i , of which there are C − 1 independent ones in each phase,
or P(C − 1) in total. Thus, including temperature and pressure, there are a total of P(C − 1) + 2
unknowns to be determined by the (P − 1)C equations given in (4), and in general the system of
equations will be either over- or under-determined. The extent to which this happens is obtained
by looking at the number of degrees of freedom, f , the difference between the number of
unknowns and equations; i.e.,

f = P(C − 1) + 2 − C(P − 1) = 2 + C − P. (5)

This simple result is known as the Gibbs Phase Rule.

As an example, suppose we have a one component system (C=1). According to Eq.
(5), if there is only a single phase, f = 2; i.e., we can pick T and P arbitrarily. If there are two
phases in equilibrium, then f = 1; i.e., we can pick at most eitherT or P, but not both. Finally, f
vanishes if there are three phases in equilibrium, which implies that we can’t pick anything at the
so-called triple point. For pure water, the triple point occurs at 0.01C and 611 Pa. Finally, note
that while our simple counting arguments rule out over-determined solutions, they don’t always
guarantee the existence of solutions, e.g., as is found above the critical temperature in one-com-
ponent systems.
We next turn to a more quantitative analysis of the equilibrium between phases.
Suppose we have a one component system containing two phases (for concreteness, a liquid and
its vapor). According to Eq. (5) we can pick one intensive quantity, e.g., the temperature, T , and
the pressure at coexistence will be determined. How does the coexistence pressure change if we
change the temperature? Since,

µ liquid = µ vapor (6)

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Phase Equilibrium -86- Chemistry CHEM 213W

both before and after the change in temperature,

d µ liquid = d µ vapor . (7)

However, since for a one component system, µ = G/N ,

d µ i = −S i dT + V i dP, (8)

where S i and V i are the molar entropy and volume, respectively in phase i. By substituting Eq.
(8) into (7) and rearranging the result, it follows that

 dP  S − S2 ∆S ∆H
= 1 = = , (9)
 dT Coexistence V 1 − V 2 ∆V T ∆V

where the last equality follows by noting that ∆H = T ∆S at equilibrium. Of course holds for any
two-phase, one-component equilibrium, and is known as the Clapeyron equation. For the liquid-
vapor equilibrium example, ∆H is just the heat of vaporization. What is it for solid-liquid equi-
libria?
There are several approximations that follow from Eq. (9). For example, if we can
ignore the temperature dependences of ∆H and ∆V , then we can integrate both sides of (9) and
obtain

∆H ∆H∆T
P2 − P1 ≈ ln(T 2 /T 1 ) ≈ , (10)
∆V T 1 ∆V

where the last approximation follows if ∆T /T 1 is small. This is a reasonable approximation for
cases where both phases are solids and/or liquids (and hence, their molar volumes don’t change
much with temperature).
Another approximation is obtained if one of the phases is a dilute gas and the other a
solid or liquid, then

RT
∆V = VVapor − V 2 ≈ VVapor ≈ , (10)
P
which allows us to rewrite Eq. (9) as

 d ln(P)  ∆H
= , (11)
 dT Coexistence RT 2

which is known as the Clausius-Clapeyron equation. Compare this with the expression we
obtained for the temperature dependence of the equilibrium constant, K P . They are the same,
perhaps as expected since, we can view the process as a chemical reaction, e.g.,

liquid→
←vapor,

for which the equilibrium would be determined from P(T ) = K p .

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Phase Equilibrium -87- Chemistry CHEM 213W

Finally, With the further assumption that that ∆H is independent of temperature, we

can integrate the Clausius-Clapeyron equation and show that the equilibrium vapor pressure of a
liquid or solid obeys (approximately)

 ∆H  1 1 
P(T ) = P(T 0 ) exp  −
 T 0 T 
, (12)
 R 
again consistent with the chemical equilibrium point of view. How would you use this result to
determine the normal boiling point of the material?

Winter Term 2001-2002

Azeotropes -88- Chemistry CHEM 213W

19. Minimum and Maximum Boiling Azeotropes: The Gibbs-Konovalov Theorem

As we discussed in class, a system where the temperature-composition phase dia-
gram has a minimum or maximum for some composition is called an azeotrope. Here we will
show that the composition of the vapor and liquid phases of azeotropes must be the same. This
result is called the Gibbs-Konovalov theorem, and is an sophisticated exercise in Maxwell rela-
tions, equilibrium conditions, and partial molar quantities.
For what follow, we will call the two components 1 and 2. Quantities pertaining to
the two phases will be distinguished by having a prime in the case of the vapor. Finally, the mole
fraction of 1 in the liquid and vapor phases are x 1 and y 1 , respectively.
The phase rule tells us that a two-phase, binary mixture has F = 2 + 2 − 2 = 2
degrees of freedom. One will be taken to be the pressure, which is held fixed. The other will be
some convenient concentration variable. In general, the chemical potentials in either phase can
be viewed as functions of T,P, and a mole fraction (e.g., x 1 or y 1 ). Hence, for arbitrary changes
of state:

 ∂µi   ∂µi   ∂µi 

d µi = dT + dP + dx . (1)
 ∂T  P,x 1  ∂P T ,x 1  ∂x 1  P,T 1

The first two partial derivatives may be rewritten by using Maxwell relations obtained from the
Gibbs free energy (recall, dG = −SdT + VdP + Σ µ i dN i ). Thus,

 ∂µi 
d µ i = −S i dT + V i dP + dx , (2)
 ∂x 1  P,T 1

where

 ∂S 
Si ≡ ,
 ∂N i T ,P,N j≠i

and

 ∂V 
Vi ≡
 ∂N i T ,P,N j≠i

are the partial molar entropies and volumes, respectively.

Equation (2) must hold for either component in either phase (in the vapor phase, just
add primes to all quantities and change x 1 to y 1 ). Moreover, for changes in state along the coex-
istence curve,

d µ i = d µ ′i i = 1, 2. (3)

If we use Eq. (2) in (3), two equations relating changes in T, P, x 1 and y 1 are obtained. In addi-
tion, for the case at hand dP = 0, and thus, we find that

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Azeotropes -89- Chemistry CHEM 213W

 ∂µi   ∂µ′ 
′
−(S i − S i )dT + dx 1 =  i  dy 1, i = 1, 2. (4)
 ∂x 1 T ,P
 ∂y 1 T ,P

Next, we divide through by dx 1 , multiply the equation for component 1 by x 1 , the equation for
component 2 by x 2 and add the results. This gives

′ ′  ∂T   ∂µ1   ∂µ2 
−[x 1 (S 1 − S 1 ) + x 2 (S 2 − S 2 )] + x1 + x2
 ∂x 1  P,coex  ∂x 1 T ,P  ∂x 1 T ,P

  ′  ∂ µ ′   ∂y
 ∂µ1 1
= x1  + x2  
2
.
  ∂y 1   ∂y  ∂x 
1 T ,P 1 P,coex
 T ,P 

(5)

The changes in the chemical potentials at constant T and P are not independent, but
are related through the Gibbs-Duhem equations,

x1 d µ 1 + x2 d µ 2 = 0 (6a)

and

y 1 d µ ′1 + y 2 d µ ′2 = 0. (6b)

Dividing Eqs. (6a) and (6b) by dx 1 and dy 2 , respectively, and using the results in Eq. (5) shows
that

∂T   ∂ µ ′   ∂y  x y 
′ ′  1
−[x 1 (S 1 − S1) + x 2 (S 2 − S 2 )] =  1  x1 − 2 1  (7)
 ∂x 1  P,coex
 ∂y 1 T ,P  ∂x 1 coex  y2 

 ∂ µ ′   ∂y (x 1 − y 1 )
1
=  1 , (8)
 ∂y 1 T ,P ∂x 1 coex
 y2

where the last equality is obtained by noting that the sum of the mole fractions in either phase is
unity.
The left hand side of the equation vanishes at a minimum or maximum of the T-X
phase diagram; hence, one of the factors on the right hand side must be zero. Thermodynamic
stability requirements (i.e., G is a minimum) can be used to show that

Winter Term 2001-2002

Azeotropes -90- Chemistry CHEM 213W

 ∂ µ 1′ 
> 0.
 ∂x 1 T ,P

It is also easy to show, using the definitions of the mole fractions and the fact that the total num-
ber of moles of each type is constant, that

 ∂y 1 
≠ 0.
 ∂x 1 coex

Hence, at an azeotropic point, x 1 = y 1 ; i.e., the compositions of the liquid and vapor phases are
the same. This is called the Gibbs-Konovalov theorem. Note that the derivation did not require
any specific properties of liquids or gases and our result will hold for any two-phase coexistence
in binary mixtures.
Finally, note that essentially the same manipulations can be used to show that

 ∂µ′ 
 ∂y 1 

1
  (x 1 − y 1 )
 ∂P   ∂y 1 T ,P ∂x 1 coex
= .
 ∂x 1 T ,coex y 2 [x 1 (V 1 − V 1′ ) + x 2 (V 2 − V 2′ )]

Hence, the P-X phase diagram will also have a minimum or maximum at the azeotropic compo-
sition.

Winter Term 2001-2002

Eutectics -91- Chemistry CHEM 213W

20. Ideal Eutectic Phase Diagrams

The ideal lead-antimony eutectic phase diagram is shown in the figure, and was cal-
culated assuming that the solids are completely immiscible and that the solution was ideal. The
liquid-solid coexistence lines are computed from the equilibrium conditions:

µ i (solid, T ) = µ i (liquid, T ) + RT ln(x i ), i = A, B.

(0) (0)
(1)
(0)
or using the fact that ∆G fus (i) ≡ µ (0)
i (liquid, T ) − µ i (solid, T ) = 0 at the normal melting point,
(0)

T = T MP
(i)
, of material i, we can rewrite Eq. (1) as

T ∆H fus ∆H fus
(i) (i)
 1 1
ln(x i ) = ∫T (i)
MP RT 2
≈
R
 (i) − ,
 T MP T 
(2)

where the last approximation follows by assuming the the heat of fusion is independent of tem-
perature.
The point where the two curves cross is called the Eutectic point. The question is
what happens below the eutectic temperature? From the point of view of the phase rule, or the
equilibrium conditions given in Eqs. (1) or (2), we could still have L+A, L+B, or A+B (i.e., a
mixture of the solid phases). Indeed, it is the last possibility which happens; WHY?
In order to answer this question, we must go back a few steps and remember that
under constant T,P,N conditions, the equilibrium state is the one with the lowest Gibbs free
energy; specifically if there are multiple local minima in G, it is the one that is lowest that should
be observed at equilibrium. This is what happens below the eutectic temperature. To see this,
consider the total free energy for the system (again for ideal solutions and immiscible solids):

A µ A (solid, T ) + n B µ B (solid, T )
G = n(s) (0) (s) (0)

A [ µ A (liquid, T ) + RT ln(x A )] + n B [ µ B (liquid, T ) + RT ln(x B )]

+ n(l) (0) (l) (0)
(3a)

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Eutectics -92- Chemistry CHEM 213W

A (solid, T ) + N B µ B (solid, T )
= N A µ (0) (0)

(0) (0)
A [∆G fus ( A, T ) + RT ln(x A )] + n B [∆G fus (B, T ) + RT ln(x B )],
+ n(l) (l)
(3b)

where n(s) (l)

i , n i , and N i are the number of moles of i in the solid, liquid, and total, respectively.
Remembering that the total number of moles of each material remains constant, the equilibrium
states must be local minima of G, and these are found by taking derivatives of Eq. (3b) with
respect to n(l) (l)
A or n b and setting the result to zero. It is straightforward to show that this results
in Eq. (1).
As was discussed above, when deciding between different possibilities, it is neces-
sary to go back to Eq. (3) and find the local minimum with the lowest free energy. For our exam-
ple, consider the following two possibilities L+A or A+B. The latter obeys the liquid-solid equi-
librium condition for A, cf. Eq. (1) and hence, from Eq. (3b) we see that the states have free ener-
gies:

G A+B = N A µ (0)
A (solid, T ) + N B µ B (solid, T )
(0)
(4a)

and
(0)
A (solid, T ) + N B µ B (solid, T ) + N B [∆G fus (B, T ) + RT ln(x B )],
G L+ A = N A µ (0) (0)
(4b)

where we have set n(l) A = n B = 0 for the A+B state and n B = N B for the L+A state. Thus, L+A
(l) (l)

state will be the equilibrium one as long as

(0)
∆G fus (B, T )
+ ln(x B ) < 0 (5)
RT
or, approximately, as long as

∆H fus  1 1
ln(x B ) <  (B) − , (6)
R  T MP T 

which, cf. Eq. (2), breaks down below the L+B coexistence line. Thus, since all points on the
L+A coexistence line are below the L+B coexistence line below the eutectic temperature, there
the L+A state has a higher free energy than A+B state. Clearly, there is nothing special about the
notation for A, and hence, exactly the same conclusion can be drawn for B. Thus we see that the
solid mixture is the minimum free energy solution below the eutectic temperature. Finally, while
we have used ideal solutions in this example, you can show that the same argument still holds for
a nonideal solution* .

*
To do this consider how Eqs. (1) and (3b) would have to be modified for the nonideal
case, and what are the signs of the various terms in different parts of the phase diagram.

Winter Term 2001-2002

Capillary Rise -93- Chemistry CHEM 213W

21. Capillary Rise and Depression

Consider a two phase system with a flat interface as shown in Fig. 1.

z
Phase I

Phase II

FIG. 1
Since the two phases are in equilibrium in the presence of a gravity field, the pressure varies with
height, z; namely,

p1 (z) = p1 (0) − ρ 1 gz (1)

in phase 1, and

p2 (z) = p2 (0) − ρ 2 gz (2)

in phase 2, where ρ 1(2) is the density in phase 1(2). Of course, at the interface (here assumed
flat) the pressures must be equal and

p1 (0) = p2 (0) ≡ p0 . (3)

Now put a capillary tube into the system as shown in Fig. 2.

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Capillary Rise -94- Chemistry CHEM 213W

Phase I

h
Phase II θ

FIG. 2
The surface tension, γ , between phase 1 and phase 2 wants the pressures between the two phases
to be unequal at the curved interface (why?). Specifically, for the convex surface shown in Fig.
2, we know that

2γ
p2 (−h) − p1 (−h) = . (4)
R

The only way in which the pressure difference can be achieved is by moving the
curved interface to a new position in the fluid. (Changing the pressure in the gas or liquid from
that of the surrounding material at the same height would cause material to flow from the high to
low pressure regions until the pressures were equal at all points at the same height). Thus, by
using our expressions for the pressure dependence in the phases at any given heights [Eqs. (1),
(2), and (3)] in Eq. (4) we find that

2γ
p0 + ρ 2 gh − ( p0 + ρ 1 gh) = (5)
R
or

2γ 2γ
h= ≈ for ρ 2 >> ρ 1 , (6)
Rg( ρ 2 − ρ 1 ) Rg ρ 2

where the approximate expression is useful for liquid-vapor interfaces. (If the interface is con-
cave then the pressures in Eq. (4) must be switched and the sign of h changes.)
Finally, if we write R, the radius of curvature of the interface, in terms of d, the
radius of the tube and the contact angle θ , it follows that

2γ cos(θ )
h=−
dg( ρ 2 − ρ 1 )

For a 45o contact angle in a capillary tube with a 1mm radius containing water
(γ = 72. 75dynes/cm the capillary rise will be 1. 05cm

Winter Term 2001-2002

Capillary Rise -95- Chemistry CHEM 213W

22. Problem Sets

22.1. Problem Set 1

DUE: Wednesday, January 17, 2001

1. a) If

1  ∂V 
α ≡ ,
V  ∂T  P,N

show that

1  ∂ρ 
α =− ,
ρ  ∂T  P,N

where ρ is the mass density.

b) More generally, show that

dρ
= −α dT + κ dP,
ρ

where

1  ∂V 
κ ≡−
V  ∂P T ,N

is the isothermal compressibility. Note: Do not use the ideal gas equation in proving a) and b).
2. At 25C a sealed, rigid container is completely filled with liquid water. If the temperature is
raised by 10C, what pressure will develop in the container? For water, α = 2. 07 × 10−4 /K and
κ = 4. 50 × 10−5 /atm.
3. Castellan, problem 3.3 (Read Secs. 3.7 and 3.8 first).
4. Castellan, problem 4.2.
5. Castellan, problem 4.5.
6. A simple model for gas reactions on a surface can be obtained as follows: Assume that every
molecule that collides with the surface will react with probability P(v x ) where

0 if |v x | < v 0
P(v x ) ≡ 
1 otherwise,
where v x is the velocity normal to the surface. Use the kinetic theory of gases to derive a molecu-
lar expression for the rate of reaction (i.e., the number of reactions per unit time per unit area).

Winter Term 2001-2002

Problem Set 1 -96- Chemistry CHEM 213W

7. Compute the number of collisions an Argon atom has per second at 1 atm pressure and 25C.
o
Assume that the argon atom has a 3A diameter. What is the mean free path under these condi-
tions?

Winter Term 2001-2002

Problem Set 2 -97- Chemistry CHEM 213W

22.2. Problem Set 2

DUE: Friday, January 26, 2001
1. How much work will be produced in the isothermal, reversible expansion from V 1 to V 2 of a
gas with the equation of state:

(bRT − a)
pV = RT +
V

2. (Barrow, Problem 5-1) The acceleration due to gravity on the earth’s surface is about 9.8
m sec −2 .
a) What is the force of gravity on a 1-kg mass?
b) How much mechanical energy could be obtained by fully harnessing the downward
movement of a 1-kg mass through a distance of 58 m (the height of Niagara Falls)?
c) How much thermal energy would be produced if the mass were allowed to fall freely
through this distance?
d) If the mass consisted of water and all the thermal energy were absorbed by the
water, How much would the temperature of the water rise?
3. a) Consider a process where the heat absorbed by the system per mole is given by:

3a  RT a 
d− Q ≡ − dT − + dV
4T 3/2V  V − b 2T 1/2V 2 

Evaluate the heat absorbed by the system along the following paths:
i) T 1V 1 → T 2V 1 → T 2V 2
ii) T 1V 1 → T 1V 2 → T 2V 2
b) Show that 1/T is an integrating factor for d− Q (i.e., d− Q/T becomes the differential
of a state function) by evaluating the integral of d− Q/T along paths i) and ii).
4. An average man (mass = 70 kg, specific heat - same as water) produces about 104 kJ of heat
each day through metabolic activity.
i) If he were a closed system, what would his temperature rise be in one
day?
ii) He is, of course, really an open system--losing heat through evaporation
of water. How much water must he evaporate per day to maintain his
constant temperature of 37o C? You must first calculate ∆H vap at 37o .
iii) The heat of combustion of cane sugar is 3.95 kcal/g. How many grams
of sugar will furnish energy for one day’s metabolism, assuming the
transfer of heat from cane sugar bonds to metabolic heat to be perfectly
efficient?

Winter Term 2001-2002

Problem Set 2 -98- Chemistry CHEM 213W

5. In the thermite reaction:

2 Al (s) + Fe2 03(s) → 2Fe(l) + Al 2 03 (s),

what is the maximum temperature attainable by the products? Assume that the reactants are at 1
atm pressure and 25C, and that all heat capacities are constant over the required temperature
ranges. You will need to go to tables of thermodynamic constants; a good place to look is the
CRC handbook. Is the assumption that Al 2 03 is solid in writing the reaction reasonable?
6. Consider the following two isomers of C 3 H 6 :
CH 2

H2C CH CH
3
CH 2
CH
2
Cyclopropane Propene

a) Calculate ∆H for the interconversion of cyclopropane and propene using a table of

standard heats of formation.
b) Calculate ∆H for this reaction using a table of bond energies.
c) Which answer is more reliable? Why? What are the sources of error?
d) Which compound would yield more heat upon complete combustion in oxygen?

Winter Term 2001-2002

Problem Set 3 -99- Chemistry CHEM 213W

22.3. Problem Set 3

DUE: Wednesday, February 13, 2002
This material is based on the First Law.
1. Castellan, Problem 7.28.
2. Castellan, Problem 7.30.
3. Castellan, Problem 7.31.
4. Castellan, Problem 7.41.
5. Castellan, Problem 7.46.
6. A chemistry 213 student was overheard arguing with a friend in management about why we
have winter heating. The latter stated that it was to make the air in the room warmer, while the
chemistry 213 student claimed that it was to increase the energy content of the air in the room.
Which is right? Why?
This next material covers aspects of the second law.
7. Castellan, Problem 8.4.
8. Castellan, Problem 8.9.
9. Castellan, Problem 8.17.
10. Castellan, Problem 9.3.
11. Castellan, Problem 9.7.
12. Consider a system comprised of two 1000g blocks of copper (c p = 0. 1 cal/g/o K). If one
block is at 300K and the other is at 400K, what is the maximum amount of work that can be
extracted from the system if no additional heat is allowed to flow into or out of the system. What
will the final temperature be after the work is extracted? Describe a process whereby you could
extract the maximum work. In working out this problem, ignore any PV work associated with
the expansion of the blocks.

Winter Term 2001-2002

Problem Set 4 -100- Chemistry CHEM 213W

22.4. Problem Set 4

Due: Friday, February 22, 2002
1. Castellan, Problem 9.1.
2. Castellan, Problem 9.10.
3. Castellan, Problem 9.18.
4. Castellan, Problem 9.26.
5. Castellan, Problem 10.7-10.9.
6. Castellan, Problem 10.23
7. Castellan, Problem 10.28

Winter Term 2001-2002

Problem Set 5 -101- Chemistry CHEM 213W

22.5. Problem Set 5

Due: Monday, March 4, 2002
1. Castellan, Problem 11.4 (you might also try 11.7, which is similar).
2. Castellan, Problem 11.8
3. Castellan, Problem 11.10
4. Castellan, Problem 11.32
5. Castellan, Problem 11.35
6. Castellan, Problem 11.40
7. Castellan, Problem 11.43

Winter Term 2001-2002

Problem Set 6 -102- Chemistry CHEM 213W

22.6. Problem Set 6

Due: Wednesday, March 21, 2001.
1. Castellan, Problem 11.38
2. Castellan, Problem 12.1
3. Castellan, Problem 12.7
4. Castellan, Problem 12.10
5. Castellan, Problem 12.15
6. Castellan, Problem 12.17

Winter Term 2001-2002

Problem Set 7 -103- Chemistry CHEM 213W

22.7. Problem Set 7

Due: Wednesday, March 28, 2001.
1. Castellan, Problem 13.1
2. Castellan, Problem 13.5
3. Castellan, Problem 13.9
4. Castellan, Problem 13.11
5. Castellan, Problem 13.20
6. Castellan, Problem 13.21

Winter Term 2001-2002

Problem Set 8 -104- Chemistry CHEM 213W

22.8. Problem Set 8

Due: Wednesday, April 4, 2001
1. Castellan, Problem 14.1
2. Castellan, Problem 14.5
3. Castellan, Problem 14.10
4. Castellan, Problem 14.17
5. Castellan, Problem 14.20
6. Castellan, problem 15.3.

Winter Term 2001-2002

Problem Set 9 -105- Chemistry CHEM 213W

22.9. Problem Set 9

Due: Wednesday, April 11, 2000.
1. Complete and balance the following reactions:

ClO−3 + As2 S 3 → Cl − + H 2 AsO−4 + SO=4 (acidic solution)

and

Cu(NH 3 )4++ + S 2 O=4 → SO=3 + Cu + NH 3 (basic solution).

In each case, identify the oxidized and reduced species and compute the standard state cell poten-
tial.
2. Consider the cell

Pt(s)|H 2 (g, 1 atm), H + (aq, 1M)||Fe3+ (aq), Fe2+ (aq)|Pt(s),

given that ∆ε o = 0. 771V for

Fe3+ + e− → Fe2+ .

a) If the measured potential of the cell is 0.712 V, what is the ratio of concentrations of
Fe2+ to Fe3+ ?
b) What is the ratio if the potential of the cell was 0.830V?
c) Plot the fraction of total iron present as Fe3+ over the voltage range 0.65 V to 0.9 V.
3. Castellan, problem 17.4.
4. Castellan, problem 17.11.
5. Castellan, problem 17.16.

Winter Term 2001-2002

Problem Set 10 -106- Chemistry CHEM 213W

22.10. Problem Set 10

Due: Wednesday, April 12, 2000.

1. Castellan, problem 15.3.

2. Complete and balance the following reactions:

ClO−3 + As2 S 3 → Cl − + H 2 AsO−4 + SO=4 (acidic solution)

and

Cu(NH 3 )4++ + S 2 O=4 → SO=3 + Cu + NH 3 (basic solution).

In each case, identify the oxidized and reduced species and compute the standard state cell poten-
tial.
3. Consider the cell

Pt(s)|H 2 (g, 1 atm), H + (aq, 1M)||Fe3+ (aq), Fe2+ (aq)|Pt(s),

given that ∆ε o = 0. 771V for

Fe3+ + e− → Fe2+ .

a) If the measured potential of the cell is 0.712 V, what is the ratio of concentrations of
Fe2+ to Fe3+ ?
b) What is the ratio if the potential of the cell was 0.830V?
c) Plot the fraction of total iron present as Fe3+ over the voltage range 0.65 V to 0.9 V.
4. Castellan, problem 17.4.
5. Castellan, problem 17.11.
6. Castellan, problem 17.16.

Winter Term 2001-2002

Past Exams -107- Chemistry CHEM 213W

23. Past Exams

23.1. Quiz I: 1999

23.1.1. INSTRUCTIONS

1. No books or notes are permitted.

2. Calculators are permitted.
3. Answer all questions and show all work clearly.
4. There are 4 questions and each is of equal value.
5. Be sure to indicate the total number of exam books handed in on book 1.
6. You may need the following data:

Useful Constants
Constant Value

Gas Constant, R 8.31442 J K −1 mole−1

Boltzmann’s Constant, k B 1. 381 × 10−23 J/K
Faraday, F 96,484.6 Coul/mole
Standard Atmosphere 1. 01325 × 105 Pa
Avogadro’s Number 6. 0225 × 1023
1 cal 4.184 J

7. You may need the following results from calculus:

∞ 1
∫0 xe−ax /2 dx =
2
,
a

B B
dx dx 1 1
∫
A
x
= ln(B/ A), ∫
A
x 2
= − ,
A B

and

ln(1 + x) ≈ x for |x| << 1.

8. Good Luck.

February 3, 1999
Quiz I -108- Chemistry CHEM 213W

(1. 25% From the Homework) A simple model for gas reactions on a surface can be obtained as
follows: Assume that every molecule that collides with the surface will react with probability
P(v x ) where

0 if |v x | < v 0
P(v x ) ≡ 
1 otherwise,
where v x is the velocity normal to the surface. Use the kinetic theory of gases to derive a molecu-
lar expression for the rate of reaction (i.e., the number of reactions per unit time per unit area).
(2. 25%) Give expressions for the following (derivations are not required, but be sure to define
your symbols):
a) The mean speed of a gas molecule.
b) The mean free path.
c) The number of collisions per second a gas molecule makes.
d) The first law of thermodynamics.
e) The enthalpy.
(3. 25%) Compute the heat of reaction for

→
1500K ,1atm
C(graphite) + O2 (g) CO2 (g).

Is the reaction exothermic or endothermic? You will need the following data:

Cp
Compound
(J K mol −1 )
−1

C(graphite) 8.53
O2 (g) 29.35
CO2 (g) 37.11

You also need ∆H of (CO2 , g) = −393. 51kJ/mol.

(4. 25%) One mole of an ideal gas expands isothermally at temperature T from volume V 1 to vol-
ume V 2 .
a) Calculate the amount of work done if the expansion is performed against a constant
pressure P 0 .
b) Calculate the amount of work done if the expansion is done reversibly.
c) What is the energy change in a) and b)? (Remember that the gas is ideal).
d) Calculate the amount of heat absorbed by the system in parts a) and b).

February 3, 2000
Quiz I -109- Chemistry CHEM 213W

23.2. Quiz I: Chemistry CHEM 213W

23.2.1. INSTRUCTIONS

1. No books or notes are permitted.

2. Calculators are permitted.
3. Answer all questions and show all work clearly.
4. There are 5 questions and each is of equal value.
5. Be sure to indicate the total number of exam books handed in on book 1.
6. You may need the following data:

Useful Constants
Constant Value

Gas Constant, R 8.31442 J K −1 mole−1

Boltzmann’s Constant, k B 1. 381 × 10−23 J/K
Faraday, F 96,484.6 Coul/mole
Standard Atmosphere 1. 01325 × 105 Pa
Avogadro’s Number 6. 0225 × 1023
1 cal 4.184 J

7. You may need the following results from calculus:

∞ 1
∫0 xe−ax /2 dx =
2
,
a

B B
dx dx 1 1
∫
A
x
= ln(B/ A), ∫
A
x 2
= − ,
A B

and

ln(1 + x) ≈ x for |x| << 1.

8. Good Luck.

February 3, 2000
Quiz I -110- Chemistry CHEM 213W

(1. 20% From the Homework) A simple model for gas reactions on a surface can be obtained as
follows: Assume that every molecule that collides with the surface will react with probability
P(v x ) where

0 if |v x | < v 0
P(v x ) ≡ 
1 otherwise,
where v x is the velocity normal to the surface. Use the kinetic theory of gases to derive a molecu-
lar expression for the rate of reaction (i.e., the number of reactions per unit time per unit area).
(2. 20%) The reaction

HCl(g) + NH 3 (g) → NH 4 Cl(s)

is carried out by placing 2 cotton balls, one dipped in concentrated HCl and the other in concen-
trated HN 4 OH, at opposite ends of a 1m long piece of glass tubing. Given the molecular weights
in the table, and other things being equal, where will the NH 4 Cl precipitate first appears (as mea-
sured from the from the HCl cotton ball)? What assumptions are you making?

Molecular Weights
Molecular Weight
Compound
(g/mol)
HCl 36.46
NH 3 17.03
NH 4 Cl 53.49
Air* 28.85
*
This is the average molecular weight in air (approximately 79%
N 2 , 21% O2 ).

(3. 20%) Derive an expression for the diffusion flux caused by a concentration gradient in a
dilute gas.
(4. 20%, From the Homework) How much work will be produced in the isothermal, reversible
expansion from V 1 to V 2 of a gas with the equation of state:

(bRT − a)
pV = RT +
V
(5. 20%, Castellan, 7.43) At 25C, the following enthalpies of formation are given:

Compound SO2 (g) H 2 O(l)

∆H of (kJ/mol) -296.81 -285.83

For the reactions at 25C:

2H 2 S(g) + Fe(s) → FeS 2 (s) + 2H 2 (g), ∆H rxn

o
= −137. 0kJ/mol,

February 3, 2000
Quiz I -111- Chemistry CHEM 213W

and

3
H 2 S(g) + O2 (g) → H 2 O(l) + SO2 (g), ∆H rxn
o
= −562. 0kJ/mol.
2
Calculate the heats of formation of H 2 S(g) and FeS 2 (s).

February 6, 2001
Quiz I -112- Chemistry CHEM 213W

23.3. Quiz I: Chemistry CHEM 213W

23.3.1. INSTRUCTIONS

1. No books or notes are permitted.

2. Calculators are permitted.
3. Answer all questions and show all work clearly.
4. There are 5 questions and each is of equal value.
5. Be sure to indicate the total number of exam books handed in on book 1.
6. You may need the following data:

Useful Constants
Constant Value

Gas Constant, R 8.31442 J K −1 mole−1

Boltzmann’s Constant, k B 1. 381 × 10−23 J/K
Faraday, F 96,484.6 Coul/mole
Standard Atmosphere 1. 01325 × 105 Pa
Avogadro’s Number 6. 0225 × 1023
1 cal 4.184 J

7. You may need the following results from calculus:

∞ 1
∫0 xe−ax /2 dx =
2
,
a

B B
dx dx 1 1
∫
A
x
= ln(B/ A), ∫
A
x 2
= − ,
A B

and

ln(1 + x) ≈ x for |x| << 1.

8. Good Luck.

February 6, 2001
Quiz I -113- Chemistry CHEM 213W

(1. 20%) Show that

  ∂E   ∂V 
C P − CV =  P +
 ∂V T ,N  ∂T  P,N
. (1)
 
What does the right hand side of Eq. (1) become for an ideal gas?
(2. 20%)
a) Describe the Joule-Thompson expansion; in particular, show what thermodynamic
quantity is constant during the expansion.
b) Define the Joule-Thompson coefficient, µ JT , and show that

1  ∂H 
µ JT = − . (2)
C P  ∂P T ,N

(3. 20%) (Castellan, 7.64) Calculate the final temperature of the system if 20g of ice at -5C is
added to 100g of water at 21C in a Dewar flask (an insulated flask); for the transformation

H 2 O(s) → H 2 O(l), ∆H o = 6009J/mol,

at 0C, C P (H 2 O, s) = 37. 7J/(K mol), and C P (H 2 O, l) = 75. 3J/(K mol) .

(4. 20%)
a) Write down the expression for the Maxwell-Boltzmann velocity distribution for one
of the components of velocity (e.g., v x ) in a gas at temperature T comprised of mol-
ecules of mass m.
b) Use your result to derive the distribution of molecular speeds.
c) How would your result in part c) change if you lived in Flatland (i.e., in a 2 dimen-
sional world)?
d) Derive expressions for the most probable speed in the real world and in Flatland.
(5. 20%) (Castellan, 30.4) Consider a gas at constant temperature. If the pressure is doubled,
what effect does this have on:
a) the number of collisions per second made by any one molecule;
b) the total number of collisions per second occurring in 1m 3 of gas;
c) the mean free path of a gas molecule;
d) the diffusion constant.

March 16, 1999

Quiz II -114- Chemistry CHEM 213W

23.4. Quiz II: 1999

23.4.1. INSTRUCTIONS

1. No books or notes are permitted.

2. Calculators are permitted.
3. Answer all questions and show all work clearly.
4. There are 5 questions and each is of equal value.
5. Be sure to indicate the total number of exam books handed in on book 1.
6. You may need the following data:

Useful Constants
Constant Value

Gas Constant, R 8.31442 J K −1 mole−1

Boltzmann’s Constant, k B 1. 381 × 10−23 J/K
Faraday, F 96,484.6 Coul/mole
Standard Atmosphere 1. 01325 × 105 Pa
Avogadro’s Number 6. 0225 × 1023
1 cal 4.184 J

7. You may need the following results from calculus:

∞ 1
∫0 xe−ax /2 dx =
2
,
a

B B
dx dx 1 1
∫
A
x
= ln(B/ A), ∫
A
x 2
= − ,
A B

and

ln(1 + x) ≈ x for |x| << 1.

8. Good Luck.

March 16, 1999

Quiz II -115- Chemistry CHEM 213W

1. (20%)
a) Use the second law of thermodynamics to obtain the formula for the maximum effi-
ciency of a Carnot engine (not necessarily using an ideal gas).
b) Prove that for any constant temperature process,

W ≤ −∆ A.

2. (20%) Fill in the required information in the following table (don’t do this on the exam sheet,
copy it to your exam book) giving the state functions etc., that govern equilibrium under the
stated conditions.

Constant State Function Differential Minimum or

Definition
Conditions Name Change Maximum at Equilibrium

E,V,N
S,V,N
T,V,N
T,P,N

3. (20%) Show that

a)

CP
dS = dT − V α dP (N constant)
T

b)

VT α 2
C P − CV = ,
κ

where α is the thermal expansion coefficient and κ is the compressibility.

4. (20%, Castellan, Problem 11.27) Consider the reaction

FeO(s) + CO(g)→
← Fe(s) + CO2 (g)

for which we have

T (o C) 600 1000
KP 0.900 0.396

a) Calculate ∆H o , ∆G o , and ∆S o at 600 o C.

March 16, 1999

Quiz II -116- Chemistry CHEM 213W

b) Calculate the mole fraction of CO2 in the gas phase at 600 o C.

5. (20%)
a) Derive the Gibbs phase rule. How does your result change if there are R chemical
reactions that can take place between the components in all phases and that come to
equilibrium.
b) Derive the Clapeyron equation (the equation giving the slope of the coexistence line
separating two phases in equilibrium with each other).

March 9, 2000
Quiz II -117- Chemistry CHEM 213W

23.5. Quiz II: 2000

23.5.1. INSTRUCTIONS

1. No books or notes are permitted.

2. Calculators are permitted.
3. Answer all questions and show all work clearly.
4. There are five (5) questions and each is of equal value.
5. Be sure to indicate the total number of exam books handed in on book 1.
6. You may need the following data:

Useful Constants
Constant Value

Gas Constant, R 8.31442 J K −1 mole−1

Boltzmann’s Constant, k B 1. 381 × 10−23 J/K
Faraday, F 96,484.6 Coul/mole
Standard Atmosphere 1. 01325 × 105 Pa
Avogadro’s Number 6. 0225 × 1023
1 cal 4.184 J

7. You may need the following results from calculus:

∞ 1
∫0 xe−ax /2 dx =
2
,
a

B B
dx dx 1 1
∫
A
x
= ln(B/ A), ∫
A
x 2
= − ,
A B

and

ln(1 + x) ≈ x for |x| << 1.

8. Good Luck.

March 9, 2000
Quiz II -118- Chemistry CHEM 213W

1. (20%) State and derive the Clausius inequality.

2. (20%)
a) (5%) State the third law of thermodynamics.
b) (5%) Show that the third law of thermodynamics implies that heat capacities must
vanish at T → 0.
c) (10%. Castellan, 9.24) In the limit T → 0 it is known empirically that the value of
the coefficient of thermal expansion of solids approaches zero. Show that, as a con-
sequence, the entropy is independent of pressure at 0K. What does this imply for
your answer in part a)?
3. (20%)
a) Show that

CP
dS = dT − V α dP, (for N constant),
T
where α is the thermal expansion coefficient. [NOTE: You don’t have to use the
derivation first presented in class].
b) (From the Homework, Castellan, 10.28). Use the result in a) to show that:

 ∂S  κ CV
i) = ,
 ∂P V ,N Tα

 ∂S  C
ii) = P ,
 ∂V  P,N TV α

and

1  ∂V  κ
iii) − = ,
V  ∂P  S,N γ

where γ ≡ C P /CV and where κ is the isothermal compressibility.

4. (20%. Castellan, 9.27) In an insulated flask (Dewar flask) 20g of ice at -5C are added to 30g
water at 25C. The heat of fusion, ∆H Fusion , is 334J/g and heat capacities are
C P (H 2 O, l) = 4. 18 J/(gK ) and C P (H 2 O, s) = 2. 09 J/(gK ). Pressure does not change.
a) What is the final state of the system?
b) Calculate ∆S and ∆H for the process.

March 9, 2000
Quiz II -119- Chemistry CHEM 213W

5. (20%)
a) (5%) Show that

Σi ν i µ i = 0
at chemical equilibrium. Under what conditions does this relation apply?
b) (15%. Castellan, 11.15) At 298.15K we have the following data:

∆G of ∆H of
Compound
(kJ/mol) (kJ/mol)
C 2 H 4 (g) 68.1 52.3
C 2 H 2 (g) 209.2 226.7

a) Calculate K P at 298.15K for the reaction:

→
C 2 H 4 (g) C 2 H 2 (g) + H 2 (g)
←

b) What must the value of K P be if 25% of the C 2 H 4 is dissociated into

C 2 H 2 and H 2 at a total pressure of 1atm?
c) At what temperature will K P have the value determined in b)?

March 12, 2001

Quiz II -120- Chemistry CHEM 213W

23.6. Quiz II: 2001

23.6.1. INSTRUCTIONS

1. No books or notes are permitted.

2. Calculators are permitted.
3. Answer all questions and show all work clearly.
4. There are five (5) questions and each is of equal value.
5. Be sure to indicate the total number of exam books handed in on book 1.
6. You may need the following data:

Useful Constants
Constant Value
Gas Constant, R 8.31442 J K −1 mol −1
Boltzmann’s Constant, k B 1. 381 × 10−23 J/K
Standard Atmosphere 1. 01325 × 105 Pa
Avogadro’s Number 6. 0225 × 1023
1 cal 4.184 J

7. You may need the following results from calculus:

∞ 1
∫0 xe−ax /2 dx =
2
, ln(1 + x) ≈ x for |x| << 1,
a

B dx B dx 1 1
∫A x
= ln(B/ A), and ∫A x 2
= − .
A B

8.

Themochemical Data at 298.15K and 1 atm.

∆H 0f ∆G 0f
Substance
kJ/mol kJ/mol
NH 3 (g) -45.94 -16.5

9. Good Luck.

March 12, 2001

Quiz II -121- Chemistry CHEM 213W

1. (20%)
a) State and prove the Clapyeron equation governing the slope of a coexistence line in
the P-T phase diagram.
b) Use your result in a) to derive the Clausius-Clapeyron equation. Clearly state what
approximations you are making and why they are valid.
c) Use your results in parts a) and b) to discuss the shape of the P-T phase diagram for
water.
d) Is the following phase diagram ever possible? If so, for what kind of system? Why
or why not?

11
00 α
11
00

2. (20%) For fixed N show that :

CV α
dS = dT + dV ,
T β

1  ∂V  1  ∂V 
where α ≡ and β ≡ −
V  ∂T  P,N V  ∂P T ,N
3. (20% From the Homework) Consider a system comprised of two 1000g blocks of copper
(c p = 0. 4184 J/g/o K). If one block is at 200K and the other is at 400K, what is the maximum
amount of work that can be extracted from the system if no additional heat is allowed to flow into
or out of the system. What will the final temperature be after the work is extracted? Describe a
process whereby you could extract the maximum work. In working out this problem, ignore any
PV work associated with the expansion of the blocks.
4. (20%) Prove LeChatellier’s principle.
5. (20%) A representative of Crimson Chemical Corporation (CCC) has just visited you and
encouraged you to invest in his company. The reason for his optimism is a new catalyst devel-
oped by CCC, which he maintains yields a minimum 80% conversion of hydrogen in the ammo-
nia synthesis reaction

N 2 (g) + 3H 2 (g) → 2NH 3 (g)

at 500o K and one atmosphere pressure when the reactants, N 2 and H 2 , are mixed in a 1:3 ratio.
By assuming that the gases are ideal, and using the data given in the table on the cover sheet,
evaluate the validity of his claim. Be sure to show your work.

March 12, 2001

Quiz II -122- Chemistry CHEM 213W

23.7. Final Exam: 1999

23.7.1. INSTRUCTIONS

1. No books or notes are permitted.

2. Calculators are permitted.
3. Answer all questions and show all work clearly.
4. There are 5 questions and each is of equal value.
5. Be sure to indicate the total number of exam books handed in on book 1.
6. You may need the following data:

Useful Constants
Constant Value

Gas Constant, R 8.31442 J K −1 mole−1

Boltzmann’s Constant, k B 1. 381 × 10−23 J/K
Faraday, F 96,484.6 Coul/mole
Standard Atmosphere 1. 01325 × 105 Pa
Avogadro’s Number 6. 0225 × 1023
1 cal 4.184 J

7. You may need the following results from calculus:

∞ 1
∫0 xe−ax /2 dx =
2
,
a

B B
dx dx 1 1
∫
A
x
= ln(B/ A), ∫
A
x 2
= − ,
A B

and

ln(1 + x) ≈ x for |x| << 1.

8. Good Luck.

April 20, 1999

Final Exam -123- Chemistry CHEM 213W

1. (From the Homework. 20%) Consider a system comprised of two 1000g blocks of copper
(c p = 0. 1 cal/g/o K). If one block is at 300K and the other is at 400K, what is the maximum amount of
work that can be extracted from the system if no additional heat is allowed to flow into or out of the sys-
tem. What will the final temperature be after the work is extracted? Describe a process whereby you
could extract the maximum work. In working out this problem, ignore any PV work associated with the
expansion of the blocks.
2. (From the Homework. Castellan-11.8 20%) At 500K we have the following data

∆H 500
o o
S 500
Substance
(kJ/mol) (J/K mol)
HI (g) 32.41 221.63
H 2 (g) 5.88 145.64
I 2 (g) 69.75 279.94

One mole of H 2 and one mole of I 2 are placed in a vessel at 500K. At this temperature only gases are
present and the equilibrium

H 2 (g) + I 2 (g)→
←2HI (g)

is established. Calculate K P and the mole fraction of HI present at 500K and 1atm. What would the
mole fraction of HI be at 500K and 10atm?
3. (From the Homework. Castellan-14.1. 20%) Benzene and toluene from nearly ideal solutions. At
o
283K, P toluene = 30 mmHg and P obenzene = 100 mmHg.
a) A liquid mixture is composed of 3 mol of toluene and 2 mol of benzene. If the pressure
over the liquid is reduced, at what pressure does the first vapor form?
b) What is the composition of the first trace of vapor?
c) If the pressure is reduced further, at what pressure does the last trace of liquid dissapear?
d) What is the composition of the last trace of liquid?
e) What will the pressure, the composition of the liquid, and the composition of the vapor be
when 1 mol of the mixture has been vaporized?
4. (20%)
a) Derive an expression for the freezing point depression of an ideal solution.
b) Derive the van’t Hoff equation for the osmotic pressure.
c) The Clausius-Clapeyron equation.
d) The Nernst equation.
In all parts, be sure to clearly state any assumptions or general principles you use.
5. (Castellan-12.8. 20%) Iodine boils at 183.0 C; the vapor pressure of the liquid at 116.5C is 100 Torr.
If ∆H ofus = 15. 65 kJ/mol and the vapor pressure of the solid is 1 Torr at 38.7C, calculate
a) The triple point temperature and pressure.

April 20, 1999

Final Exam -124- Chemistry CHEM 213W

b) ∆H vap
o
and ∆S vap
o
.
c) ∆G of (I 2 , g) at 298.15K.

April 28, 2000

Final Exam -125- Chemistry CHEM 213W

23.8. Final Exam: 2001

23.8.1. INSTRUCTIONS

1. No books or notes are permitted.

2. Calculators are permitted.
3. Answer all questions and show all work clearly.
4. There are five (5) questions and each is of equal value.
5. Be sure to indicate the total number of exam books handed in on book 1.
6. You may need the following data:

Useful Constants
Constant Value

Gas Constant, R 8.31442 J K −1 mole−1

Boltzmann’s Constant, k B 1. 381 × 10−23 J/K
Faraday, F 96,484.6 Coul/mole
Standard Atmosphere 1. 01325 × 105 Pa
Avogadro’s Number 6. 0225 × 1023
1 cal 4.184 J

7. You may need the following results from calculus:

∞ 1
∫0 xe−ax /2 dx =
2
,
a

B B
dx dx 1 1
∫
A
x
= ln(B/ A), ∫
A
x 2
= − ,
A B

x2
ln(1 + x) ≈ x − +. . . for |x| << 1,
2
and

x2
ex ≈ 1 + x + +. . . for |x| << 1.
2!

8. Good Luck.

April 28, 2000

Final Exam -126- Chemistry CHEM 213W

1. (20%) Derive or prove the following. Be sure to clearly state any approximations or assumptions you
make.
a) The Gibbs phase rule.
b) An expression for the temperature dependence of the cell potential (EMF); i.e., for
(∂∆ε /∂T ) P,N .
c) The lever rule.
d)

TV α 2
C p − CV = ,
β

where

1  ∂V  1  ∂V 
α ≡ and β ≡ −
V  ∂T  P,N V  ∂P T ,N

e) The expression for the boiling point elevation of an ideal solution containing a single
volatile component.
2. (20%, Castellan, 13.16) The melting point of iodine is 113.6 o C and the heat of fusion is 15.64kJ/mol.
a) What is the ideal solubility of iodine at 25 o C?
b) How many grams of iodine dissolve in 100g of hexane at 25 o C? [The molecular weights of
I 2 and hexane are 253.81 and 86.18 g/mol, respectively].
3. (20%, Castellan, 14.14) The Henry’s law constant for argon in water is 2. 17 × 104 at 0 o C and
3. 97 × 104 at 30 o C. Calculate the standard heat of solution of Argon in water. What assumptions are
you making?
4. (20%)
a) Derive the equation(s) governing the coexistence lines in the ideal eutectic phase diagram
and describe how to use your result to construct the phase diagram.
b) Sketch the phase diagram, clearly indicating where the eutectic point is.
c) Choose a composition either to the right or left of the eutectic point, and describe what hap-
pens as you cool a liquid with that composition. Discuss at least four different temperatures
(high, at the coexistence line, intermediate and low) and be sure to indicate (at least approxi-
mately) the compositions and amounts of the phases you have present.
d) Briefly repeat your analysis in part c) for a liquid whose mean composition is the eutectic
composition.
5. (20%, Castellan, 17.9) The standard potentials at 25 o C are:

Pd 2+ (aq) + 2e− → Pd(s) ε o = 0. 83V

and

April 28, 2000

Final Exam -127- Chemistry CHEM 213W

PdCl 42− (aq) + 2e− → Pd(s) + 4Cl − (aq) ε o = 0. 64V .

a) Calculate the equilibrium constant for the reaction

Pd 2+ + 4Cl − → 2−
← PdCl 4 .

b) Calculate ∆G o for the reaction.

Wednesday, April 18, 2001

Final Exam -128- 180-213B

23.9. Final Exam: 2001

23.9.1. INSTRUCTIONS

1. No books or notes are permitted. Calculators are permitted.

2. Answer all questions in the answer book and show all work clearly. The exam has
of two (2) pages including this one and five (5) questions, each is of equal value.
3. Be sure to indicate the total number of exam books handed in on book 1.
4. You may need the following data:

Useful Constants
Constant Value

Gas Constant, R 8.31442 J K −1 mol −1

Boltzmann’s Constant, k B 1. 381 × 10−23 J/K
Faraday, F 96,484.6 Coul/mol
Standard Atmosphere 1. 01325 × 105 Pa
Avogadro’s Number 6. 0225 × 1023
1 cal 4.184 J

5. You may keep the exam.

6. Good Luck.
7. You may need the following results from calculus:

∞ 1
∫0 xe−ax /2 dx =
2
,
a

B dx B dx 1 1
∫A x
= ln(B/ A), ∫A x 2
= − ,
A B
and

x2
ln(1 + x) ≈ x − +. . . for |x| << 1,
2

Wednesday, April 18, 2001

Final Exam -129- 180-213B

1. (20%) Derive or prove the following. Be sure to clearly state any approximations or assump-
tions you make.
a) The Nernst Equation.
b) The expression for the saturation solubility (mole fraction solute) in an ideal solu-
tion.
c) The expression for the temperature dependence of the equilibrium constant K P (T ).
d) The maximum work you can get out of a constant temperature process.
2. (20%, Castellan, 11.16) At 25o C, for the reaction

Br 2 (g)→
←2Br(g)

we have ∆G o = 161. 67 kJ/mol and ∆H o = 192. 81 kJ/mol.

a) Compute the mole fraction of bromine atoms present at equilibrium at 25o C and
P = 1atm.
b) At what temperature will the system contain 10 mole percent bromine atoms in equi-
librium with bromine vapor at a total pressure of 1 atm?
3. (20%, Castellan, 12.20) For the phase transition

S rhombic → S monoclinic ,

the value of ∆S is positive. The transition temperature increases with the increase in pressure.
Which is denser, the rhombic or monoclinic form? Prove your answer mathematically.
4. (20%, Castellan, 14.2) Two liquids, A and B, form an ideal solution. At the specified tempera-
ture, the vapor pressure of pure A is 200 mmHg while that of B is is 75 mmHg. If the vapor over
the mixture consists of 50 mole percent A, what is the mole percent A in the liquid?
5. (20%, Castellan, 17.19) H.S. Harned and W.J. Hamer [J. Amer. Chem. Soc. 57, 33 (1935)]
present values for the potential of the cell,

Pb(s)|PbSO4 (s)|H 2 SO4 (aq, a)|PbSO4 (s)|PbO2 (s)|Pt(s),

over a wide range of temperature and concentration of H 2 SO4 . In 1M H 2 SO4 , they found,
between 0o C and 60o C,

∆ε = 1. 91737 + 5. 61 × 10−5 t + 1. 08 × 10−6 t 2 ,

where t is the temperature in Celsius. What are ∆G, ∆H and ∆S for the cell reaction at 0o C and
25o C?