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Classical thermodynamics deals with the flow of energy under conditions of equilibrium or

near-equilibrium and with the associated properties of the equilibrium states of matter. It is a

macroscopic theory, ignoring completely the details of atomic and molecular structure, though not

the existence of atoms and molecules to the extent required for writing chemical reactions. Time

is not recognized as a variable and cannot appear in thermodynamic equations. For students who

have become familiar with atoms and molecules, it may be surprising to find how far one can go

toward treating chemical and physical equilibria without employing any simplified models or

delving into theories of molecular structure.

The detachment of thermodynamics from molecular theory is an important asset. The

fundamental principles of thermodynamics were developed during the 19 th century on the

foundation of two principal axioms, supplemented by a small number of definitions, long before

atomic structure was understood. Because of this lack of dependence of theory on models, even

today we need not worry about our vast ignorance at the molecular level, especially in the areas of

liquids and ionic solutions, in applying thermodynamics to real systems. It has been said, with

some justification, that if you can prove something by thermodynamics you need not do the

experiment. Such a strong statement must be handled with care, but it should become clear in the

following pages that common practice is quite consistent with this assumption.

Two developments associated primarily with the 20 th century introduced substantial new

insights into thermodynamics. Statistical thermodynamics, or statistical physics, originated with

the efforts of Maxwell and of Boltzmann in the late 19 th century and grew with additions by

Gibbs, Planck, Einstein, and many others into a companion science to thermodynamics. Because

statistical thermodynamics relies on specific models of atomic and molecular structure and

interactions, it provides important tests of those models, at the expense of substantially greater

mathematical complexity than classical thermodynamics. More important for present purposes,

statistical mechanics provides much greater insight into the quantities that appear in

thermodynamic equations, and thus a clearer view of why things happen. Thus we will not

hesitate to introduce some basic principles of statistical mechanics (without the extensive

mathematics) when necessary to explain what is going on.

The other new development, largely responsible for the change in physics from what is

generally considered purely Newtonian to relativistic and quantum physics, arose from the

introduction of operational definitions at the end of the 19 th century. This viewpoint requires that

any definition (of energy, position, or time, for example) must include a statement of how we can

measure the quantity. Application of this criterion demands clarification of some quantities that

were introduced casually, without a solid foundation, in the early days of thermodynamics. We

will try to be more careful in explaining what is meant by our symbols, and what can or cannot be

measured, than has been customary in thermodynamic textbooks.

One of the characteristics of thermodynamics is that most of the terms are familiar. Everyone

has heard of energy, of heat, and of work. The difficulty is that we must sharpen our definitions

to distinguish between loosely associated ideas. We will therefore be particularly careful to define

these familiar quantities carefully, often emphasizing what our technical meanings do not include

as much as specifying the intended meanings.

7/10/07 Intro- 1

One of the guidelines of early thermodynamics was that all energy transfers (under

equilibrium conditions) can be classified as either heat transfer of energy because of

temperature differences (thermo) or as work transfer of energy because of forces and

motions (dynamics). It seems appropriate, therefore, to begin with definitions of energy, heat,

and work.

ENERGY. Energy has been a difficult quantity to define because it has so many faces, or forms in

which it may appear. Initially, energy was defined to be the energy of motion, or kinetic energy,

which for most objects under usual conditions is half the mass times the square of the speed,

E = mv2 (1)

The most convenient, and generally reliable, definition of energy is that it is kinetic energy or

any of the other forms of energy which can be changed into kinetic energy or obtained from

kinetic energy. These other forms of energy include rotational energy (a spinning ball or

weathervane), vibrational energy (a mass oscillating up and down on a spring), and potential

energy (a skier at the top of a slope), as well as energy within an object, called internal energy.

HEAT. Most of the internal energy is associated with the nuclei or with the chemical state of the

object. We will generally ignore the nuclear energy. For any given sample of matter, the nuclear

energy typically remains unchanged. Changes of chemical energy will be considered when there

are chemical reactions. For now, we are more concerned with the relatively small portion of the

internal energy that changes when the temperature changes; it is most often called heat, or more

narrowly defined as thermal energy.

The meaning of the thermodynamic term heat can best be explored by consideration of a

few qualitative or semiquantitative experiments. For each of these we will develop a working

hypothesis, select a crucial test, and revise the hypothesis as necessary.

Our understanding of heat is based upon common experiences. When we stand before a fire,

or when we place a pan of water over a gas fire or in contact with an electrically heated coil, our

senses and the change in character of the water tell us that something passes from the fire or hot

coil to nearby objects (specifically to us or to the pan of water). The effect is to heat the

objects, by which we mean that there is a sensation of warmth that can be verified by a

thermometer. The thermometer, in some way, measures this heat. We seek to find the

relationship between temperature, heating, and heat.

Temperature balance? As an initial hypothesis, assume that a thermometer measures the

amount of heat. If so, we should find that a loss of temperature by one body is compensated by a

gain of temperature by another. To test this we put 200 g of hot water, at 90 oC, into each of two

Dewar flasks1 (Figure 1). To the first flask we add 50 g of water initially at 20o C, and stir until

1

These are also called vacuum flasks, because the space between the silvered double walls

has been evacuated, a design developed by Sir James Dewar. Another common name for these

and for containers of different design but for the same purpose is Thermos bottle, which is the

trade name of the American Thermos Products Co.

7/10/07 Intro- 2

the temperature becomes steady. The new temperature is found

to be about 76.0oC. To the second flask we add 25 g of water, at

20oC, and find the final temperature to be about 82.2o C. We must

ask now whether the experiment shows the initial hypothesis to be

fully satisfactory or not.

There has indeed been a loss of temperature by the water in

the flask and a gain in temperature by the water added. But there

is clearly no temperature balance. The water in the flasks

changed temperature only slightly, whereas the water added

increased in temperature several times as much. Also, the water

in the second flask dropped in temperature less than that in the

first flask, but the water added to the second flask increased in

temperature more than that added to the first flask. Examination

of the results (Table 1) shows that the drop in temperature of the

water originally in the flasks is roughly doubled when twice as

much cool water is added.

The experiment just described suggests how the original

hypothesis might be revised. It appears that a larger amount of

water can absorb more heat for a given temperature increase. The

temperature, therefore, is more nearly a concentration of heat.

From this revised hypothesis we predict that the temperature

change times the amount of the substance should be the same for both the added and the original

water (see Table 1).

Table 1 Temperature Measurements*

Sample Tfinal Ts Tw -Tw/Ts -TwMw/TsMs

H2O,50g 76.0 56.0 -14.0 0.25 1.0

H2O,25g 82.2 66.2 -7.8 0.125 1.0

Al, 50g 86.35 66.35 -3.65 0.0050 0.22

Al, 25g 88.12 68.12 -1.88 0.0276 0.22

Tw is the temperature change of the water originally in the flask.

Initial temperature of the water is 90oC and of the sample, 20o C.

Ms is the mass of the sample added and Mw the mass of water in the flask.

It is necessary to find out whether the same relationship will hold if we exchange heat

between two different substances. To do this we again prepare two flasks, each containing 200 g

of water at 90oC, then add to one a block of aluminum, at 20o C, with a mass of 50 g and to the

second a block of aluminum, at 20oC, with a mass of 25 g (Figure 2). After a few seconds we

may assume that the temperatures of the aluminum blocks are equal to the temperatures of the

surrounding water about 86.35oC for the larger block and 88.12oC for the smaller block.

7/10/07 Intro- 3

Multiplying temperature change by mass and comparing the result for the aluminum block and the

water shows that the ratio is the same for both parts of the experiment with aluminum, but

appreciably different from the results of the earlier experiment. We conclude, therefore, that

aluminum and water have a different heat capacity, so that a given amount of heat added to a

certain mass of one produced a different temperature change than equal heat added to the same

mass of the other.

the heat capacity depends upon the volume or the mass of the

substance that is absorbing the heat. The choice can be easily made by

means of an experiment employing a substance, such as air, that can

readily change volume without changing mass. We fill one flask with

air, evacuate a second identical flask, and immerse both in water, with

a connection provided between the flasks, as shown in Figure 3. The

temperature of the water is measured; then the stopcock is opened,

allowing the air to expand to twice its initial volume, and the

temperature is remeasured. The temperature is found to be

unchanged. From this we conclude that the temperature of the air did

not change with the change in volume, and therefore that it is better to

define the heat capacity in terms of mass rather than of volume.

(The result is confirmed by more sensitive tests.)

Is heat gained or lost? In each of the measurements described

thus far it has been possible to follow heat as it flows from one body to

another; the amount lost by one substance has been equal to the

amount gained by the other. It is necessary to determine whether this is always true. (If it is, we

would say that heat is conserved, or that the amount of heat is constant.) Taking a hint from

the famous observations of Count Rumford, who noted the great quantities of heat evolved during

the boring of cannons, we design our next experiment to include mechanical motion, in which

energy will be added from motion (i.e., by doing work). Instead of expanding the air from one

flask into an evacuated flask, we can let it expand against a piston, as shown in Figure 4. This

time the temperature of

the gas drops (about

50oC) during the

expansion, even though

we add insulation

around the cylinder to

prevent the flow of

heat outward from the

gas. The change of

temperature cannot be

solely because of the

volume change; the

7/10/07 Intro- 4

previous experiment showed that the change of volume did not cause any change of

from 25oC to about - 25oC.

temperature. The fact that the gas pushes on the piston, causing it to move, must be the

important difference.

A few additional experiments will provide more information on the relationship between

expansion, with work being done, and temperature effects on gases. (For brevity, only the results

of these experiments will be discussed.) Compression of a gas causes an increase in the

temperature just equal to the decrease of temperature during expansion, if both expansion and

compression processes are slow. It is therefore possible, by repeated expansion and compression,

to cycle the temperature between two values. Any other property of the gas that we might

measure, such as density, volume, or viscosity, will be found to depend only on the temperature as

measured by a thermometer, and not on how that temperature was achieved (for any specified

pressure). In other words, the heating effect of a compression seems to be exactly the same as

the heating effect of a flame or other source of heat. Thus it is possible to compress a gas,

thereby raising its temperature; then extract heat from it by removing the insulation until the gas

has returned to room temperature; expand it into an evacuated space without change of

temperature; compress it to again increase its temperature; extract heat; and so forth, as many

times as we wish.

Clearly, heat is not a quantity that retains its identity after it is absorbed by a substance, for

we can add any amount of heat without changing the properties of a gas in any way (provided

only that the proper amount of work is done by the gas). There is no property that will enable us

to determine the amount of heat added to any substance, or the amount of heat removed. The

description of temperature as the concentration of heat is therefore untenable, and must be

abandoned.

If not heat, then what? Temperature is related to a concentration of something more

fundamental, which can give rise to heat or can cause a gas to do work and which is increased

when the substance absorbs heat or when work is done on the substance. This quantity so

directly related to temperature is called energy.

In classical physics, any measurement of energy is necessarily an energy difference. We often

7/10/07 Intro- 5

write E for energy, where we mean E, the difference between the current energy value and some

implied reference level of energy. There are several meanings for energy. Total energy includes

information on where the sample is located and how it is moving. Measure-ments made on a

sample at rest with respect to our apparatus would measure the internal energy. A small portion

of that internal energy is the thermal energy, which is a collection of several different forms of

energy, or modes of storage of energy, in matter, that can be changed by a change of temperature.

It will be sufficient to let E represent total energy, keeping in mind that the changes we are

primarily concerned with will be changes of internal energy and, most often, changes of thermal

energy.

Transfer of heat. Furthermore, in thermodynamics we are primarily concerned with the

transfer of energy to or from a system, including the transfer of thermal energy. This quantity is

nearly always represented by the symbol Q. Thus Q represents a change of energy of the system; 2

Q = E (2)

To ensure that all the energy transfer occurs as transfer of thermal energy, only, we sharpen

the definition of Q:

Q (thermal energy transfer) is the transfer of energy between two objects in

physical contact as a consequence of a difference in temperature between the

objects.

The importance of this refinement will become apparent later.

WORK. We distinguish work from play; we say that machinery works or doesnt work;

and we read that if a force acts on a body and the body moves through some distance, work is

done on the body. But in thermodynamics, work has a special meaning.

First of all, work is a transfer of energy from one object to another by the action of a force. If

work is done on an object, that increases the energy of the object. 3 Thus, if the only energy

transfer is as work,

W = E (3)

Second, and equally important, all investigations thus far of transfer of energy as work

2

Be particularly careful to distinguish between Q, which is an amount of thermal energy

transferred, and the change in a property, such as thermal energy or E. To write Q displays a

confusion to all who may read your notes.

3

Be aware that older thermodynamic literature quite generally defined work with opposite

sign. Because of an emphasis on steam engines, W was taken to be work done by an object,

rather than work done on an object. Some textbooks have chosen both definitions, changing from

one chapter to another. Again, the amount of energy transferred is W, not W.

7/10/07 Intro- 6

indicate that the amount of work done is equal to a product 4 of the force exerted (on the object)

times the displacement of the point of application of the force.

If more than one force is acting, each force must be multiplied by the distance through which

it acts. Then the work terms may be added.

W = Wi

i =

i

f i dx i (4)

What is the imposter equation? The expression for work done is often abbreviated to work is

equal to force times distance, but this is often interpreted to mean a net force times the distance

traveled by the object. Is this imposter equation ever wrong?

Imposter equation ? Ifnetds =

W=

i ds

f i (5)

Yes, if it is interpreted as giving the work done. We give here just two examples. First, if

you jump, you move upward because the floor exerts a force on you (which is the reaction force

to the force you exert on the floor). You move, and momentum p = (mv) is transferred between

you and the floor, but the force exerted on you times the distance you move (while in contact

with the floor) cannot be equal to work done on you because the floor does not transfer any

energy to you. The point of application of the force is at the floor, and that point doesnt move.

Second, if you drag a box across the floor, it is easy to find the force you exert on the cord

and the distance the cord moves, so work done by you on the cord is known. Similarly, the force

exerted by the cord on the box can be measured, as well as the distance the box moves, so work

done by the cord on the box is known. (Energy transferred, as work, to the cord is equal to

energy transferred, as work, by the cord to the box) But the forces of friction between the box

and the floor are molecular-level forces, not known in detail. And the distances over which these

molecular-level forces act, individually, cannot be known. A simple force times distance

calculation gives an answer, but it is demonstrably wrong! 5

Analogues. Fortunately, we can usually avoid ambiguities in the definition of work in our

4

The product of force and distance is an integral of a scalar product, or dot product.

That will be automatically taken care of in most of our applications. In mechanics, we often

measure work done on a particle (or, better, a physical particle), which can change only its

kinetic energy. For such a particle it is easily shown that work is Ifds. We are concerned here

with more general bodies, subject to rotation and deformation, for which the definition of work

must be more explicit.

5

The imposter equation, (p)2 /2m = Ifnetds, where p = mv, has been called the second-

law equation, SLI. It is a valid statement of Newtons second law, net force is equal to mass

times acceleration, but except for special circumstances it has no connection to W.

7/10/07 Intro- 7

analysis of equilibrium thermodynamics. We must, however, be sensitive to the differences

between what is transferred and what is stored.

The description of energy transfers as heat (thermal energy transfer) and as work may be

compared with deposits and withdrawals from a savings bank. The deposit slip may ask for a

separate listing of bills and coins, and a withdrawal may be in the form of bills or coins. Yet the

account balance itself is neither bills nor coins. In the same manner, energy may be put into a

substance, or withdrawn from it, either as Q, a thermal energy transfer (heat) or as W, work,

but it exists within the substance only as energy not as Q or W. (Remember that money may

also be deposited by check or electronic transfer. We must be alert to the possibility of

transferring energy by means other than Q and W.)

If we are being very casual, it may be sufficient to describe thermal energy and thermal

energy transfers as heat, without additional labels. That, however, is very much like an

accountant choosing a single label (perhaps money) to indicate income and net worth, or trying

to balance your check book without distinguishing between net deposits for the month and

balance at the end of the month. Learning to distinguish between thermal energy and Q, the

transfer of thermal energy, will go a long way toward helping you understand discussions of

thermodynamics.

By going beyond thermodynamics, into statistical mechanics, the internal energy can be

described in terms of thermal energy and other forms of energy (such as chemical), and the

thermal energy may be further broken down into kinetic energy and potential energy of individual

atoms and molecules. But for purposes of thermodynamics we need know nothing more about

energy than that it includes a component related to the temperature. This component, called

thermal energy, can be internally converted to increase or decrease the temperature without

changing the internal energy. (If a mixture of oxygen and hydrogen is ignited, the gases become

substantially hotter, without any transfer of energy to or from the surroundings.) Or the thermal

energy can be transferred to or from the surroundings either as thermal energy transfers or as

work. We can find by experiments, such as the compression-cooling experiment or a variety of

others performed by Joule, how much thermal energy transfer is equivalent to how much work

and, for a given substance, how much energy (by either transfer method) must be put in for a

given temperature rise. The relationships between temperature, energy, thermal energy transfer,

and work will be considered quantitatively in the discussion of the first law of thermodynamics.

7/10/07 Intro- 8

1 The First Law of Thermodynamics

Thermodynamics is based on a small number of postulates, or assumptions. These are called

the laws of thermodynamics because they are suggested by a great amount of accumulated

experimental evidence. In fact it is extremely important to keep in mind that thermodynamics is

important just because there is total agreement between the results of thermodynamics (properly

applied) and all careful experimental results available to us. Because it is not possible to prove

the fundamental assumptions of thermodynamics, both the postulates and the derived results of

thermodynamics have often been challenged. In every showdown thus far, thermodynamics has

been shown to be correct.

Energy

The first step in understanding thermodynamics, and making it serve your purposes, is to

learn how to evaluate changes in energy in any object. As you probably recognize already, that

means understanding how to evaluate Q and W, the transfer of thermal energy to (or from) the

object and the work done on (or by) the object. To do so, we will write what is known as the

first law equation, which directly relates Q and W to the change of energy. But before we can

move ahead, we must look at how we define the object or quantity that is to give up or receive

energy; we must consider what is meant by a property; and we must examine the meaning of a

conservation law.

System and Surroundings. When we consider a ball projected through the air, or a block

sliding down a plane, it is quite satisfactory to talk about the ball, or the block, or simply the

object. If we wish to consider a gas or a solution, object is no longer a very appropriate

description, but we could still refer to the gas or the solution or simply call it it. A better

method is to call whatever is of primary interest (ball, or block, or gas, or solution, or whatever)

the system. One advantage is that we neednt change descriptions when we substitute one gas for

another, or a solution for a gas, and so forth. Another advantage is that it allows for a smooth

transition to problems in which we choose an open system, that is, where we allow material, as

well as energy, to pass back and forth, into or out of the system. Unless specifically indicated

otherwise, however, we will assume our systems to be closed.

Whatever else is around, we simply call the surroundings. Then, ideally, we need consider

only system and surroundings. To avoid difficulties that we might encounter in trying to describe

the far reaches of the universe, it is quite sufficient to limit the term surroundings to include all of

the universe that might be affected by whatever change, or process, we are considering.

It is important that we clearly define what we mean by our system. When we have done so,

the surroundings is usually adequately defined.

There will be times when you will find it more convenient to deal with the interactions of two

bodies, or two systems, with each other, ignoring anything outside those systems. That is

perfectly legal. Terminology such as system and surroundings is meant to be an aid, not a

liability. On the other hand, it has been shown many times that disdaining the definitions of

7/10/07 1- 9

system and surroundings provides sufficient ambiguity to allow erroneous conclusions to be

"proved". Also note that system and surroundings are essentially equivalent and arbitrary labels,

so we are free to interchange them if we wish.

Properties, or State Functions. Examine a block of copper and you will find that it has a

certain shape, a certain volume, a certain temperature, a certain density, and various other

properties that characterize the sample. Each of these may be changed, by changing the

temperature of the copper, or to some extent by changing the pressure exerted on the copper.

Neglecting the shape, which depends on the specific sample but not on the nature of the copper

itself, we call each of these measurable quantities a property of the copper. The state of the

copper, or state of the system, is defined by these properties, so they are often called state

functions.

A gas, such as a gram of oxygen, O2, is adequately described if we know the temperature, the

pressure, and the volume, but two of these are sufficient to determine the third, so only two state

functions are sufficient to define the state of the system. Other substances, such as iron or plastic,

may have additional properties (such as magnetic state or strain) that must be specified.

Conservation Laws. In mechanics we pay special attention to quantities that do not change

during a process we are studying. A free particle (not acted on by any net force) will have a

constant velocity no change in speed or in direction. Such a constant of the motion may be

said to be preserved under the special conditions of the process. In a frictionless system, energy

will be preserved, or unchanged. When a liquid is poured from one container to another, the

volume of the liquid is preserved. Unfortunately, it has become common practice to refer, in such

instances, to the unchanging quality as being conserved, although the term conservation has

quite a different, very important meaning.

Volume is something we can see and often measure with a meter stick, whether the sample is

a copper block or the gram of oxygen gas (in a rigid container). For many processes, the volume

of the system (the liquid) is "preserved", but we also are aware that the volume of such a system

can be changed. With a gas, we need only move a piston, or change the pressure or the

temperature. With the block of copper or a free liquid, a change of temperature will change the

volume.

What we cannot do is change the volume of our selected system without causing some

change elsewhere. If the volume of the system increases, then less volume is available outside the

system, so the volume of the surroundings must decrease, by the same amount. Thus we have the

seemingly trivial, but very important, conclusion that the volume of the system plus the volume of

the surroundings is constant. That, of course, is because of the assumed properties of local space.

We state this result as a conservation law. Volume is a conserved quantity. The volume of a

gas, or liquid, or a solid may be changed, but the volume of the system plus the volume of the

surroundings remains unchanged for all changes we make. Let V = V 2 - V 1 represent the change

in V, the volume. Then the law of conservation of volume would be written

The best-known of the three thermodynamic postulates is known as the first law of

7/10/07 1- 10

thermodynamics. It is just the principle of conservation of energy. It may be stated in the form:

First Law The energy of the universe is constant.

A better form for our purposes is to write

Remember that (Greek capital delta) indicates a change in the quantity that follows, in this

instance a change in the energy, E. Expressed in symbols,

Because we are primarily interested in changes within that part of the universe that we

choose to call the system, which generally is a small, fixed quantity of substance, a symbol such as

E (unless specifically labeled otherwise) will always refer to the system under discussion. When

the energy of the system increases, E is positive; when the energy of the system decreases, E is

negative. In any given problem, the system to be considered must be carefully defined. The

surroundings are then adequately defined by what is outside the system. It should be clear that

equation 2 is, indeed, a statement of a conservation law, equivalent to the previous statement of

the first law.

It is often convenient to think in terms of a system that is totally isolated from its

surroundings. Unfortunately, such arrangements are not possible. We may prevent energy from

moving to or from a system, or hold volume of the system constant, or keep the pressure on the

system (exerted by the surroundings) constant, or make other special provisions, but there is no

practical way to define a truly isolated system and, if we had one, we could not make

measurements on the system. We must therefore carefully specify in what sense we want our

system to be isolated. It may be isolated in the sense that no energy is transferred to or from the

system, or it may be isolated in a more narrow sense. If the system is insulated, there is no

thermal energy transfer, Q. If the volume of the system is being held constant, there can be no

transfer of energy as work of expansion or compression. To simply call the system isolated

leaves the question indeterminate as to what is being prevented or what is maintained constant.

Heat, Work, and the First-Law Equation. Thus far we have considered energy transfers, to

or from a system, only as Q or as W. These will suffice for the present. Then we can write the

total energy change for the system in the form

but this is awkward. It is better, and conventional, to introduce new symbols for the terms on

the right-hand side, as we have already indicated. We let Q be the amount of thermal energy

transferred to the system from the surroundings, and let W be the amount of work done on the

system. Then, allowing for both modes of energy transfer, at the same time,

7/10/07 1- 11

Note that this first-law equation, by itself, tells us nothing about whether the energy for the

entire universe changes or not.

Roughly, the division of energy transfers into heat (thermal energy transfer) and work

corresponds to a division into random motion and directed motion (or collective motion). At this

point we have no good criterion for deciding whether light, for example, should be called heat

or work, but for the present it is arbitrary. Later we will find that the second law of

thermodynamics deals with these distinctions.

Insofar as all energy transfers may be measured either as heat (thermal energy transfer) or as

work, or a sum of these, this equation accounts for all possible changes in the energy of the

system. This equation is called the first-law equation. If we combine this equation with the first

law (conservation of energy) we may conclude that Q system = - Q surroundings and that W system = -

Wsurroundings. It is necessary to add additional terms to the first-law equation when there are other

modes of energy transfer (including especially the transfer of matter to or from the system). A

few simple examples of energy changes, in the following sections, will show the meaning of the

terms in equation 4.

TEMPERATURE CHANGES AND HEAT CAPACITY, CV. Consider first the process of heating a gas

confined in a container of constant volume. Because there is no directed motion, no work is

done.

(V) E = Q (5)1

We are often concerned with very small (infinitesimal) changes in energy, which would imply

an infinitesimal value for Q. The temptation is to write dQ, 2 but that would be misunderstood.

Because Q = E, it follows that Q = (E) and dQ = d(E), which is not at all what we

intend. We therefore choose the notation

q = dE (5a)

intended to serve as a reminder that we want an infinitesimal amount of thermal energy transfer.

The amount of thermal energy absorbed by the system, Q, divided by the temperature rise is

the quantity commonly called heat capacity, C. C = Q/T. However, because C may itself vary

with temperature, it is better to take the limiting value of the ratio for small changes of

1

The notation (V) at the left of the equation indicates that the equation is valid when the

volume of the system is held constant. We are also assuming, for the present, that there is no

other form of work, such as electrical work.

2

Other choices are Q and Q, each of which is often misinterpreted, including confusing

the small magnitude with an inexact differential (i.e., change).

7/10/07 1- 12

temperature. This is just a derivative. 3

E Q q

CV = Lim = Lim = (6)

T 0 T T 0 T dT

It is common practice to represent a derivative, such as dE/dT, which is evaluated with some

variable (in this case V) held constant, by the special symbol

E

T V

These are called partial derivatives. Employing this notation we arrive at the usual form of

equation 6.

E

CV = (6a)

T V

Consider now the change in energy for 2 mol of H2 warmed at constant volume from 25 oC to

50 C.4 For a diatomic gas near room temperature, C V is constant and is about 5/2 R = 21

o

J/molK. The gas can do no work at constant volume so the total energy change is equal to the

thermal energy transfer (heat absorbed).

E

(V ) dE =

dE

dT = dT = CV dT (7 )

dT T V

The total energy change is obtained by integration.

(V ) (8)

T2

E = E2 E1 = dE

T1

= CV dT = CV (T2 T1 )

T2

T1

3

See Appendix.

4

For convenience, numbers specified for illustrative purposes, such as amounts of

material, temperatures, and pressures, will be treated as integers, known exactly. Also, for

present purposes we approximate CV for hydrogen as 5/2 R (see Table I), although the actual

value is somewhat less and increasing with temperature.

7/10/07 1- 13

temperature on the Celsius5 scale. Temperature differences are the same for the two scales. With

the appropriate numerical substitutions,

= 1.05 kJ/mol

This is the amount of (thermal) energy that must be added to the gas to raise its temperature

25oC.

IDEAL-GAS EXPANSIONS. Now let 2 mol of hydrogen, at 3 atm pressure, expand at a constant

temperature of 50oC through a pinhole (to maintain a slow expansion) and against a piston.

Assume the external pressure acting on the piston is 1 atm, as in Figure 1. The work done on the

gas is the product of the force exerted on the gas (by the piston) and the distance through which

the piston moves, with a negative sign because the pressure (of the gas) acts opposite to the

pressure acting on the gas. The force, on the gas, times the displacement, is f dx = - (PA) dx = -

P (Adx) = - P dV. Because of the unusual arrangement (effusion controlled), the pressure acting

on the gas at the point of displacement is the external pressure, P ext. Therefore the work done on

the gas is

5

This scale was formerly called centigrade in English-speaking countries, a name that

can be confused with 1/100 degree in other languages.

7/10/07 1- 14

The initial and final volumes can be calculated from the ideal-gas equation 6, PV = nRT.

V1 = 5

= 0.0530 m 3

1 . 013 x 10 Pa

V2 = 5

= 0.01767 m 3

3 x 1.013 x 10 Pa

= - 1.013 x 105 Pa (0.0530 - 0.01767) m3 = - 3.58 kJ

Table 1 GAS CONSTANT

AND CONVERSION FACTORS

1 cal (thermochemical)* = 4.1840 joule = 41.3 mlatm

1 mlatm = 0.1013 joule = 0.0242 cal

1 atm = 1.01325 x 105 N/m2

8.314 J 1.987 cal 82.06 ml atm

R= = =

mol K mol K mol K

* Various experimentally defined values of the calorie appear in

the literature (including the dietician's Calorie = 1 kcal). Only the

thermochemical calorie is defined exactly.

In order that the temperature may remain constant it is necessary to supply thermal energy to

the gas to compensate for the energy expended in doing work. From the first-law equation,

6

The term ideal means simply that the substance obeys a certain equation. An ideal gas

obeys the equation PV = nRT; in later chapters we will encounter the ideal solution, which

obeys an equation known as Raoults law. The ideal-gas equation combines Boyles law and

Charles, or Gay-Lussacs, law into a single, more convenient expression. The temperature must

be on an absolute scale, which we will always take as the Kelvin scale; n is the number of moles of

gas; and R is a universal constant, whose value depends on the units chosen for pressure and

volume. It should be noted that the product of pressure and volume has the dimensions and units

of energy (although PV is not a measure of energy). Such gases as He, H 2, O 2, and N 2 closely

follow the ideal-gas equation at room temperature; such easily condensable gases as CO 2 or H 2O

vapor follow the equation less closely.

7/10/07 1- 15

Q = E - W

For the special case of an ideal gas, the energy depends only on the temperature, not on the

pressure or volume. At constant temperature, therefore, E = 0 and the thermal energy that must

be supplied is

Q = - W = 3.58 kJ

A more important example than the expansion against a constant external pressure is the

reversible and isothermal (constant temperature) expansion. A process is said to be

thermodynamically reversible if it can be reversed at any stage by an infinitesimal increase in the

opposing force or an infinitesimal decrease in the driving force. It should be clear that such a

reversible process is an example of a limiting case, which is only approximately achieved in

practice. Not only does it require a frictionless mechanism, but if the unbalance of forces is

infinitesimal, the rate will be infinitesimal and the time required will be infinite. The question of

reversibility will be considered in more detail later.

From the assumption that the operation is isothermal and the gas is ideal,

E = 0

and

Q = - W = I P dV

Because the expansion is to be reversible, the pressure on the piston differs only infinitesimally

from the equilibrium pressure of the gas, P = nRT/V. The work done on the gas is then

7/10/07 1- 16

For example, if 2 mol of hydrogen at 3 atm and 50oC is expanded isothermally and reversibly

to a final pressure of 1 atm,

Q = - W = 5.37 kJ ln 3 = 5.90 kJ

Notice that the amount of thermal energy that must be supplied is greater for the reversible

expansion than in the previous example of expansion against a constant external pressure. A

reversible expansion (or compression) must always give a maximum value for Q, and accordingly

a minimum value for W.7

An integral may be represented by the area under a curve (see Appendix) and the three

examples considered above may be compared graphically. When the gas was warmed, at constant

volume, the pressure increased by the factor T f /T i = 323/297 = 1.09. In a plot of pressure against

volume, this is represented by a vertical line (Figure 2a) and the area under such a line is zero.

No work is performed.

The expansion against a constant opposing force is represented by the plot in Figure 2b. The

gas, in escaping through the pinhole, changes its pressure from 3 atm to 1 atm, but there is no

force exerted on moving surroundings during this escape. When the gas is through the pinhole,

however, it has the pressure of 1 atm and the volume increases, at this pressure, while the gas

pushes against the piston (the surroundings), until all of the gas has reached the same pressure

and occupies the total volume Vf . The work done by the gas, - W, is the area under the vertical

line, which is zero, plus the area under the horizontal line, which is 1 atm times the volume

change.

When the pressure of the gas changes smoothly, as in Figure 2c, the area under the curve (-

W) is a maximum for the given temperature. The pressure follows the curve PV = constant

7

A completely general proof that the reversible work is a minimum for the isothermal

reversible process cannot be given here, but this important result can be illustrated by considering

the expansion or compression of a gas. When the piston moves away from the gas molecules, the

molecules do not strike the piston as hard as when the piston is stationary. The pressure exerted

by the gas on the piston, and hence by the piston on the gas, is therefore less than the equilibrium

pressure of the gas. Hence IPeff dV < I P dV; the work done by the gas is a maximum for a

reversible expansion. Changing the sign, to obtain the work done on the gas, changes the

direction of the inequality; the work done on the gas, W, is a minimum when the effective pressure

is equal to the equilibrium pressure, for expansion or compression.

One may see elsewhere the expression W = - I P ext dV applied when Pext, the external

pressure, differs from the pressure of the system (= the gas). Except in unusual circumstances

(e.g., an effusion-controlled expansion), this is not even a good approximation. See Am. J. Phys.

37, 675-679 (1969).

7/10/07 1- 17

(where the constant is nRT) which is part of a hyperbola.

The condition to be satisfied in order that an expansion or compression of any fluid should be

thermodynamically reversible, and thus that the work done on the fluid should be - IP dV, is

simply that the fluid have a well-defined, uniform pressure throughout. In other words, there

must be no leaks, allowing different pressures at different points, and the motion of the piston

confining the fluid must be slow compared to the relaxation time of the fluid, or the time for

pressures to equilibrate in the fluid. For a gas, the expansion or compression must be very slow

compared to the speed of sound in the gas. Unless there is such a well-defined pressure, or in

certain situations (see Figure 1) two or more well-defined pressures, for the system,

thermodynamics cannot be applied. It is then necessary to apply the more difficult methods of

non-equilibrium, or irreversible, thermodynamics. That is, equilibrium thermodynamics is

sufficient for reversible processes and certain types of irreversible processes, whereas irreversible

thermodynamics deals with the time-dependent equations that become necessary in other

problems involving irreversible phenomena, such as diffusion rates and shock-wave propagation.

The existence throughout the process of a well-defined state (an equilibrium state, for

which pressure is defined) for the system is sufficient to ensure that the expansion or compression

will be reversible, but there may well be other irreversibilities in the total process. Some of the

work done by the gas may be against frictional forces (in the surroundings), or work done on a

massive piston may appear as kinetic energy of the piston, subsequently converted to thermal

energy by collision of the piston with mechanical stops (in the surroundings). Or there may be

conduction of thermal energy to or from the surroundings at a lower or higher temperature. Thus

the total process may consist of a sum of parts, some of which are reversible and some

irreversible. It is particularly important in such circumstances to define carefully the system and

surroundings and the exact process to be considered. Interchanging system and surroundings

labels may be helpful in analyzing the total process.

PHASE CHANGES. Let 5 g of ice melt at 0oC under 1 atm pressure. Experimental measurements

have shown that the amount of thermal energy that must be supplied, called the heat of fusion,

is 334 J/g. The work done is -IP dV = - 1 atm x V. The volumes of ice and water are 1.09

cm3/g and 1.00 cm3/g at 0oC. The energy change for the ice can be calculated from the first-law

equation.

E = Q + W = 5 g x 334 J/g - 1 atm(1.00 - 1.09)ml/g x 5 g

Conversion of the work term from mlatm to J gives

Although the total energy absorbed by the ice, E, is slightly greater than the heat of fusion, Q,

the work done on the ice-water system by the atmosphere (0.05 J) is negligible for nearly all

purposes.

If 5 g of water is vaporized at 100oC and 1 atm pressure, the energy change can be calculated

7/10/07 1- 18

in the same manner. The heat of vaporization is 2.258 kJ/g, 8 and for calculation of the work done

it is sufficient to assume that the water vapor is an ideal gas.

E = Q + W

= 2.258 kJ/g x 5 g - 1 atm[ 5/18 mol x (8.314 J/molK)/1 atm x 373.15 K - 5 x 10 -6 m 3]

= 11.290 kJ - 0.861 kJ = 10.43 kJ

In problems of this type, however, an important shortcut is often satisfactory. The volume of

the liquid is sufficiently small compared to that of the vapor that it may be neglected. Then the

work term becomes

W = - P(Vf - Vi) = - PVf = - PnRT/P =- nRT

The value of R in J/molK may be inserted into this expression to avoid completely the units of

volume and the conversion from atm to Pa. The entire problem can thus be written

= 11.290 kJ - 0.861 kJ = 10.43 kJ

hydrogen at 100oC and 1 atm pressure (or slightly less) to give water vapor.

2 H2 + O2 &6 2 H2O

The heat of reaction (the amount of thermal energy absorbed by the system) is - 242.5

kJ/mol(H2O). That is, a negative amount of thermal energy is absorbed by the reacting system, or

a positive amount of thermal energy is given up by the reacting system to the surroundings. The

work done on the system is

= - (n)RT (11)

and the energy change of the reacting system is

E = Q + W

= 2 mol(- 242.5 kJ/mol) - (- 1 mol) x 8.314 J/molK x 373 K

= - 481.90 kJ + 3.10 J = - 481.90 kJ/(2 mol H2O)

The same reaction, at 100oC and 1 atm pressure (or slightly more) but producing liquid water

rather than water vapor, will have a heat of reaction that differs from that of the preceding

8

This heat of vaporization is required to separate the molecules from each other that is,

it represents an increase in the potential energy of the molecules. Because the temperature does

not change, the kinetic energy remains constant.

7/10/07 1- 19

problem by the heat of vaporization of water.

= - 563.19 kJ/(2 mol H2O)

The work differs, also, because V is different. Neglecting the volume of the liquid, V =

(n)RT/P = (- 3)RT/P.

W = - P V = 3 RT = 3 mol x 8.314 J/molK x 373K = 9.30 kJ

E = Q + W = - 563.19 kJ + 9.30 kJ

= - 553.89 kJ/(2 mol H2O)

Enthalpy

We have covered, in brief outline, the methods of finding the change of energy of any system,

by measuring or calculating the amount of thermal energy transfer, Q, and the amount of work

done, W. But already, we have seen that complications arise, such as having to find work done,

against the atmosphere, when that work term is itself of little interest.

The way to avoid these annoying correction terms, in general, is to define a new quality that

focuses on what we do want to know. Our second step, therefore, in understanding an applying

thermodynamics, is to learn how to define and calculate new variables that will simplify our

measurements and calculations.

Chemical reactions and phase changes are more often carried out at constant pressure than at

constant volume. At constant volume (no work done) the energy change is equal to Q, the

amount of thermal energy transferred to the system, but under constant pressure a correction

must be made for the work performed on the system by the external pressure. Consider a

completely general constant-pressure process in which the only work done is because of the

volume change.9

(P) E = Q + W = Q - P(V2 - V1)

E = Q - (P2V2 - P1V1)

Q = E2 - E1 + P2V2 - P1V1

9

Later we will consider work done in other ways, especially by electrical fields. We are

explicitly excluding such work terms for the present because they are unnecessary here.

7/10/07 1- 20

= E2 + P2V2 - (E1 + P1V1)

or

(P) Q = (E + PV) (12)

This last equation will be encountered so often that it is a great convenience to introduce a new

symbol for the quantity E + PV.

Then, if pressure is constant and the only form of work is W =- IP dV, equation 12 becomes

(P) H = Q (14)

Note that the enthalpy is actually defined by equation 13, which contains no restrictions on

pressure, temperature, or volume. Nevertheless, the enthalpy will be found to be most convenient

for problems in which pressure is constant.

A comparison between energy and enthalpy, E and H, can be made by calculating the

enthalpy changes for the same processes for which energy changes were previously found.

TEMPERATURE CHANGES AND HEAT CAPACITY, CP. We found that for 2 mol of H2 warmed at

constant volume from 25oC to 50oC, E = 1.05 kJ. For the same process, the enthalpy change is

H = (E + PV) = E + (PV) = E + V P

= E + V(nRTf /V - nRTi /V) = E + nRT

= E + 2 mol x 8.3144 J/molK x 25 K

= 1.05 kJ + 416 J = 1.47 kJ

The enthalpy change is greater than the energy change because the increase in temperature causes

an increase in P and thus in the product PV.

If the gas is warmed at constant pressure, rather than at constant volume, the enthalpy

change can be calculated in much the same way.

H = E + (PV) = E + P V = E + nR T

= 1.47 kJ

The enthalpy, like the energy, depends only on the temperature, for an ideal gas. It is for this

reason that we find the same H (as well as the same E) when the hydrogen gas is warmed by

25oC whether the process is at constant volume or constant pressure, or under other conditions.

10

As you might guess, H was chosen as a symbol because H = Q, the heat (i.e., the

amount of thermal energy transfer). One must, however, avoid any attempt to associate H with

the (total) thermal energy. Warning: PV has the dimensions, and units, of energy but, as shown

explicitly in equation 13, PV is not energy.

7/10/07 1- 21

It should be observed that in the constant-pressure process the correction term to obtain the

enthalpy change from the energy change is a work term, -W = P V. But in the constant-volume

process the correction term, though of equal magnitude, is not a work term, having instead the

form V P. (You will learn very quickly that I V dP W.)

The constant-pressure warming process can be treated in a somewhat different manner.

Employing equation 14, for constant pressure,

(P) dH = q

Then, dividing by dT,

(P) dH q

=

dT dT

or

H

= CP (15)

T P

For a diatomic gas near room temperature, C P is about 7/2 R = 29 J/molK. Inserting this

(approximate) value for H2,

H

H = dT = CP dT

T P

= 2 mol x 29 J/molK x 25 K

= 1.45 kJ

The heat capacity at constant pressure, C P, is greater than, or occasionally equal to, the heat

capacity at constant volume, CV. The difference is small for solids and liquids (typically about 1.7

J/molK), but for an ideal gas the difference is appreciable and is easily calculated. The constant-

pressure and constant-volume restrictions can be dropped from the derivatives of equations 6a

and 15 for the special case of an ideal gas, because both the energy and enthalpy of an ideal gas

are independent of pressure and volume. Taking 1 mol of gas,

dH dE d (PV ) dE d (RT )

CP = = + = + = CV + R

dT dT dT dT dT

or

(I.G.) CP = CV + R (16)

IDEAL-GAS EXPANSIONS. The work performed on an ideal gas as it expands isothermally was

calculated previously for two important special cases (equations 9 and 10). Because the energy

of the ideal gas is independent of pressure and volume, the energy change must be zero in an

isothermal expansion. Thus we conclude that Q + W = 0; the work done on the gas is equal and

7/10/07 1- 22

opposite to Q, the thermal energy absorbed by the gas in the expansion.

At constant temperature, the product PV is also constant for an ideal gas. Therefore, at

constant temperature, H = (E + PV) = E = 0. Enthalpy change is also zero for any

isothermal expansion (or compression) of an ideal gas.

One often sees the generalization that a gas cools on expansion. That is generally not true

except when the gas does work on its surroundings (thus giving up energy to the surroundings)

with no compensating transfer of thermal energy to the gas (or for certain situations involving

non-ideal gases). Obviously there is no cooling in an isothermal expansion.

PHASE CHANGES. The heat of fusion is the amount of thermal energy absorbed by a solid when it

melts (fuses) under constant pressure. From equation 14 this is identically H for the melting

process. Similarly, the heat of vaporization is H vap. Although Efusion is nearly the same as

Hfusion, because of the small volume changes involved, the difference between Evap and Hvap

can be appreciable, as was shown above. Tabulated values are invariably the enthalpy changes.

CHEMICAL REACTIONS. The heat of reaction, as tabulated, assumes constant pressure and is

therefore identical with the H of reaction. 11 That is, it is assumed that the pressures associated

with each reactant and each product are the same before and after the reaction, so the total

pressure remains constant during the reaction.

The assumption of constant individual pressures is much less important when considering

heats of reaction than in some later applications. Keep in mind, however, in interpreting

thermodynamic processes, that we are not considering a process that starts with reactants, only,

and concludes with products, only. Rather, we assume the only change is the chemical reaction.

Thus we begin with a mixture of products and reactants and allow the reaction to proceed

without change in the physical conditions (temperature, pressure, or concentrations) of the

substances. One way of achieving this experimentally would be to have the total amount of

material large, and allow only a small part of the reactants to combine. (The measured values are

then calculated per mole of a reactant or a product.) We will find, in Chapter 4, an alternative

method is often to measure a reaction in an electrochemical cell, under equilibrium conditions.

We will return to this assumption of fixed conditions when we explicitly consider chemical

equilibria.

State Functions

We have seen that those properties such as energy, enthalpy, temperature, pressure, and

volume that depend on the state of a system are called state functions. If measurements

carried out in Boston, Brooklyn, Birmingham, and Berkeley are to be compared, we must be

11

An exception is that heat of combustion is given as a positive number (although the

amount of thermal energy absorbed by the system is negative) and is therefore - H. If there is

any question concerning the convention followed, look for a reaction such as hydrogen plus

oxygen to give water, where we know energy is given off, so Hreaction is negative.

7/10/07 1- 23

certain that we are dealing with substances in substantially identical states. An important question

is how much information we must have about any system in order to determine its state, and

hence to fix completely its physical and chemical properties.

EXTENSIVE AND INTENSIVE PROPERTIES. If the amount of the system is important, it must be

specified, either by mass or by equivalent measure such as the number of moles. 12 Some

properties, such as energy, heat capacity (C P or C V), or volume, will be proportional to the

amount of material. These are called extensive properties. Other quantities, such as pressure,

temperature, and density, are independent of the amount of material and are called intensive

properties. Properties such as molar volume, density, and molar heat capacity are examples of

intensive properties derived from extensive properties. 13

Apart from the size of the system, the most obvious variable to control is the composition.

For a pure substance, the degree of purity and the nature of the residual impurities should be

known. For a solution, the concentration of each of the components is required (one less

concentration value than the number of components in the solution). Where there are possible

differences of phase (solid, liquid, or vapor, or more than one crystal structure) the phase studied

must be reported. In addition, each worker must be able to reproduce exactly such properties of

the system as temperature, pressure, volume, density, viscosity, and refractive index.

Fortunately, if each system can be assumed to be at equilibrium (in its most stable form, or

state), not all of these variables are required. If the composition and mass are known, it is in

general necessary to know only two additional variables (with occasional others as already

mentioned). For example, if the temperature and pressure are known the volume can be

calculated (assuming the necessary measurements have been previously made) whether the

substance is solid, liquid, or gaseous, and from this the density, viscosity, and refractive index

follow. To define the state of a gas it would be equally satisfactory to specify the pressure and

volume, or the volume and temperature. On the other hand, knowing that 1 g of water has a

12

A mole is a certain number of molecules or other particles (Avogadros number, equal

to 6.02 x 1023). Thus it is necessary to indicate what kind of molecules are being counted (e.g., H

is not the same as H2). In practice, the number of moles is determined from the mass and the

molar mass (or so-called molecular weight) with units of g/mol understood. At one time,

quantities such as gram mole and kilogram mole were defined, but under the modern SI

terminology there is only one mole (symbol mol). Nevertheless, a weight equal to the molar mass

number in pounds may appear under the title of pound mole.

13

Specific quantities are generally defined as dimensionless ratios of the (extensive)

properties of a substance to the (extensive) properties of another substance. Thus specific gravity

is the ratio of the density of a substance to the density of water (or, for gases, the ratio to the

density of air). Specific heat was originally the ratio of heat capacity of a substance to the heat

capacity of water. With Q measured in calories, the heat capacity of water is 1 cal/gK, so the

specific heat was equal to numerical value of the heat capacity in cal/gK. Over time, specific heat

has been taken to be equal to the heat capacity per unit mass (per degree), regardless of the units

of mass or energy. Therefore, units must now be specified.

7/10/07 1- 24

volume of 1.000132 cm3 under 1 atm pressure does not determine whether the temperature is 0o C

or 8.1oC, because the water has a minimum volume, or maximum density, at 4o C. Nor could one

determine the pressure accurately if given the volume and temperature of a liquid or solid. This

demonstrates that some discretion is required when variables other than pressure and temperature

are selected, even if extra variables such as electric or magnetic fields are not relevant.

EXACT DIFFERENTIALS AND LINE INTEGRALS. A property, or state function, can depend only on

the present state of a system. It cannot depend on history that is, on how the system arrived at

that state provided we limit the discussion to equilibrium states, so that there can be no strains

in solids, or other residual effects. It follows, therefore, that the change in such an equilibrium

property, in going from one state to another, can depend only on the initial and final states.

Mathematically, this means that the change, described by an integral, depends only on the limits of

the integral. For example,

E2

E = E 2 E1 = E1

dE

Nothing need be known about the process except the energy of the initial state, E 1, and the

energy of the final state, E2, to find E. Integrands of this type are called exact differentials.

Most integrals we will encounter are well defined in

themselves. For example,

x2 1 2 1 2

x1

xdx =

2

x2

2

x1

(xdy + ydx ) = d ( xy ) = x 2 y 2 x1 y 1

x2 , y2 x2 , y2

x1 , y1

x1 , y1

x ,y

2 2

ydx

x1 , y1

known as a function of x, then we can make a plot of y vs. x, as

in Figure 3. Then, for example, if y = x2 + 3,

(x )

x2 , y2 x2 1 3 1

ydx = + 3 dx = x 2 + 3 x 2 x 13 + 3 x 1

2

x1 , y1 x1 3 3

7/10/07 1- 25

We can say that Iy dx has been integrated along the line shown in Figure 3. This is called a line

integral.14

Line integrals appear in thermodynamics when it is necessary to evaluate a quantity that

depends on the path. Letting y = P and x = V in the example above gives the familiar integral for

work,

W = -IP dV

It is not sufficient to know initial and final states (the end points of the line); the exact path must

be known. This was demonstrated for the calculation of work in Figure 2. Thermal energy

absorbed by a system also depends on the path, so Q is given by a line integral.

It is worth noting that P dV is a change (in P and V, because P changes with V), so P dV is an

inexact differential. W is an amount, not a change in work or any other property, so it is at best

misleading to describe W as a differential (exact or inexact). Careful terminology can be an aid to

understanding. Careless terminology is a hindrance to understanding.

know, in principle, all other state functions (for that equilibrium state, if there are no extraneous

variables such as electric or magnetic fields). For example, if the pressure and temperature of n

moles of an ideal gas are known, the volume can be found from the equation of state, V =

nRT/P, or PV = nRT. Any substance, whether an ideal gas or not, follows an equation of state

relating the pressure, volume, and temperature, but the true equation of state may be a very

complicated function and, indeed, may not be known accurately.

Several functions have been proposed as good approximations to the equations of state for

real gases. The best-known is that suggested by van der Waals:

n2a

P + 2 (V nb ) = nRT

V

In this equation, a and b are constants that depend on the particular gas to be described.

When the volume is large and the temperature is high, the terms involving a and b are negligible

and the gas behaves as an ideal gas; but as the gas is cooled and/or compressed, the behavior

deviates more and more from the ideal-gas law, until eventually the gas condenses to a liquid or

solid.15

14

For a more thorough treatment of exact differentials and line integrals see advanced

calculus books. There is a direct mathematical test to determine whether or not a function of two

variables is an exact differential.

15

The constant b is a measure of the volume physically occupied by the molecules, and

thus not available to the gas. The constant a is best visualized as arising from the curved paths of

the molecules, because of mutual attractions. This decreases the frequency of wall collisions

7/10/07 1- 26

It should also be possible to relate the volume of any liquid or solid to its temperature and

pressure, or to express such other properties as refractive index, heat capacity at constant volume

or pressure, thermal conductivity, heats of vaporization or fusion, or vapor pressures of solids or

liquids, in terms of the temperature and pressure. Some of these equations will be encountered in

later chapters.

Thermochemistry

The application to chemical reactions of the principles developed thus far is called

thermochemistry. In particular, the heats of reaction are measured and tabulated and from these

and from measured heat capacities the enthalpy changes are calculated for other reactions or for

other experimental conditions.

HESSS LAW. The enthalpy change for a chemical reaction, such as the oxidation of sulfur dioxide

to sulfur trioxide

can be expressed as the difference between the enthalpies of the initial and final states.

= H(2 SO3) - H(2 SO2) - H(O2)

enthalpy. Only energy, and enthalpy, changes can be determined. However, knowing that these

energy and enthalpy changes depend only on the initial and final states, it is possible to add and

subtract chemical reactions and add and subtract the corresponding enthalpy changes. That is, we

may quite arbitrarily select a reference energy and/or enthalpy level and measure all values from

that arbitrary level. In particular, it is possible to tabulate heats of formation, the enthalpy

changes in the reaction of the elements to form each compound, and from these to calculate

enthalpies of other reactions. This principle is known as Hesss law.

The reactions for the formation of the gases SO 2 and SO3 from the elements are

S + O2 ----- SO2

S + 3/2 O2 ----- SO3 (liq)

without changing their effect, and therefore decreases the pressure on the walls, requiring the

supplement to P to fit the ideal gas equation form; see Phys. Teach. 34, 248-249 (April, 1996).

16

The reader with some knowledge of special relativity may recognize that the total

energy of any system is measured by its mass, multiplied by the square of the speed of light.

However, it would be necessary to measure masses about a million times more accurately than is

now possible to be able to determine energies to the accuracy required in thermochemistry.

7/10/07 1- 27

The measured enthalpy changes for these reactions at 25 oC and 1 atm pressure are -296.90 kJ/mol

and -437.94 kJ/mol. Subtraction of the first reaction from the second gives

SO2 + O2 &6 SO3 (liq)

and subtraction of the enthalpy changes gives -141.04 kJ/mol, which is the heat of reaction for the

oxidation of SO2 to SO3 (liq).

Exactly the same elements, in the same quantities, always appear on both sides of a chemical

equation (which is why reactions as written are called equations). Subtraction of the elements

from both sides of an equation will yield, on each side, product minus reactants for the reactions

of formation of each of the substances appearing in the original equation. In the example above,

the original equation was SO2 + O2 &6 SO3. Subtract 1 mol of S and 3/2 mol of O2 from each

side. The equation can then be written as the formation of each compound (i.e., of SO 2, O 2, and

SO3) from the elements.

(SO2 - S - O2) + ( O2 - O2) &6 (SO3 - S - 3/2 O2 )

and therefore

Hreaction = Hform(SO3) - Hform(SO2) - Hform( O2)

= -437.94 kJ/mol -296.90 kJ/mol - 0

= -141.04 kJ/mol(SO3 liq)

(Notice that the heat of formation of any element, in its standard state, is necessarily zero.)

An entirely equivalent way of obtaining the same numbers is to consider the enthalpy of each

compound on a scale taken with reference to the elements. Such enthalpy values are called

standard enthalpies of the compounds; they are identical with the standard enthalpies of

formation.

Hesss law can often be applied to find heats of reaction that could not be directly measured

experimentally. For example, the reaction of two molecules of ethylene, C 2H 4, to form

cyclobutane, C4H8, would not readily occur quantitatively under conditions conducive to

measurement of the heat of reaction. But both ethylene and cyclobutane can be burned in

oxygen, and subtraction of these reactions gives the reaction equation desired.

C4H8 + 8 O2 &6 4 CO2 + 4 H2O

2 C2H4 &6 C4H8

and, therefore, subtraction of the H for the second combustion from the H for the first

combustion gives H for the condensation reaction. Heats of combustion (equal to - H reaction )

are comparatively easy to measure and are often tabulated.

KIRCHHOFFS LAW. The heat of reaction at a temperature other than that given in a table can be

7/10/07 1- 28

found by calculating enthalpy changes along an arbitrary path. The total enthalpy change is

independent of this choice of path. The method is known as Kirchhoffs law.

Assume that H is known for a reaction at a temperature T 1 and the H at another temperature,

T2, is to be found. Starting with the hot reactants at T2 (Figure 4), the reaction could be carried

out isothermally to obtain products at the same temperature. An alternative path would be to

cool the reactants to the temperature T 1, carry out the reaction isothermally at T1 , and warm the

products to T2. The heat of reaction at T1 is already known and if the heat capacities at constant

pressure are known, the enthalpy changes can be calculated for the processes of cooling reactants

and warming products. This path must give the same H as the isothermal reaction at T 2.

T1 T2

H 2 = T2

C P ( reactants ) dT + H 1 + T1

C P ( products ) dT (17)

or,

because interchanging limits of an integral will change the sign,

[C ] dT

T2

H 2 = H 1 + P ( products ) C P ( reactants )

T1

If the difference in heat capacities is independent of temperature, this may be rewritten in the form

H2 = H1 + [Cp (products) - CP (reactants)](T2 - T1 ) (18)

For example, given that the heat of reaction for rhombic sulfur burning in oxygen to yield

sulfur dioxide gas is - 296.9 kJ/mol at 25 oC (298 K), find H at 95oC (368 K). The heat

capacities are given in Table 2. Insertion of the numerical values into equation 18 gives

Average values (in J/mol-K) for temperature ranges indicated

Compound CP Temperature, oC

He 20.8 -200 up

H2 28.8 25 to 200

O2 29.4 25 to 200

H2O(g)* 36.4 25 to 200

SO2(g) 41.9 25 to 200

S (r) 23.7 25 to 200

S (m) 25.9 95 to 120

*For rough calculations it is sufficient to set

CP(steam) = CP(ice) = CP(liq H2O).

7/10/07 1- 29

H368 = - 296,900 J/mol + (41.9- 29.4 - 23.7) x 70 J/mol

= - 296.1 J/mol

Sometimes there will be a phase transition during the warming or cooling process. Sulfur has

a phase change at 95oC, at which point rhombic sulfur goes to monoclinic sulfur; the monoclinic

sulfur melts at 119oC. The enthalpy changes are 11.78 and 39.24 kJ/mol. The heat of reaction

for liquid sulfur burning in oxygen to form SO2 at 119oC (392 K) can be calculated as follows (see

Figure 5).

H392 = - Hfusion - CP (m) (119 - 95) - Htr - CP (r) (95 - 25) - CP (O2 ) (119 - 25)

+ H298 + CP (SO2) (119 - 25)

H392 = - 39,240 - 25.9 x 24 - 11,780 - 23.7 x 70 - 29.4 x 94 - 296,900 + 41.9 x 94 J/mol

= - 349.0 kJ/mol

Note that temperature differences can be found without conversion to the Kelvin scale.

Both Hesss law and Kirchhoffs law are simply applications of the principle that changes in

a state function, such as the enthalpy, are completely determined by the initial and final states. 17

This principle is combined with the equation arising from the first law that shows that i f the

pressure is constant, the enthalpy change will be equal to the heat absorbed by the system. Thus

the heat of reaction, by which we mean Hreaction (at a particular temperature, pressure, and

concentrations of reactants and products), is only equal to the heat absorbed i f the reaction

proceeds at constant pressure (and at the specified temperature and concentrations). It is

sometimes more convenient to carry out a reaction at constant volume. Then the heat absorbed is

not equal to the heat of reaction (that is, to H reaction), but it is still determinate because heat

absorbed equals the change in energy when the system follows a constant-volume path and

because Ereaction is fixed by the initial and final states.

17

This property associated with state functions has sometimes been confused with a

conservation principle. Enthalpy is not conserved.

7/10/07 1- 30

The experimental determination of a heat of reaction is called calorimetry. A typical

calorimeter (Figure 6) consists of a reaction chamber, surrounded by a layer of water, enclosed

by sufficient insulation to prevent heat loss to the surrounding laboratory. The reactants, at room

temperature, are placed in the reaction chamber, the calorimeter is closed, and the reaction is

initiated by an electrically heated wire or other controlled energy source. The reaction will

normally be exothermic and the reaction chamber will therefore become quite hot, but the heat is

conducted into the surrounding water layer so that the products, and the water, reach a final

temperature only slightly above the initial temperature. The E reaction is the same as if the entire

process had occurred at the initial temperature even though the materials may have become quite

hot during the course of the reaction. The heat given off by the reaction is calculated by

observing the temperature rise of the water, using the condition that all heat given off by the

reaction must have been absorbed by the water. Small corrections are required for the change of

temperature, from the initial room temperature, of the products, and for the small amount of

energy added by the hot wire or other initiation method. Some systems may also require a

correction for changes of concentrations during the reaction.

7/10/07 1- 31

Problems

1. At room temperature the heat capacity (C V) of most solid elements (except the very light ones)

is about 3R. Specific heat is the heat capacity per unit mass, or the value in J/gK. (For solids the

difference between constant volume and constant pressure conditions is small and may be

neglected here.)

a. Find the specific heat of Pb (molar mass = 207.19).

b. Find the specific heat of Cu (molar mass = 63.546).

c. Find E for 25 g of Cu when it is warmed from 20oC to 35oC.

2. Estimate the final temperature when 10 cm 3 of iron (density 7.86 g/cm3) at 80oC is added to 30

ml of water at 20oC.

3. Find the work done when 3 mol of N2 gas at 4 atm pressure expands slowly at 25 oC against a

constant pressure of 1 atm.

4. Calculate the work done when 0.25 mol of SO2 at 27oC and 1 atm expands reversibly and

isothermally to a final pressure of 0.20 atm. Find Q for the gas during this process.

5. Calculate the final temperature if an ice cube (25 g) at - 5 oC is added to a cup of coffee (150

ml, or 2/3 cup) at 90oC, neglecting heat loss to the surroundings.

6. The heat of vaporization of benzene, C6H6, is 30.72 kJ/mol and the normal boiling point is

80.1oC.

a. What is Evap if the vapor is an ideal gas?

b. Part of the thermal energy absorbed by a liquid as it vaporizes to a gas is required to

perform work on the atmosphere as the substance expands to a vapor. What fraction of the total

Q goes into work against the atmosphere when benzene (density about 0.88 g/cm 3) vaporizes at

its normal boiling point?

7. Find E at 25oC for the oxidation of S (rhombic) to give SO2 (gas) and for the oxidation of S

to give SO3 (liq). The heats of reaction are - 296.81 and - 441.0 kJ/mol. Assume gases are ideal.

8. Calculate H and E for the reaction, at 25oC,

9. Manganese can be prepared by a thermite process,

The standard enthalpy of formation of Mn3O4 is - 1387.8 kJ/mol and for Al2O3, - 1657.7 kJ/mol.

Find the amount of thermal energy given off by the reaction as written above, starting with the

reactants at room temperature and ending with the products at room temperature.

10. The interconversion of graphite and diamond does not occur at room temperature. Explain

how you could determine H for this transition by measurements in the laboratory.

11. Calculate the heat of vaporization of water at 50 oC.

12. Find H for the hydrogenation of ethylene to produce ethane,

7/10/07 1- 32

at 150oC. The standard heats of formation, at 25o C, of ethylene and ethane are 52.4 and - 84.0

kJ/mol, respectively. Heat capacities (C P) of ethylene, hydrogen, and ethane within this

temperature interval are approximately 42.9, 28.8, and 52.5 J/molK. All three compounds are

gases at room temperature and above.

13. Benzene, C6H6, is reduced commercially with hydrogen to give cyclohexane, C6 H12 .

At room temperature (25oC) the benzene and cyclohexane are liquids and the heat of reaction is

- 205.5 kJ/mol. Benzene boils at 80.1oC with a heat of vaporization of 47.8 kJ/mol; cyclohexane

boils at 80.7oC with a heat of vaporization of 33.0 kJ/mol. The average heat capacity of liquid

benzene is 136.0 J/molK, of liquid cyclohexane 154.9 J/molK, of benzene vapor 82.4 J/molK,

of cyclohexane vapor 150 J/molK, and of hydrogen 28.8 J/molK. Find H for the reduction of

benzene with hydrogen at 150oC.

[0.44 cal/gK; 0.41; 26.7 35.8 cal/molK; 6.94 cal/molK]Check numbers

14. Air is approximately 20% O2 and 80% N2, by volume. Find the effective molar mass of air.

Calculate the density of air at 25oC and 1 atm in kg/m3, assuming it acts as an ideal gas.

15. A gaseous compound, containing only sulfur and fluorine, is 62.7% (by weight) sulfur. At

27oC and 750 torr18 the density of the gas is 4.09 g/L. What is the molecular formula of the

compound? Assume the gas is ideal.

16. Find the pressure exerted by 32 g of methane in a 2 L steel bomb at 127 oC, assuming the gas

is ideal.

17. Find the pressure exerted by 32 g of methane in a 2 L steel bomb at 127 oC assuming the gas

obeys van der Waals equation. The constants may be taken as a = 2.25 L 2atm/mol 2 and b =

0.0428 L/mol.

18. Find the volume occupied by 32 g of methane at a pressure of 5 atm at 27 oC if the gas is

ideal. Calculate, with this value, the n2a/V2 correction term in the van der Waals equation and

find, from this, an approximate value for the volume occupied by the methane if it obeys van der

Waals equation. Recalculate the correction term, with this better volume, and recalculate the

volume if necessary.

19. A good vacuum obtained with a mechanical pump and a mercury diffusion pump will

measure 10-5 torr, or better, of noncondensable gases (such as air), but there is 10-3 torr of

mercury vapor present unless this has been trapped out. Very good vacuum systems can give 10 -

9

torr.

a. How many molecules/cm3 are there at a pressure of 10-3 torr?

b. How many molecules/cm3 are there at a pressure of 10-9 torr?

c. What pressure would be required to achieve 1 molecule/cm 3?

18

The torr is a unit of pressure equal to 1/760 atm. It is numerically equivalent to the unit

mm of Hg but is less awkward, especially when mercury is one of several vapors present. The

torr is named after Evangelista Torricelli, who invented the barometer in the 17 th century.

7/10/07 2- 33

2 The Second Law of Thermodynamics

During the 19th century several men, of quite different backgrounds and interests, struggled

with the basic problems of thermodynamics. Brilliant flashes of understanding were followed by

years of doubting, testing, and interpreting. Among the fundamental difficulties was a confusion

between two concepts. One of these was the concept of energy. The other, which is related to

the general concept of equilibrium and the direction of changes with respect to equilibrium, was

stated first, but the language was such that it was long misunderstood and therefore rejected. It is

now accepted as the second law of thermodynamics.

Very few people today who have any acquaintance with modern science would doubt the

following generalizations:

1. Perpetual-motion machines dont work.

2. Bodies in equilibrium have the same temperature. When two bodies in contact have

different temperatures, energy flows, as heat (Q), from the warmer to the cooler body.

3. Bodies in equilibrium have the same pressure. When two bodies in contact, at the same

temperature, have different pressures, the body at the higher pressure tends to expand and

compress the body at the lower pressure.

None of these statements is required by the first law, 1 which requires energy balance in any

process but does not say whether a process will actually occur. For example, both exothermic

and endothermic reactions are known that do proceed without external forcing. There is, despite

the variety in these generalizations, a similarity of pattern and intent saying, for example,

whether a specific process will or will not occur that suggests a common basis. The basis is

found in the postulate known as the second law of thermodynamics.

We have seen that thermodynamics largely ignores the atomic structure of matter. It is quite

sufficient, for almost all purposes, to measure the macroscopic (large scale) variables such as

temperature, pressure, volume, and energy. The difficulty with this approach is that it effectively

hides from us one key property that may be called the spread function, S.

Consider the thought experiment of adding 10 grains of yellow rice to a large bag of white

rice, which will subsequently be mixed and poured and just thoroughly scrambled. Initially the

yellow grains were carefully arranged, on top in one corner. Where will they be a little later after

mixing?

There is no energy advantage for the yellow grains to move to the bottom, or back to the

top, or to any other specific location. We know that, once mixed, there is close to zero

1

The first law prohibits certain perpetual-motion machines, called perpetual-motion

machines of the first kind. The more interesting attempts, called perpetual-motion machines of

the second kind, do satisfy the first law.

7/10/07 2- 34

probability that they will spontaneously reassemble. Even if the bag of rice is only 100 grains

deep, 100 grains wide, and 100 grains in the third direction, each yellow grain has 100 x 100 x

100 = 106 possible locations, which means that two grains have 106 x 106 = 1012 possible locations

and the 10 grains have (106)10 = 1060 possible locations. The probability they will all collect in

one location is not much more than 1 in 1060, which is awfully close to zero for most purposes.2

Now imagine a very small number of molecules (say 10 6) to which we add 10 molecules that

are excited perhaps they are each vibrating, or rotating, or otherwise have some extra energy

that can be transferred to a neighboring molecule. After a very short time, the extra energy will

be spread throughout the 106 molecules, so there is no significant chance the energy will ever

again (in the lifetime of the universe) be collected in the original 10 molecules. With a more

typical number of molecules (such as 6 x 10 23) and many ways for each to store energy, it is not at

all unreasonable to say the probability of unspreading the energy goes quickly to zero.

If we have a small steel ball (which will typically have 10 23 or more atoms), one way of

storing energy in the ball is to start it rolling. Another very large group of ways of storing energy

in the ball is to let some of the atoms begin to vibrate. The mechanical energy of rolling may be

converted by rolling friction to thermal energy of internal motions. There are so many possible

internal motion states that we dont expect the energy to ever spontaneously reappear as

mechanical energy of rolling.

Entropy

Fortunately, there is an easy way to keep track of S, the spread function, without even having

to count molecules. Any energy passing into an object by thermal energy transfer, Q, is gone in

terms of having been spread around. It shows up afterward only as an increase (perhaps slight) in

the temperature of the system. So the first step is to keep track of Q, and in particular, we want

Q for a reversible path, or one that is as close as possible to equilibrium.

Then we want to know whether this amount of energy is important to the system, or whether

there is already so much energy spread around that this addition is relatively unimportant. That

average energy we will find is nicely measured by the (absolute) temperature of the system. So

we measure the increase in average energy as Q rev and divide by the temperature, T.

Q rev

Definition of Entropy Change S = (1)

T

2

If the ten yellow grains were regarded as indistinguishable, we should remove 10! = 3.6 x

6

10 possibilities that only interchange yellow grains among themselves. That would still leave

more than 1053 possibilities, scarcely different qualitatively from 1060 . The problem of overlapping

positions (two yellow grains being assigned to the same location) may safely be ignored at this

level of probability.

7/10/07 2- 35

The official name of the spread function, S, is entropy 3. By the methods of statistical

mechanics we can show that S is a measure of the actual number of individual states over which

the energy of the system is spread. The greater the number of states (hence S), the greater the

probability associated with the overall state.

It is, of course, possible to transfer energy to our system without increasing the spread of

energy. For example, we can transfer just enough energy, in the proper form, to make the steel

ball start rolling. In a reversible process, this energy transfer is measured as work. As we saw for

ideal gas expansions and compressions, the work done on the system is a minimum (and Q is a

maximum) when the process is reversible. When the process is purely one of transferring energy

to a mechanical mode, such as rolling or moving in a straight line, the amount of thermal energy

transfer, Q = Qmax, is equal to zero. There is no increase in entropy.

An alternative way of approaching the second law is to recognize that E is independent of

path, so we can write, for any process at constant temperature, 4 between fixed end points

There can be only one value of Qmax and one value of Wmin, so we can represent these, also, as

values independent of path, which for the moment we will label as A (= W rev) and as B (=

Qrev) and regard A and B as state functions.

(T) E = A + B

or

E=A+B (3)

In any isothermal process in which the energy of the system changes by E, some part of this

energy change, equal to A, must appear as work done on the system. The second energy term,

called B for the moment, cannot be lost, because of the first law (conservation of energy);

however, it may be regarded as spilled energy, which is lost for useful purposes during the

transfer operation because it has become spread through the system.

From equation 3, two important functions are obtained. One, temporarily given the symbol

A, is called the Helmholtz free energy, or sometimes the work function, and is characterized, as

above, by the constant temperature equation

3

The name was chosen by Clausius from the Greek verb entrepo (), meaning to

turn, implying change, and because it somewhat resembles the word energy, one of the

important quantities involved in finding the number of states Entropy, S, is proportional to (or for

suitable units, equal to) the logarithm of the relative probability, i.e., to the number of states

accessible to the system. Unfortunately, it is also vaguely suggestive of enthalpy, H, which has

different dimensions, units, and meaning.

4

We also assume here that the process satisfies the first-law equation, E = Q + W.

However, equations 1 and 5, and equation 6 (obtained below), are not subject to this restriction

against other forms of work.

7/10/07 2- 36

(T) A = Wrev (4)

This function (which we will subsequently designate by the more current notation, F), and an

even more useful quantity derived from it, will be investigated later.

The spread function, S, is obtained from the second function, B, when we divide by the

temperature, T. That is, S = B/T or B = TS, where S is the spread function, entropy, previously

introduced. Then a small change in B breaks into two parts.

d(TS) = T dS + S dT

and at constant temperature

q rev

dS = (5)

T

Statistical mechanics tells us something about the value of S, representing the number of

molecular states, but thermodynamics (which never quite admits the importance of molecules)

tells us only how to find changes in entropy, S.

ice, at 0oC and 1 atm pressure, by bringing it into contact with a thermostat, or heat reservoir.

The thermostat might be a very large block of metal, well insulated from its surroundings and

large enough so that the reasonable amount of thermal energy added or withdrawn will not

change its temperature. For the ice,

Q rev 333 .6 J/g

S = = = 1 .22 J/g K

T 273 .15 K

333.6 J/g (ice)

Sthermostat = = 1.22 J/g K

273.15 K

Taking the ice as the system and the thermostat as the surroundings, (S) system + surroundings = 0. Thus

far it might appear as if entropy also is conserved (compare equation 1, Chapter 1). But we know

that unless there is at least a small temperature differential between the thermostat and the ice, the

ice will not melt. We cannot melt an ice cube by bringing it into contact with a large block of ice;

it must be touched to something warmer. If the temperature of the thermostat is higher than

273.15 K, Sthermostat will be smaller in magnitude than Sice , and S for the ice plus the

thermostat, or system plus surroundings, will be positive. This is the essence of the second law of

thermodynamics, which states

7/10/07 2- 37

(S)system + surroundings > 0 (6)

for any process whatever that actually occurs. The similarity, and contrast, to the statement of

the first law (equation 2, Chapter 1) should be noted. In the limit of a process that is truly

reversible (for example, thermostat and ice at the same temperature, so that the ice can melt or

refreeze by exchange of thermal energy with the thermostat), the total entropy change will

approach the value zero. Recognizing the importance of this limiting condition we may write

with the understanding that the equality can be approached as closely as we wish, if we have

sufficient patience.

From equation 6 or 6a, taken as the second basic postulate, it is possible to derive results that

are well established from our experience. There are, in general, many different paths that a

system may follow between any two specified states, of which at least one (actually, an infinite

number) will be thermodynamically reversible. Let q i and w i be the amount of thermal energy

transferred and the amount of work done along the i th path, or more generally, q 1, q 2, q rev are

the various amounts of thermal energy transferred and w 1, w 2, w rev the various amounts of

work done along these paths. Then, in general, q1 q2 qrev and w1 w2 wrev. But dE

is the same for each of these paths. That is, regardless of which path the system actually follows,

dE = q1 + w1 = q2 + w2 = = qrev + wrev

and, because qrev = T dS and wrev = - P dV (if the only work is work of expansion or compression),

it follows that, for any path,

dE = T dS - P dV (7)

This equation is valid for any process occurring in a system of constant composition. (If there is a

change of chemical composition, as would be required if electrical work were produced, or a

change of concentrations, additional terms should be added to the first-law equation and to

equation 7.) At constant volume the second term of equation 7 becomes zero and we obtain

E

=T (8)

S V

or

S 1

= (8a)

E V T

7/10/07 2- 38

Take an arbitrary system, at constant volume, that

is thermally isolated from its surroundings (so that Q =

0 and E = 0). The second law then requires that dS $

0 for any changes within this system. Divide the system

into two parts in any fashion (Figure 1). For example,

the total system might be a cup of water, which is

considered to be divided into two equal parts, or it

might be a bar of lead, with one cm3 in the center

considered as one part and the remainder as the second

part. Let E1 be the energy of the first part and E2 the

energy of the second part, and consider a flow of

energy (as thermal energy transfer, Q) from one part to

the other, holding the two sub-system volumes

constant. Then

dE = dE1 + dE2 = 0 (9)

dE1 = - dE2

The total entropy change, dS, arising from a flow of energy between the two parts, is

dS dS dS

dS = dE1 = 1 dE1 + 2 dE1

dE1 dE1 dE1

(E, V) dS1 dS

= dE1 2 dE1 (10)

dE1 dE2

1 1

dS = dE1 0 (11)

T1 T2

The necessary condition for equilibrium is that dS = 0 for the process in which q 1 = dE 1 flows

between the two parts. This can be satisfied only if T 1 = T 2. This proves that bodies in

equilibrium have the same temperature. (This is sometimes called the zeroth law of

thermodynamics, for historical reasons, although it is a consequence of the second law.)

Suppose that T1 > T2 . Then (1/T1 - 1/T2) is negative and dE1 must also be negative, showing

that part one loses energy to part two. This proves that when two bodies in contact have

different temperatures, energy flows, as a thermal energy flow (Q), from the warmer to the cooler

body.

From equation 7 we can derive a relationship for the dependence of entropy on volume.

1 P

dS = dE + dV

T T

and therefore S P

= (12)

V E T

7/10/07 2- 39

Again consider a system constrained to constant total volume, and to have a uniform temperature.

Then, as before, we can write the total change in entropy that might result from a change in

volume of either part in the form

dS1 dS

(T, V) dS = dV1 + 2 dV1

dV1 dV1

and, because total volume is constant, dV 1 = - dV2. Substitution of equation 12 gives 5

P P

dS = 1 2 dV1 0 (13)

T1 T2

This proves that two bodies in equilibrium must have not only the same temperature but also the

same pressure. It also proves that, when two bodies in contact, at the same temperature, have

different pressures, the body at the higher pressure will tend to expand and compress the body at

the lower pressure.

ISOTHERMAL ENTROPY CHANGES. Entropy changes at a single temperature follow directly from

equation 5. (Calculations involving a temperature difference or temperature change will be

treated later.)

A change of phase, under equilibrium conditions, will be at constant temperature and

constant pressure. The thermal energy transfer, Q = Q rev, will be H. Therefore,

H

S = (14)

T

For example, the entropy change for the melting of ice was found to be 1.22 J/gK or 22.0

J/molK. The entropy of vaporization of water at 100 oC is

40 , 657 J/mol

S vap = = 108 . 96 J/mol K

373 . 15 K

More typical liquids, not involving such strong intermolecular forces, have S vap values of about

92 J/molK at their normal boiling points. This is known as Troutons rule.

The work done in a reversible, isothermal expansion of an ideal gas was found to be

(equation 10, Chapter 1) Wrev = - nRT ln V2/V1. For an ideal gas at constant temperature E = 0

and therefore Qrev = -Wrev. The entropy change is thus

5

It is assumed that T1 = T2 and thus the total entropy is unchanged by a transfer of thermal

energy between the two parts. The constant-energy restriction of equation 12 is satisfied because

any work done by one part on the other can be compensated by such a transfer of thermal energy.

7/10/07 2- 40

Qrev

(T , I.G.,rev.) S = = nR ln V2 / V1 (15)

T

If the gas expands through a pinhole or stopcock (an effusion-controlled leak) into an

evacuated container (Figure 2), no work is done because the gas exerts forces only on the

immovable walls of the container. By insulating the containers we can ensure that Q = 0. The

energy is unchanged and therefore, if the gas is ideal, the temperature remains constant. This

serves as an experimental demonstration (performed by Joule, in 1844) of the dependence of

energy only on the temperature, although it is not as sensitive as a later method by Joule and

Thomson. The entropy change of an ideal gas in such an irreversible, adiabatic 6 expansion can be

calculated as follows.

Entropy is a state function, so the entropy change depends only on the initial state and the

final state. Entropy changes are independent of the path taken between the initial and final states.

When an ideal gas expands at constant temperature from V 1 to V 2, the final state is the same

whether the process is reversible or irreversible. Therefore, the entropy change for the adiabatic

expansion of the ideal gas into a vacuum is

The example just cited illustrates a general method for evaluating entropy changes in

irreversible processes. Having determined what are the initial and final states, a path is found

between those states that will be entirely reversible. Then equation 5 tells us S = Q rev/T. 7

It is of interest to calculate the entropy change for the surroundings in the reversible and

irreversible expansions above. In the reversible expansion, Q = Q rev = - Q surr = -(Q rev) surr.

6

Diabatic, like its better-known twin diabetic, implies that something passes through

(thermal energy or sugar). Thus adiabatic tells us there is no thermal energy transfer; Q = 0. In

practice we achieve adiabatic conditions by insulating the system, by maintaining system and

surroundings at the same temperature, or by carrying out the process very rapidly. Most gas

expansions are fast enough to be nearly adiabatic.

7

One sometimes sees the statement that S = Q/T for a reversible process. This is not

really wrong, but it is doubly misleading. It de-emphasizes the need to find Q rev (which is often

different from Q) and it provides no clue to finding S for an irreversible process. Equation 5, S

= Qrev /T, covers both irreversible and reversible processes.

7/10/07 2- 41

Therefore

The adiabatic expansion into a vacuum produces no change at all in the surroundings, and

therefore

Ssurr = 0

Adding together the entropy changes for system and surroundings, we obtain, for the reversible

expansion,

(S)system + surroundings = 0

The particular irreversible path chosen is an extreme case. If the gas had been allowed to

expand against a constant external pressure (as in Figure 1, Chapter 1) the entropy change for

system plus surroundings would have been positive, but less than that for the expansion into a

vacuum. The magnitude of the total entropy change (system plus surroundings) can be taken as a

measure of the degree of thermodynamic irreversibility of any process.

INTERPRETATION OF ENTROPY. We have seen that we can measure the increase in entropy by

measuring the amount of energy transferred to the system, as thermal energy transfer, Q, divided

by the (absolute) temperature, provided we measure Q along a path between initial and final

states that is completely reversible. To know whether a process will actually occur, we must

make a similar measurement for changes in the surroundings, as we will emphasize below.

Without getting involved in the detailed calculations of statistical mechanics, it is important

to look more carefully at the meaning of entropy as a spread function. In particular, there are two

ways of measuring the spreading, or the randomness, of a state. We have seen that entropy is

appropriately called the spread function because it is a measure of the amount of spreading of

energy among the molecules of a substance. However, in addition to considering where the

packets of energy are located we should look also at where the molecules are (like the yellow and

white rice molecules we mixed earlier). Remarkably, the same measurement of Q rev /T gives

information on this second type of spreading.

Consider a sample of an ideal gas, occupying an initial volume V i (e.g., 1 m 3). Assume, quite

arbitrarily for the moment, that each molecule requires some very small volume, V o (e.g., 2 3,

most of which volume elements are unoccupied at any given instant). Then we can say there are

spaces for Vi /Vo molecules (5 x 1029 in our example). If we let the gas expand to a larger volume,

Vf , then by the same reasoning there are now spaces for Vf /Vo molecules. The important thing is

7/10/07 2- 42

that we have increased the number of available spaces by the ratio V f /V i . But we already know

that if we expand an ideal gas, the entropy increases by S = nR ln V f /V i . In other words, when

we increased the number of available, or accessible, spaces by the ratio V f /V i , the entropy

increased by the logarithm of this same ratio.

We could equally well make the same kind of argument for molecules in a crystal, where the

number of available spaces is more readily counted. If some number of stray molecules are

introduced and given an opportunity to diffuse throughout the crystal, we would obtain a

substantial increase in entropy per molecule. Or we may simply drop a crystal of salt into water.

When we return, very likely the salt molecules will have diffused throughout the water. The salt

molecules, or their constituent ions, are attracted to each other and roughly equally attracted to

water molecules, so there is negligible energy difference, but there is a very high probability of

the salt diffusing into the water, never to return to the crystal unless external conditions are

changed. It is like a drop of water on the pavement. Even though energetically the water drop

would prefer to remain with its neighbors, the lure of wide open spaces is enough to make the

drop evaporate. The process is driven by an increase in entropy, or in probability.

The crystal is highly ordered; the solution is highly disordered, or random. There are more

states accessible to the salt when it is dissolved in water, or accessible to gas molecules when a

larger volume is available to the molecules. More available, or accessible, states can be equated

to a greater probability. Thus entropy is variously described as measuring disorder, or

randomness, or probability. We can always organize molecules, forming crystals or condensing a

gas to a liquid or arranging conditions such that molecules will form living structures. To do so

always has a cost involved, specifically the cost of increased randomness in the surroundings.

The second law of thermodynamics does not tell us we cannot decrease entropy in any given

sample. It tells us only that, for the universe as a whole (system plus surroundings), entropy will

always increase.

A study of how signals may be communicated from one place to another gave rise to a new

understanding of probability under the heading of information theory. Information theory turned

out to be of major importance in understanding the meaning of entropy as well as in discovering

better ways to organize the storage and distribution of information over telephone lines, as radio

or television signals, or in computers.

When investigating equilibrium or reversibility, it was necessary to find the change for the

system but also for the surroundings. Usually we prefer to ignore the surroundings most of the

time. The free energy functions provide a means of doing just that.

We began with the variables P, V, and T, to which we added energy, E, and subsequently

have added enthalpy, H, entropy, S, and now the two free energy functions, F and G, as shown in

equations 17-19 and in Figure 3.

H = E + PV (17)

F = E - TS (18)

G = H - TS (19)

7/10/07 2- 43

G = F + PV (19a)

G = E + PV - TS (19b)

We introduced the Helmholtz free energy 8 from the relationship (eqn. 4) A = F = W rev and

the observation that a change in F represents the minimum amount of work that must be done on

the system, at constant temperature, to get from the initial to the final state. For example, you

cannot put a box on a shelf without doing some work on the box (and gravitational field), nor can

you compress a gas without doing work on the gas. There is good reason for picking the correct

function. Recall that we found enthalpy, H, to be much more convenient than energy, E, when

measuring thermal energy transfers under conditions of constant pressure. For much the same

reasons, we will find G to be generally more convenient than F. The Helmholtz free energy is

more appropriate at constant volume; Gibbs free energy is better for constant pressure.

FREE ENERGY AND EQUILIBRIUM. Assume for the moment that the only work done is work of

expansion or compression, and that the composition of the system does not change. Then, from

equation 19b,

dG = dE + d(PV) - d(TS)

dE = q + w = qrev + wrev

regardless of path. We may therefore substitute q rev + w rev for dE, to obtain

dG = V dP - S dT (21)

We effectively split this equation into two parts, by holding constant first the temperature,

then the pressure:

G

=V (22)

P T

G

= S (23)

T P

8

For many years the Gibbs free energy and the Helmholtz free energy were not clearly

distinguished, and thus both were designated by the symbol F. In recent decades the symbol F

has been selected for Helmholtz free energy and the symbol G for Gibbs free energy. Unless

specifically indicated otherwise, the term free energy will always mean the Gibbs free energy in

this book. [Fig. 3: A becomes F.]

7/10/07 2- 44

Note, of course, that P and V naturally go together, as do

T and S.

An equally valid alternative to equation 20 is obtained

by substituting dE = q + w, giving

dG = q + w + P dV + V dP - T dS - S dT

(T,P) dG = q + w + P dV - T dS

(24)

But at constant pressure we may safely assume the pressure of the system is the same as the

pressure of the surroundings (meaning the part of the surroundings that is in actual contact with,

and therefore may affect, the system), so w = - P dV, where, as usual, P is the pressure of the

system. Also, we know9 that qrev $ q. Therefore,

(T,P) dG = q - T dS = q - qrev # 0

Thus

(T,P) dG # 0 (25)

in general, and for the limiting case of the reversible, or equilibrium, process,

(T,P) dG = 0 (25a)

This shows that G must be negative, or, in the limit of a reversible process, zero. That is, G is a

minimum for an equilibrium state. This is the more convenient criterion for equilibrium that was

sought. Looking for the change in free energy, G, under our normal operating conditions of

9

We introduced the assumption that wrev # w by considering an expansion or compression

of an ideal gas, and from that and the independence of dE on path, we concluded that q rev = dE -

wrev $ q. Now we may work backward from the second law, which is one of our basic postulates,

(dS)syst + surr = qrev/T + (qrev)surr/Tsurr $ 0. This inequality must be valid for any process occurring in

the system, including if qsurr = (qrev)surr, which may therefore be assumed without loss of generality.

But we know that qsurr = - q (by combining the first law with the first-law equation), and because

we are assuming temperature is constant, we may set T surr = T. Therefore (dS)syst + surr = q rev/T -

q/T $ 0 and thus qrev $ q. It follows from this that wrev # w .

7/10/07 2- 45

constant temperature and constant pressure, we need only look at changes of the system. It is not

necessary to make separate calculations for the surroundings.

We began this section with the assumption that the only work done was P dV work, or work

of expansion or compression. Now we revisit that question. Retain the conditions of constant

temperature and constant pressure, but from equation 20 we obtain

(T, P) dG = P dV + wrev

The total work done on the system may be broken into expansion/compression work and other

forms (e.g., electrical work) which we label w. For reversible processes,

wrev = - P dV + wrev

It follows that

(T,P) dG = wrev (26)

Thus, apart from providing a convenient measure of whether the system is or is not at equilibrium

(with only P dV work), the free energy tells us how much other work can be expected from a

process. In an electrochemical cell, w is the electrical energy generated by the chemical reaction.

Work against a gravitational field or against a magnetic field would also be included in w.

IDEAL-GAS EXPANSIONS. The change in free energy of an ideal gas in an isothermal expansion or

compression is particularly important because it has been found possible to express free energy

changes of all systems, whether gases or not, in this same form. The broader theory will be

developed in the discussion of physical equilibria.

Start with the definition of G, equation 19. At constant temperature,

(T) G = H - T S (27)

S = qrev /T = nR ln V2/V1

G = - T S = - nRT ln V2/V1

or

(T, I.G.) G = nRT ln P2 /P1 (28)

The same result could be obtained from equation 22.

G

G = dG = dP = V dP = nRT dP/ P = nRT ln P2 / P1

P T

FREE-ENERGY CHANGES IN CHEMICAL REACTIONS. A very important application of the free-

energy function is to the description of chemical reactions. Because G is a state function, free

energies can be added and subtracted in the same manner as enthalpies. It is not possible to

7/10/07 2- 46

assign meaningful absolute values to free energies, but handbook tables give values of G relative

to the elements from which compounds are formed. Thus the free energy of formation of any

element is, by definition, zero. From Table 1 we can see that the standard free energy of

formation of SO3 in its standard state (gas, at 1 atm pressure, at 25 oC) is - 370.4 kJ/mol, whereas

Gof (SO2) = - 300.2 kJ/mol. Subtracting (and setting Gof (O2 ) = 0) gives Greaction = - 70.2

kJ/mole. The negative value indicates that the reaction is spontaneous, showing that oxygen gas

will combine with sulfur dioxide to form sulfur trioxide at this temperature and pressure, at least

in the presence of a suitable catalyst.

Compound State Hfo Gfo Compound State Hfo Gfo

AgBr c -100.4 -96.9 H2O g -241.8 -228.6

AgCl c -127.0 -109.8 lq -285.8 -237.1

AgI c -61.8 -66.2 H2O2 g -187.8 -120.4

Ag2O c -31.1 -11.2 lq -136.3 -105.6

Al2O3 c -1675.7 -1582.3 H2S g -20.6 -33.4

Br2 g 30.9 3.1 I2 c(rh) 0 0

C diamond 1.9 2.9 NH3 g -45.9 -16.4

C graphite 0 0 aq -362.5 -236.5

CF4 g -933.6(639.9) 66.2 NH4Cl c -314.4 -202.9

CCl4 lq -139.3 -68.6 N2O g 81.6 103.2

CO g -110.5 -137.2 NO g 91.3 87.6

CO2 g -393.5 -394.4 NO2 g 33.2 51.3

CaCO3 calcite -1207.6 -1129.1 N2O4 g 11.1 99.8

aragonite -1207.8 -1128.2 NaCl c -411.2 -384.1

CaCl2 c -795.4 -748.8 aq -407.3 -393.1

aq -877.2 -816. NaOH c -425.8 -379.5

CaF2 c -1228.0 -1175.6 aq -470.1 -419.1

aq -1208 -1031.2 O3 g 142.7 163.2

CaO c -634.9 -603.3 SO2 g -296.8 -300.1

Ca(OH)2 c -985.2 -897.5 SO3 g -395.7 -371.1

aq -1002.8 -858. CH4 g -74.6 -50.5

FeO c -272.0 -244.3 C2H2 g 227.4 209.9

Fe2O3 c -824. -742.2 C2H4 g 52.4 68.4

Fe3O4 c -1118.4 -1015.4 C2H6 g -84.0 -32.0

HBr g -36.3 -53.4 CH3OH g -201.0 -162.3

aq -121.6 -104.0 lq -239.2 -166.6

HF g -273.3 -275.4 C2H5OH g -234.8 -167.9

HI g 26.5 1.7 lq -277.6 -174.8

C6H6 lq 49.1 124.5

g 82.9 129.7

*Values are in kJ/mol, for 25oC, 1 atm. The standard states for liquids (lq) and crystalline solids (c) are the pure

materials at 1 atm pressure and the standard states for gases (g) are the pure gases at 1 atm pressure in the ideal

gas state (that is, extrapolated from low pressures assuming ideal gas behavior). aq refers to the (hypothetical

ideal) 1 molal solution in water.

7/10/07 2- 47

Free energy values do not tell us anything about rates of reaction. There may be a significant

activation energy required to get a reaction to proceed, even when it is thermodynamically

allowed. (That is what catalysts are good for. By offering a different path, they may involve a

substantially lower activation energy and therefore a faster rate.) On the other hand, if G > 0,

the reaction cannot proceed, under the specified conditions, regardless of catalysts or time.

LECHATELIERS PRINCIPLE AND EQUILIBRIUM. For every chemical reaction there exists an

equilibrium point at which there is no further tendency for the reaction to proceed forward or

backward. Although the equilibrium point of most reactions is far to one side or the other, a true

equilibrium point can be calculated, and for nearly all systems the equilibrium point can be

demonstrated if the experimental techniques are sufficiently sensitive.

LeChateliers principle states that when any stress is applied to a system at equilibrium, the

system will respond in a manner that will reduce the stress. For example, the reaction

2 NO + O2!6 2 NO2

releases thermal energy (H = - 56.53 kJ/mol(NO 2)) but causes a decrease of volume, or

pressure. Therefore an increase of temperature will tend to drive the reaction to the left, so that

the reaction will absorb thermal energy, but an increase of pressure, by compression, will tend to

drive the reaction to the right to decrease the number of moles of gas and hence the pressure.

These relationships can be derived, quantitatively, from the second law.

The change in Greaction = Gproducts - Greactants with change of pressure is

G (G products Greactants )

=

P T P T

G Gproducts Greactants

=

P T P T P T

G

= V products Vreactants

P T

or

G

= V (29)

P T

7/10/07 2- 48

Similarly, from equation 23,

G

= S (30)

T P

This equation tells how G (measured at some constant temperature and pressure) depends upon

the temperature at which the process occurs. The S on the right-hand side is similarly to be

measured at a constant pressure and at a constant temperature (the temperature at which the

derivative, or the slope of G vs. T, is determined). We may therefore substitute for - S the

quantity (G - H)/T.

G G H

= (30a)

T P T

G H

= (31)

T P T

The first result, equation 29, says that if there is a volume increase during the process, a pressure

increase will cause an increase in G, making the process less spontaneous. The second equation

(31) says that if the process is endothermic (H positive), a temperature increase will make G

more negative, thus making the process more spontaneous. The equations apply to phase

changes or other equilibrium processes as well as to chemical reactions. 10 The importance of the

equations is that they give a quantitative description of how G changes, and therefore of how

the equilibrium point changes.

For the formation of ammonia, we may write the equation

G = - 16.4 kJ/mol, H = - 45.9 kJ/mol, and S = -99.2 J/molK. The reaction clearly is

spontaneous at room temperature and pressure, but it doesnt go. The activation barrier is too

great. From LeChateliers rule, we can see that an increase in temperature, to overcome the

10

It is assumed that there are no other changes that might cause a reverse effect. For

example, changes in the relative concentrations of the reactants, or addition of an inert gas, are

not within the scope of equations 29 and 30 or 31.

7/10/07 2- 49

activation barrier and reaction kinetics, will make the reaction less spontaneous, but an increase in

pressure will drive the reaction back to the right. The synthesis of ammonia is therefore carried

out at high temperature (to get the reaction to go) and at high pressure (to recover yield).

We can look at the reaction in a somewhat different way. Write

G = H - TS = -45.9 kJ/mol - T x (-99.05 J/molK)

Examining the numbers suggests that the reaction as written (25 oC and 1 atm of each gas) is

spontaneous because the reactants give off thermal energy (H = Q < 0 at const. P) without a

major change in the thermal energy of the system (T is constant). The system, as a whole, is

falling into a potential well, giving off energy that is conducted to the surroundings as thermal

energy. On the other hand, this drop in internal energy drives the system to a more ordered

internal arrangement two gas molecules collapse into one gas molecule, something like a

crystallization (loss of internal degrees of freedom, or a more orderly arrangement). Thus if we

raise the temperature (neglecting for the moment the change in values of H and S), the extra

degrees of freedom of the molecules of the elements become more important (for example, at

constant pressure they will occupy a larger volume and as speeds increase, the spread in speeds

will increase as well), so the condensation of elements to compound(s) becomes less probable.

They must be driven together by increasing the pressure.

Of course, common sense tells us much the same thing, qualitatively. At high temperatures,

compounds tend to decompose. At low temperatures, substances tend to condense, to liquids or

to crystals. Energy differences are important at low temperatures. The spread function, entropy,

is increasingly important as the temperature is raised.

A rough rule of thumb is that formation of 1 mole of gas molecules raises the entropy by

about 125 J/molK (compare Troutons rule, p. 33, which is for vaporization only at the normal

boiling point). At room temperature, the resultant increase in TS would be on the order of 40

kJ/mol of gas formed. This is a small term compared to the enthalpy change of very exothermic

reactions, such as most combustions, but it is not small for many other reactions.

Entropies of reaction for a few representative chemical reactions are given in Table 2.

Table 2. STANDARD ENTROPIES OF REACTION, 25oC

Reaction So, J/molK

2 Al (c) + O2 ----- Al2O3 (c) -313.3

C (gr) + O2 ----- CO2 +3.0

CO + O2 ----- CO2 -86.36

H2 + Cl2 ----- 2 HCl +19.6

H2 + F2 ----- 2 HF +14.1

H2 + I2 (c) ----- 2 HI +166.2

H2 + O2 ----- H2O (lq) -163.1

H2 + S (rh) ----- H2S +43.14

N2 + 3H2 ----- 2 NH3 -198.2

S (rh) + O2 ----- SO2 +11.2

3 C2H2 ----- C6H6 (lq) -333.3

7/10/07 2- 50

The fundamental equation for entropy change, equation 5, gives the infinitesimal entropy

increase for the absorption of an infinitesimal amount of thermal energy at some temperature T.

If the temperature changes continuously during the process, the sum of the entropy changes can

be written as the integral

q rev

S = dS = T

(32)

It is not at all obvious from equation 32 how this integral is to be evaluated, but it can be handled

qrev q dT q dT dT

S = = rev = rev = C (33)

T T dT dT T T

The heat capacity, C, is often nearly independent of temperature (over temperature intervals of

tens of degrees) so the equation can be simplified to the form

T2

S = C ln (34)

T1

Note that the heat capacity has not been given a subscript in equations 33 or 34; this is because

no conditions such as constant pressure or constant volume have thus far been specified. If

pressure is constant, CP is inserted in these equations; if volume is constant, CV is required. If

neither pressure nor volume is constant, it may be necessary to find an alternative path consisting

of constant pressure and constant temperature segments, or constant volume and constant

temperature segments. It may be, too, that it will be simpler to return to equation 32. For

example, in a reversible, adiabatic expansion or compression, q = q rev = 0, and therefore it is clear

that the integral, and the entropy change, must be identically zero. To apply equation 34 one

would have to define an adiabatic heat capacity that would always be zero.

7/10/07 2- 51

The entropy change for the transfer of thermal energy between two bodies at different

temperatures requires a different approach. In Figure 4, the body at the left is at a temperature

T1, the body at the right is at a lower temperature T2 , and each body is assumed large enough that

its temperature will not be appreciably affected by the flow of thermal energy.

The primary method of energy transfer in such a situation (e.g., between the Sun and the

Earth) is by radiation. But the radiation process is not at equilibrium. (Radiation at equilibrium is

called black body radiation and requires the radiation field to be in equilibrium with the radiating

body, which cannot be the case if radiation is being leaked to the low-temperature body.) We

must therefore look for a reasonable substitute that will give us an answer suitably close to reality.

We achieve this approximation to reality by a thought experiment. Add a thermal insulator

connecting the two bodies. When a steady state has been achieved, the temperature will vary

continuously with the distance, as shown in the lower part of Figure 4, but the temperature will be

constant at each point in the system even though a small amount of thermal energy is flowing past

each point. The entropy change is the sum of three terms: the entropy change of the left-hand

body at T1; the entropy change for the insulator; and the entropy change for the right-hand body

at temperature T2.

S = S1 + Sinsulator + S2

Q

S1 =

T1

where S1 is the entropy change of the body at T1 . Similarly, the entropy change for the body at

temperature T2 is

Q

S 2 =

T2

The insulator may be considered part of the surroundings and need not be further included in the

calculation for the system.11 Then for the system, which consists of the two bodies at the two

temperatures,

Q Q 1 1

S = S1 + S 2 = + = Q > 0 (35)

T1 T2 T2 T2

Superficially the thermal insulator added to the problem of Figure 4 plays no significant part

in the calculation. It can make little difference to the state, or the entropy, of a body that loses a

given amount of thermal energy at the temperature T 1 what happens to this energy after it is gone.

11

Actually, the entropy change of the insulator is zero, after the steady state has been

reached, because the state of the insulator is not changing.

7/10/07 2- 52

Similarly, to the body absorbing a certain amount of thermal energy at the temperature T 2, it can

make little if any difference to the state, or entropy, of the body, where the energy came from. At

the same time, we must recognize we have introduced an approximation by assuming the energy

transfer was thermal energy transfer under equilibrium conditions. If, for example, the energy is

transferred by radiation, higher-temperature radiation has a greater chance of knocking electrons

free as photoelectrons, so the state of the receptor may depend, at least to some extent, on the

temperature of the higher-temperature radiator. The closer the experimental situation approaches

true equilibrium, the more assurance we can have that the answers are adequate. For example, in

the paragraph preceding equation 6, in which thermal energy is transferred to the system (ice)

from the surroundings (a thermostat) at a slightly higher temperature, there is no reason to doubt

the conclusions.

Problems

1. Figure 5 shows a capillary tube dipping into a dish of water. The tubing is bent, and water

dripping from the suspended open end turns a paddle wheel before returning to the dish. By

covering the apparatus, water can be retained and the energy required is returned to the dish by

thermal conduction from the surroundings. What is wrong?

magnets. The force between the fixed magnet and the

individual magnets attached to the wheel may be taken as

proportional to 1/d, where d is the distance separating the

magnets. Show that the force between the fixed magnet

and the nearest magnet is smaller than the sum of the forces

pulling the magnets along the right-hand side. That is, 1/d 1

< 1/d2 + 1/d3 + . A magnetic shield (readily available) is

placed as shown. The wheel then rotates

counterclockwise. What is wrong?

7/10/07 2- 53

3. Find S when 2 mol of an ideal gas at 25oC is expanded into vacuum to 10 times its original

volume.

4. A vessel containing 5 mol of an ideal gas, A, is connected to an identical vessel containing 5

mol of another ideal gas, B, and the two are allowed to reach equilibrium. For this process, at

27oC, find

a. S for the gas A.

b. S for the gas B.

c. S for the entire system (S(A) + S(B)).

d. What would S be if A and B were the same gas?

5. If a gas at pressure P and volume V1 is mixed isothermally with another gas at pressure P and

volume V2 to give a mixture at pressure P and volume V = V1 + V2 , the mole fractions are N1 =

V1/(V1 + V2) and N2 = V2/(V1 + V2 ). Show that the entropy of mixing of ideal gases in this

fashion is

S = nR i

N i ln N i

where n = Gni is the total number of moles and Ni = ni /n is the mole fraction of the i th gas.

6. A vessel containing 5 mol of an ideal gas, A, is connected to an identical vessel containing 10

mol of an ideal gas, B, and the two are allowed to reach equilibrium. For the process, at 27 oC,

find

a. S, assuming A and B are different gases.

b. S, assuming A and B are the same. Explain the distinction between these two cases and

between these and problem 4.

7. Which of the following have the higher value of S?

a. CO2 at 25oC, 1 atm or dry ice at 1 atm

b. a coiled spring or the spring relaxed

c. 1 g of liquid water at 25oC or 1 g of water vapor, at the vapor pressure of water at

25oC.

d. silica glass or quartz (crystalline silica)

8. When a gas escapes through a pinhole into an evacuated chamber, the first gas to escape is

later compressed by the following gas. Explain why W = 0, despite this compression.

9. Calculate G for the processes described in problems 3, 4, and 6.

10. The heat of vaporization of cyclohexane, C6H12, is 30.46 kJ/mol at its normal boiling point,

80.7oC.

a. Calculate S for the vaporization of 1 mol of cyclohexane at 80.7 oC and 1 atm. Compare

with the Trouton constant.

b. Calculate G for the same process.

11. Calculate the free energy change when 3 mol of Ar is compressed isothermally from 2 to 6

atm at 50oC.

12. The standard free energies of formation of ethylene (C 2H 4) and of ethane (C2H6) at 25 oC and

1 atm are 68.4 and -32.0 kJ/mol. The standard enthalpies of formation are 52.4 and -84.0

kJ/mol. For the reduction of ethylene with H2 to give ethane,

7/10/07 2- 54

a. find Go

b. find So.

13. Calculate So, the entropy change under standard conditions at 25o C, for the reaction of

carbon (graphite) with fluorine gas to give the gas CF 4, using values as necessary from Table 1.

14. For each of the following reactions at 25oC calculate (using Table 1)

a. Ho b. Go c. So

2 Fe3O4 + O2 ----6 3 Fe2O3

3 FeO + O2 ----6 Fe3O4

Which form of iron oxide FeO, Fe3O4, or Fe2O3 is most stable in the presence of an oxygen

atmosphere at this temperature? Explain.

15. Would Fe3O4 (see problem 14) become more or less stable, with respect to FeO and oxygen,

as temperature is increased? Explain.

16. For the reaction at 25oC, with each gas at 1 atm,

3 H2 + N2 ----6 2 NH3

a. Find H. b. Find E.

c. Find G. d. Find S.

e. Is the reaction as written, at constant T and P, spontaneous?

f. Does the reaction as written take up or give off thermal energy?

g. Find the pressure, P, of NH3 for which G = 0.

17. In the following reactions, would you expect S to be positive or negative? Explain.

a. Ag2O (s) ----6 2 Ag (s) + O2 (g)

b. 2 CO (g) + O2 (g) ----6 2 CO2 (g)

c. 2 C (s) + O2 (g) ----6 2 CO (g)

d. CaH2 (s) + 2 H2O (l) ----6 Ca(OH)2 (s) + 2 H2 (g)

e. H2 (g) + I2 (g) ----6 2 HI (g)

f. 2 H2 (g) + O2 (g) ----6 2 H2 O (l)

g. n C2H4 (g) ----6 (C2H4)n (polyethylene)

18. A Dewar flask contains 500 ml of water at 25oC. To the flask is added 100 g of ice at - 6o C.

For the process which then occurs, find

a. H

b. S

c. the final temperature

19. Find

a. S b. H c. E

for the process of subliming 6 g of ice at - 10 oC and warming the vapor to 200oC and 4 atm.

20. One kilowatt hour of energy passes from a heater, at a temperature of 1000 K, to a room at

27oC. Find S.

21. For the freezing of 5 g of supercooled water, at - 10 oC, to ice at - 10oC, calculate

a. H b. S c. G

7/10/07 2- 55

22. The standard free energies (1 atm) of NO 2 and N2O4 at 25 oC are 51.3 and 99.8 kJ/mol For

the reaction

2 NO2 (1 atm) ----- N2 O4 (P atm)

a. find G if P = 1.

b. find the value of P (i.e., the pressure of N 2O 4) that would make G = 0.

23. In a reversible, adiabatic expansion, q = 0. Show, by setting dE = n C V dT and w = - P dV

that, if P = nRT/V, the equation w = dE can be integrated (after dividing through by T to separate

variables) to give

T2 V

(I.G., rev, adiabatic) CV ln = R ln 1 (36)

T1 V2

24. Show that, by replacing dV by d(nRT/P), the equation for a reversible, adiabatic expansion

integrates (after separating variables) to give

T2 P

(I.G., rev, adiabatic) C P ln = R ln 2 (37)

T1 P1

(Note that alternatively equation 37 may be obtained from equation 36 by replacing V 2 by nRT 2

/P2 and V1 by nRT1 /P1.)

25. Show that equations 36 and 37 for an adiabatic, reversible expansion of an ideal gas can be

put into the following forms:

a. TV R/CV = constant, or T1/T2 = (V2/V1)R/C V.

b. PV = constant, or P1/P2 = (V2/V1) , where = CP /CV .

26. An increase of entropy may correspond to an increase of randomness of velocities, or

momenta, rather than of positions. For example, when a gas is heated at constant volume there

can be no change in the spatial disorder but there is more of a spread in the molecular speeds.

What conclusions can be drawn concerning the change in temperature when an isolated

supersaturated solution spontaneously separates into two phases by precipitation of solute?

7/10/07 2- 56

3 Physical Equilibria

The power of thermodynamics lies in its applicability to all substances in all states. It is not

limited to such abstractions as ideal gases, ideal solutions, or perfect crystals, although certain of

the equations take on especially simple forms for such special cases. In the following discussions

of physical equilibria and chemical equilibria the exact thermodynamic equations will be derived

wherever possible. This will enable a rational choice of approximations for each application and a

clearer understanding of when, and what, approximations are being introduced.

The fundamental requirement for a system to be at equilibrium, with respect to a certain

process, is that under the existing conditions the process should be thermodynamically reversible.

The requirement is, from the second law, that the entropy of the system and the surroundings

should remain unchanged for small changes in the state of the system. This is a basic statement,

from which other conditions can be derived. It is not necessarily, however, the most useful way

of stating the condition of equilibrium. In this chapter the conditions for equilibrium not involving

chemical change will be put into a variety of forms. Depending upon the process considered, one

or another of these will be found most convenient.

CONDITIONS OF TEMPERATURE, PRESSURE, AND FREE ENERGY. It was shown in the previous

chapter that the second law requires that two bodies in equilibrium should have the same

temperature and the same pressure. It will therefore be assumed in the following discussion that

these conditions are satisfied. We will be interested in the question of what that temperature and

pressure must be, and how these parameters are affected by each other and by changes in

chemical composition.

It was also shown that a necessary and sufficient condition for equilibrium at constant

temperature and pressure is that the free energy of the system be a minimum, and hence that the

free-energy change of the system be zero for small changes in the system. The condition will

form the basis of the derivations in this chapter.

CLAPEYRON EQUATION. Pure water freezes at 0oC and boils at 100oC, but only under normal

conditions of 1 atm pressure. An increase of pressure will lower the freezing point but will raise

the boiling point. Both effects are easily predicted by the Clapeyron equation, which is to be

developed.

Let some substance exist in two phases, A and B, in equilibrium at some temperature and

pressure. This might be the equilibrium between ice and liquid water, or liquid water and its

vapor, or some other solid-solid, solid-liquid, solid-vapor, or liquid-vapor equilibrium. Then the

condition for equilibrium is

G = GB - GA = 0 (1)

7/10/07 3- 57

We change the temperature and simultaneously change the pressure in such a way that

equilibrium is maintained. This requires that G A and G B change by the same amount.

From equations 21, 22, and 23 in Chapter 2, the change in free energy with temperature and

pressure is

dGB = VB dP- SB dT

dGA = VA dP- SA dT

and therefore

VB dP - SB dT = VA dP - SA dT

dP SB SA S

(Equil. between two phases)

= = (3)

dT VB VA V

Because equilibrium is maintained, G = 0 and S = H/T. This gives the Clapeyron equation in

its usual form:

dP H

(Equil. between two phases) = (4)

dT TV

From this equation the change in a freezing point, or other phase transition, with change of

applied pressure can be calculated.

For example, the freezing point of water under 1 atm of air is exactly 0 oC. The freezing point

under 20 atm pressure can be calculated as follows. 1

= = = x

T T TV 273 K x 9.035 x 10 m / g 1 .013 x 10 Pa 1 J/m 3

-8 3 5

T = K = 0.14 o C

334

where we have inserted the value 0.917 g/cm 3 for the density of ice and 1 atm = 1.01325 x 105 Pa

(1 Pa = 1 pascal = 1 N/m2 = 1 J/m3).

1

The substitution of P/T for dP/dT is justified because the change in temperature is

small. More generally, one could carry out the integration to obtain IdP = P = H/V IdT/T =

H/V ln T2/T1. However, ln T2/T1 = ln (1 + (T2 - T1 )/T1 ) and for small values of x, ln(1 + x) = x.

Therefore, for (T2 - T1)/T1 small, P = H/V T/T1 or P/T = H/TV.

7/10/07 3- 58

Escaping Tendency

The thermodynamic picture of equilibrium is static, with no tendency for change in the total

amounts of material in the two phases. The molecular picture of equilibrium is dynamic, with

molecules continually passing back and forth from one phase to the other; but this dynamic model

is entirely consistent with the static concept of equilibrium because the number of molecules

passing in one direction is just equal, at equilibrium, to the number of molecules passing in the

other direction.

Employing either the macroscopic and static picture or the dynamic molecular view, we may

say that at equilibrium the tendency for molecules, or material, to escape from one phase to the

other is the same as the tendency for molecules, or material, to escape in the reverse direction.

In this language, the condition for equilibrium is that the escaping tendency for any substance

must be the same in all phases in equilibrium.

The free energy is a measure of this escaping tendency. The higher the free energy, the

greater the escaping tendency and the lower the stability of a phase. The minimum free energy, or

minimum escaping tendency, represents the most stable, or equilibrium, condition. However, for

many problems the free energy itself is not convenient. First, we cannot know an absolute value

for the free energy. We know only values relative to arbitrary standard states. Second, whatever

the arbitrary value assigned for a standard state, the value of G will become negative and infinite

as the pressure of a gas or concentration of a solute approach zero. Gases at low pressures, and

dilute solutions, are too important to permit such awkward behavior of the function chosen to

describe them. We turn, therefore, for this purpose to the vapor pressure or to an idealization of

the vapor pressure.

molecules leave the surface of the liquid at a rate equal to that at which molecules of the vapor

strike the surface, if the vapor is also at room temperature and at a pressure of 23.756 torr 2; that

is, at 100% relative humidity. If the temperature is raised the molecules in the liquid have higher

speeds and more of them will escape from the surface. The molecules in the vapor will also have

higher speeds and they will strike the surface more frequently. Is this enough to maintain

equilibrium? It is not, because as so often happens, we encounter an exponential dependence

relating energy and temperature.

The number of molecules escaping from the surface depends on the number having speeds

above some limiting value. The number of molecules having speeds above a limiting energy value

depends exponentially on the temperature, whereas the increase in average speed in the vapor

depends only on the square root of temperature. Therefore, in order to maintain equilibrium, the

density of molecules, or the pressure, must be increased, and in fact it must increase

exponentially.

An approximate equation describing the change of vapor pressure with temperature can be

derived from the Clapeyron equation by assuming the vapor to be an ideal gas. The volume of

2

1 torr = 1 mm of Hg = 1/760 atm = 133.3 Pa

7/10/07 3- 59

one mole of the vapor is RT/P and the volume of the liquid is negligible in comparison, so RT/P

may be taken as V. Thus

dP H P

=

dT T RT

or

dP d ln P H

(Ideal vapor in equil. with liquid or solid) = = (5)

PdT dT RT 2

This is called the Clausius-Clapeyron equation. It serves for calculations of changes of boiling

point, or sublimation point, with change of pressure, which is equivalent to saying that it gives the

variation of the vapor pressure of a solid or liquid with change in temperature. Vapors at their

condensation points are not ideal gases, so it is only an approximation, but it is often adequate.

The percentage change in vapor pressure, P/P, for a one-degree change in temperature for

water at its normal boiling point, can be found from the Clausius-Clapeyron equation. The heat

of vaporization of water is 2.258 kJ/g or 40,657 J/mol, at 100 oC. Therefore,

P 40,657 J/mol x 1 K

= = 0.035 = 3.5%

P 8.314 J/mol K x (373) 2 K 2

For larger ranges of temperature the differential form of the Clausius-Clapeyron equation

(equation 5) must be integrated to give the equation

P2 HT

ln = (6)

P1 RT1T2

This form assumes that the heat of vaporization (or heat of sublimation) is a constant over the

temperature range T = T2 - T1. It should be recognized that H does depend on temperature,

because the heat capacities of condensed phase and gas phase are different. The change in H is,

however, usually small compared to H itself if T is small, and the error can be further reduced

by substitution of an average value for H into equation 6.

From equation 6 the vapor pressure of water at room temperature would be calculated as

follows:

P2 2258 x 18 x(-75)

ln = = 3.30 = ln 0.0369

760 8.314 x 298 x 373

P2 = 760 x 0.0369 = 28.1 torr

Substitution of an average value for H of about 2.34 kJ/g would change the final answer to P 2 =

25.2 torr. The experimental value is 23.756 torr. Over a smaller temperature range better

agreement would be expected.

The pressure appearing in the Clausius-Clapeyron equation is the pressure of the (ideal) pure

vapor in equilibrium with the liquid. It is not necessarily the same as the total pressure applied to

7/10/07 3- 60

the liquid. For example, the pressure on water in the laboratory is 1 atm, applied by the air, but

the pressure of the water vapor at equilibrium is only 23.756 torr, or about 0.03 atm. The

pressure of a single component is often called the partial pressure, to distinguish it from the

total pressure. It is the equilibrium partial pressure, or vapor pressure, that is a measure of the

escaping tendency of the liquid. The escaping tendency of the liquid is affected, but only slightly,

by the total applied pressure.

FUGACITY. When the vapor is ideal there is a simple, exact relationship between vapor pressure

and the thermodynamic properties, especially the free energy, G (equation 28, Chapter 2). It

would be a great help to have an exact relationship for real gases and the escaping tendencies of

liquids and solids that could be employed for thermodynamic calculations.

The logical requirement for this new function, f, is that it should coincide with the vapor

pressure of a solid or liquid, and with the partial pressure of a vapor, whenever the vapor is ideal,

but it should retain the same functional relationship to G even when the vapor is non-ideal. This

new measure of escaping tendency may be considered a more practical vapor pressure. We define

the function, f, by the two equations

f2

G = RT ln (7)

f1

and

f

Lim =1 (8)

P 0 P

An alternative form of the first of these equations is to write

G = RT ln f + B(T) (7a)

with the unknown function B(T), depending on temperature, added so that absolute values can be

assigned to f even though absolute values are not known for G. The function f is called fugacity,

from the same Latin root (fugere) as fugitive. The value to be inserted for G when the

substance is not pure is an effective value, to be discussed later.

From the defining equations (7 and 8) a value for the fugacity can be found experimentally

for any substance. At a sufficiently low pressure of the vapor, fugacity will equal pressure. The

change in free energy with pressure can be found from equation 22, Chapter 2,

G = IV dP (9)

If the volume is known for each pressure, this integral can be evaluated (by numerical integration

if necessary) and the fugacity at the higher pressure can be found from the change in free energy:

7/10/07 3- 61

P2 f2 f

G = VdP = RT ln = RT ln 2 (10)

P1 f1 P1

may be written

RT

V = +

P

where is a correction term that varies with pressure and is zero for zero pressure. Then, for any

P1 and P2,

P2 P2

G = RT ln + dP (10a)

P1 P1

Fugacity tables are available for gases. When the actual volume of a gas is known at a

certain temperature and pressure, the fugacity may be approximated by means of the equation

f . P2V/RT

f P

(11)

P Pi

This equation can be derived from van der Waals equation or other similar equations of state by

neglecting second-order correction terms. Note that the fugacity differs from the true pressure of

a non-ideal gas in the opposite direction from that of the ideal pressure, P i = RT/V.

In many applications we need not know the absolute value of the fugacity but only a relative

value compared to some standard state. The ratio, f /f o, where f o is the fugacity in the particular

standard state chosen, is called the activity. The activity is a dimensionless ratio; the value of the

ratio depends on the choice of standard state as well as the state of the substance being described.

Different standard states are frequently employed in different problems, or often even in the same

problem, so different values of the activity are obtained for a given state of any substance.

In the discussions that follow the reader may, without appreciable error, substitute the term

vapor pressure for fugacity, or else the term partial pressure if the substance is itself a vapor.

The equations are exactly true as given and are approximately true if vapor pressures (or partial

pressures) are chosen as approximations to the fugacity. (Note, however, that the total applied

pressure may be very different from the vapor pressure, or fugacity, of a solid or liquid.)

7/10/07 3- 62

expression relating total applied pressure to the temperature. From it an approximate equation

(equation 5), the Clausius-Clapeyron equation, was derived by assuming the vapor to be ideal and

by neglecting the volume of the condensed phase. It is now possible to derive an exact form of

the Clausius-Clapeyron equation, which will prove invaluable in later applications where the

assumptions of ideal vapors will be unnecessary or inappropriate.

Recall that fugacity is a measure of tendency to escape. Now we wish to consider the process

of escape of molecules from a condensed phase into the vapor phase at a sufficiently low pressure

(of vapor) that interactions in the vapor are negligible. Thus we take as the escaped state a

pressure, P*, sufficiently low that f* = P*. If H* is the enthalpy of the vapor at such a low

pressure, and H is the enthalpy of the substance (at the equilibrium pressure) in the condensed

phase (liquid or solid), the Clausius-Clapeyron equation may be written in the exact form

d ln f H * H

(Vapor in equil. with liquid or solid) = (12)

dT RT 2

The enthalpy difference, H* - H, is the heat of vaporization (or the heat of sublimation) plus a

small correction term for the change of pressure from the equilibrium pressure to the very low

pressure.

P* H

H * H = H vap + dP (13)

P

P T

The second term, the variation of enthalpy of the vapor with pressure, is sufficiently small that it

can usually be neglected; for an ideal gas it would be identically zero. Also, for an ideal gas the

fugacity is equal to the vapor pressure, so for an ideal gas, equation 12 becomes identical with

equation 5.

The exact Clausius-Clapeyron equation may be derived as follows. The free-energy change

in going from the condensed phase, at some pressure P, to the vapor at the very low pressure P*

is

f*

G = G * G = RT ln

f

(For the vaporization step there is no change in free energy, or fugacity, but there is a change in

free energy with change of pressure.) This is easily rearranged to give

G G*

ln f = + ln f *

RT

To find the temperature dependence we take the derivative with respect to temperature (with

pressure constant and maintaining equilibrium between the two phases):

7/10/07 3- 63

d 1 1 d

= (G G *) (G G *) + d ln f *

d ln f

+

dT dT RT RT dT dT

The last term is zero, because f* = P* was chosen as an arbitrary but fixed value, independent of

temperature. Employing equation 23, Chapter 2, the remaining terms give

d ln f G * G S * S

= +

dT RT 2 RT

H * H

=

RT 2

The liquid phase is the most difficult to understand and to describe quantitatively. The

molecules cannot be considered independent of each other, as in a gas, nor are they arranged in a

regular, fixed structure, as in a crystal. There is great individuality of behavior of pure liquids,

and of solutions, so that few generalizations can be made.

The one area in which thermodynamics has been most extensively and successfully applied to

solutions is that of very dilute solutions. The laws that can be derived for very dilute solutions are

largely independent of the nature of the solute molecules but depend on the number of such solute

molecules. The properties are called colligative (meaning collective). The dilute-solution laws

are commonly applied to solutions of moderate or even high concentrations, much as the ideal-

gas law is applied to real gases as an approximation. Indeed, just as the ideal-gas laws were

suggested by measurements on real gases, the dilute-solution laws were suggested by

measurements on non-dilute solutions. However, the errors encountered in extrapolation of the

equations to moderate or high concentrations can be quite large. It is best to remember that these

equations must hold for infinitely dilute solutions and may hold for greater concentrations.

In the following derivations and formulas it will be convenient to call the major constituent

the solvent and designate it by the subscript 1; minor constituents will be called solutes and

designated by subscripts 2, 3, etc. Concentrations will be expressed as mole fractions or, later, as

molarity or molality. The mole fraction of any component in a mixture is the number of moles of

that component divided by the sum of the number of moles of all components. Letting n 1, n 2,

represent the number of moles of components 1, 2, etc., the mole fraction, N i, of the i th

component is

ni

Ni =

n1 + n2 +

Mole fractions are also sometimes represented by the symbol X i. Molarity is the concentration

expressed as moles of solute per liter (or 1000 cm 3) of solution. For example, 0.3 mol of NaCl in

7/10/07 3- 64

sufficient water to give one liter of solution gives a 0.3 molar solution, written 0.3 M. Molality

is the concentration expressed as moles of solute per kilogram of solvent. 3 Thus 0.3 mol of NaCl

in 1 kg of H2O gives a 0.3 molal solution, written 0.3 m. For dilute water solutions, molarity

and molality are nearly the same, but for concentrated water solutions or, especially, solutions in

other solvents, the molarity and molality may be very different.

DILUTE-SOLUTION POSTULATE. The laws of dilute solutions rely on a single postulate, which has

been demonstrated to have wide validity for solutes that do not dissociate upon dilution. Thus

the following equations apply to sugar or to Na+ ions and Cl- ions (because NaCl is fully

dissociated at moderate concentrations) in water, or to solutions of polymeric materials, such as

polystyrene, even though these may have molar masses of hundreds of thousands. The range of

validity that is, what constitutes a very dilute solution will differ from one solute to another,

so some judgment is required is estimating the accuracy of the dilute-solution laws in particular

examples. The methods of statistical mechanics show that the condition to be satisfied is that

solute-solute interactions should be negligible as compared with solute-solvent and solvent-

solvent interactions. When the solute does dissociate upon dilution, as does acetic acid, the

dilute-solution laws generally can be applied to the dissociation products. In practice it is often

adequate to consider the solute to be a mixture of undissociated and dissociated solute and treat

these as different solutes.

If the fugacity of a solute is plotted against concentration it is obvious that the fugacity (or

vapor pressure) of the solute must decrease to zero as the concentration of the solute decreases to

zero. There are, in principle, three possibilities, as shown in Figure 1. The slope at the origin

might be infinite, or zero, or have some finite, non-zero value. On the basis of many experimental

3

By convention, variables (such as mole fraction, or mass) are written in italics, whereas

units are written in roman type faces (e.g., g and mg for gram and milligram). Concentrations

(which are variables) are an exception in that the units (molarity or molality) are written in italics.

7/10/07 3- 65

measurements, the following statement is put forth as a postulate: For all solutes that do not

dissociate upon dilution, the slope of fugacity against concentration, df/dN 2, at the origin is

finite and non-zero.

HENRYS LAW. In 1803 William Henry proposed, on the basis of his measurements, that the

solubility of a gas in a liquid increases in proportion to the pressure of the gas. This result can

be easily derived from the dilute-solution postulate, which can be written

df2

=k (14)

dN2 N2 0

The number k is the slope at the origin, which will depend on the solute and on the solvent, and

the notation N2 !6 0 indicates that the solution is very dilute. (That is, as N2 approaches zero the

equation must become valid.) A derivative is, by definition, the limiting value for the ratio of the

changes in the dependent and independent variable or, in this case, the limiting value, as N 2 is

made small, of the ratio f2/N2. But f2 cn be written f2 - 0, for a small increment of fugacity at

the origin, and N2 can similarly be written N2 - 0. With these substitutions, we write

df 2 f f 0 f

= 2 = 2 = 2

dN2 N2 0 N 2 N2 0 N 2 0 N2 0 N 2 N2 0

( N 2 0) f2

=k

N2

or

(N2 0) f 2 = kN2 (15)

For a very dilute solution the fugacity, and vapor pressure, of the solute are very small and

therefore the fugacity is equal to the vapor pressure.

( N 2 0) P2 = kN 2 (15a)

This is Henrys law. For dilute solutions the concentration, c 2, expressed as molarity or molality,

is proportional to the mole fraction, N 2, so Henrys law may be written in the more general form

or

7/10/07 3- 66

(c2 0) P2 = kc2 (15c)

The value of k depends on the solute, the solvent, the temperature, the units in which c 2 is

expressed (mole fraction, molarity, or molality), and the units in which f 2 or P 2 is expressed

(usually atm, Pa, or torr). Small deviations from equation 15c may be observed at moderate

concentrations because the vapor is not ideal; large deviations may occur because the solution

may not obey equation 15b (or 15) in solutions that are not highly dilute.

An example of Henrys law is provided by the human respiratory-circulatory system. Blood

entering the lungs is exposed to air containing approximately 0.20 atm oxygen, and it becomes

saturated, at this pressure, with oxygen. When the blood reaches the capillaries, the pressure of

oxygen in the surrounding tissues is less than 0.20 atm, so oxygen is given up by the blood to the

surrounding tissues. Meanwhile, the blood picks up carbon dioxide at a comparatively high

pressure in the tissues surrounding the capillaries and loses carbon dioxide in the lungs where the

partial pressure of the CO2 is comparatively low. Both gases are bound chemically within the

blood (with hemoglobin or as carbonates), but that equilibrium is controlled by the fugacity of the

free gas in the liquid phase, which is controlled in turn, through Henrys law, by the partial

pressure of the gas in the surrounding medium (the air of the lungs or the fluids around the

capillaries.).

NERNSTS DISTRIBUTION LAW. When two solutions, containing the same solute but different,

immiscible solvents, are brought to equilibrium, the final concentration of the solute will generally

be higher in one solvent than in the other. However, the ratio of the concentrations remains

unchanged if more solute is added, provided the solutions are dilute.

Consider one solute distributed between two immiscible solvents, A and B (Figure 2). The

concentration of the solute in solvent A is c 2A and the concentration of the same solute in solvent

B is c2B. From Henrys law,

(c

A

2 0) f2A = kAc2A

(c

B

2 0) f2B = kBc2B

In order that the system be at equilibrium, the free energy of the solute must be the same in the

two solutions. This requires that the fugacity of the solute be the same,

f 2A = f 2B

and therefore

k Ac2A = kB c2B

or

(c A

2 0, c 0

B

2 ) c 2A k B

= = KD (16)

c 2B k A

7/10/07 3- 67

The ratio of the two Henrys law constants, k B/kA , is also a constant, which is known as the

distribution constant, or distribution coefficient, K D . Nernsts distribution law states that

for dilute solutions, a solute will divide itself between

two immiscible solvents to give a constant ratio of concentrations

(over a range of concentrations for which k A and kB are

constant).

The distribution law is the basis of solvent extraction

procedures. Distribution coefficients are also important, for

example, in the storage of gasoline, which is a mixture of many

hydrocarbons. The storage tanks must be vented to the air and

consequently water vapor can condense in the tanks. The water

is not significantly soluble and simply sinks to the bottom of the

tank, where it might be expected to cause no trouble. However,

the blending of gasolines, especially for winter driving, requires a

carefully controlled percentage of the lighter hydrocarbons, such

as butane and pentane. Because these hydrocarbons are more

soluble than the heavier hydrocarbons in water, the water layer

becomes richer in light hydrocarbons and the gasoline becomes

slightly depleted in the lighter, more volatile compounds. The

effect is to make the gasoline lack cold-weather starting

properties if the fractionation is not properly compensated for.

IDEAL SOLUTIONS. Henrys law states that, over the concentration range for which it is valid,

the fugacity, or vapor pressure, of a solute is proportional to the concentration of that solute.

The proportionality constant for each solute-solvent system must be determined by experiment.

In certain solutions the Henrys law constant takes on a particular value the value of the

fugacity, or vapor pressure, of the pure component when the concentration is expressed as a

mole fraction. Then, for the ith component,

A solution for which each component obeys equation 17 is called an ideal solution. Equation 17

is called Raoults law. It will be shown later that Raoults law will necessarily apply for the

solvent (the major component) when a solution is very dilute, just as Henrys law must then apply

to the solute (the minor component).

One of the properties of an ideal solution is that there is no heat effect upon mixing the

components. Another property is that the volumes are additive.

(I.Soln.) V A+ B = V A + V B

Let vA and vB represent molar volumes of liquids A and B, and let V represent the volume of the

solution of A and B. Then, for an ideal solution comprising n A mol of A and nB mol of B,

7/10/07 3- 68

(I. Soln.) V = nA vA + nB vB (18)

equation, for non-ideal solutions, similar to equation 18, by which

the total volume may be ascribed to the effective contributions

of the two components. These effective molar volumes (further

defined below) will be indicated

by V A and V B . Then

solution is ideal or not. The equation may be extended to any

number of components.

If the number of moles of A is held constant and more B is

added to the solution, how much will the total volume increase?

Assume V A and V B are not significantly changed. 4 Then

dV = d (n A V A ) + d (n B V B )

(nA ) dV = VB dnB

V

= VB (20)

n B nA

The partial molal volume (or partial molar volume) is the effective volume per mole. A graphical

interpretation of the partial molal volume is that it is the slope of the plot of total volume against

moles of the component added, at constant temperature and pressure, with the amounts of all

other components held fixed (Figure 3).

Even for an ideal solution, we cannot write an equation for free energy comparable to

equation 18.

G n1G1 + n2G2 + n3G3 + ...

because the mixing process introduces an increase of entropy that decreases the free energy. It is

particularly important, therefore, to define an effective, or a partial molal free energy. For the i th

4

It will be shown later that even this restriction is not important, because the changes

would be compensating.

7/10/07 3- 69

component of a solution,

G

Gi = (21)

ni T,P,n

This definition shows that the effective free energy per mole of the i th component is the rate of

change of the total free energy of the solution upon addition of a small additional amount of the i th

component, holding temperature, pressure, and the amounts of all other substances constant. As

in equation 19, one can write, for any solution,

The partial molal free energy includes correction terms for the heat of mixing as well as the

entropy of mixing. One should therefore employ the partial molal free energy, or the effective

free energy per mole, in all equations. For a pure substance the partial molal free energy is

identical with the molal free energy.

The significance of the partial molal free energy in chemical thermodynamics cannot be

overemphasized; it is the necessary key to the treatment of all solutions, whether solid, liquid, or

gaseous. And, inasmuch as it includes pure materials as a special case, it provides a single

function for the thermodynamic treatment of all substances. A necessary condition for physical

equilibrium is that, for each substance, the partial molal free energy must be the same in every

phase. Furthermore, chemical reactions can occur only in a manner that will minimize the total

free energy (for the isothermal process), which is a sum of partial molal free energies, each

multiplied by the number of moles (equation 22). Thus Gi is a measure of the potential reactivity

of the ith species. Because of this particular importance, the partial molal free energy is often

called the chemical potential, and given the symbol i.

Chemical potential Gi = i

The free energy of a solution depends on the number of moles of each of the constituents, on

the temperature, and on the pressure. Therefore the change in free energy arising from changes in

any of these quantities can be written as the sum

G G G G G

dG = dn1 + dn2 + dn3 + + dP + dT

n1 n2 n3 P T

It is to be understood that each of the partial derivatives is evaluated with the other variables held

constant. Substitution of equation 21 and of equations 22 and 23 of Chapter 2 puts this equation

into the form

7/10/07 3- 70

Equation 22 arises from the definition of partial molal free energy, and therefore is

completely general. It can be differentiated, term by term, to give

which relates the changes in partial molal free energies to changes of the amount of any

constituent, changes of temperature, or changes of pressure all evaluated, of course, at some

particular concentration, temperature, and pressure. An important variation of this equation is

obtained by assuming constant temperature and pressure:

(T , P ) n1 dG1 + n2 dG2 + n3 dG3 + = 0 (25a)

This shows explicitly that the extra terms appearing in equation 24 (beyond equation 23) dont

add anything they add up to zero. But more important, equation 25a shows clearly that the

sum of changes in free energy terms vanishes; the changes compensate. A similar derivation for

partial molal volumes would justify the earlier assumption about compensating changes for

different components.

RAOULTS LAW. The addition of a small amount of solute to any solvent will, of course, increase

(from zero) the vapor pressure of the solute. It will also decrease the vapor pressure of the

solvent below the value for the pure solvent. The solute vapor pressure is given by Henrys law

(equation 15); the solvent vapor pressure is given by Raoults law, which says that the vapor

pressure of the solvent is proportional to the mole fraction of the solvent.

From equation 25 we can derive the relationship between the fugacity or vapor pressure of

the solvent and the composition of the solution. Substitution of equation 7a into equation 25a

gives, for three components,

n1 d ln f1 + n2 d ln f2 + n3 d ln f3 = 0

Dividing by n1 + n2 + n3 gives

(T,P) N1 d ln f1 + N2 d ln f2 + N3 d ln f3 = 0 (26)

For N2 and N3 very small, equation 15 requires that f2 /N2 = df2 /dN2 . Therefore,

(N2 0) N2 d ln f 2 = N2

df2 dN

= N2 2 = dN2 (27)

f2 N2

7/10/07 3- 71

(N2 0, N3 0) N1d ln f1 + dN2 + dN3 = 0 (28)

and integration from pure solvent (N2 = N3 = 0) to dilute solution (N2 and N3 very small) gives 5

f1

N1 ln + N2 + N3 = 0

f1o

The logarithm can be expanded by means of the approximation

ln (1 - x) = - x

for x << 1.

f1 f1o f1 f1o f1

ln = ln

1 =

f1o f1o f1o

Divide by N1 and rearrange, writing N2 for N2 /N1 and N3 for N3 /N1 because N1 is practically one in

the dilute solution. (This approximation, like others in the derivation, ignores terms of the order

of N22.)

f1 = f1o(1 - N2 - N3)

The sum of the mole fractions is, from the definition, 1. Therefore,

(N1 1) f1 = f1o N1 (29)

This is Raoults law, which must apply for the solvent in a very dilute solution. It gives the

fugacity of the solvent, in the solution, in terms of the fugacity of the pure solvent, f 1o, at the same

temperature and pressure. The notation (N 1 !61) at the left means that the equation is valid when

N1 is very nearly equal to 1, just as the notation (N2 !60) means N2 has been required to be very

nearly equal to zero.

Raoults law applies for nearly pure liquids, for which the vapor pressure is not necessarily

small and therefore the fugacity is not in general exactly equal to the vapor pressure. However,

the ratio of the fugacities will be equal to the ratio of vapor pressures when f 1 . f 1o and P 1 . P 1o.

5

N1 may be considered as constant during the integration, because it is always nearly 1.

Alternatively, equation 28 may be expressed in terms of n 1, n 2, and n 3 and the integrated equation

divided by N1 to give the same result.

7/10/07 3- 72

f1 P1

o

=

f1 P1 o

An ideal solution is defined as one in which all components obey Raoults law at all

concentrations.

(I.Soln. ) fi = fio Ni (29b)

Because fi and fio may be quite different, fi /fio may be quite different from Pi /Pio . That is, the non-

ideality correction for the vapor may be quite different at different values of the pressure of the

gas (Pi vs. Pio). If the vapors can be assumed to be ideal, then

(I.Soln.,IdealVapors) Pi = Pi o N i (29c)

additive volumes (equation 18) and additive enthalpies (no heat of

solution).

reservoir of pure solvent, at the same temperature and pressure,

solvent will necessarily pass from the pure solvent to the solution

because the fugacity of the solvent in the solution, f 1 = N 1f 1o, is

less than the fugacity of the pure solvent, f 1o.

achieve equilibrium.

Equilibrium can, however, be reached if the fugacity, f 1, of

solvent in the solution is increased by an increase of pressure on

the solution (but not on the pure solvent reservoir). The

additional pressure required, which may be quite large, is called

the osmotic pressure.

One effective experimental arrangement for demonstrating

osmotic pressure is shown in Figure 4. The solvent, in the

7/10/07 3- 73

beaker, passes through the membrane (called semipermeable because it allows the solvent

molecules to pass, but not the solute molecules, which typically are larger). This dilutes the

solution in the thistle tube and forces the solution up the stem, increasing the hydrostatic pressure

on the solution.

Consider a system in which there is pure solvent, at atmospheric pressure, on both sides of a

membrane. Addition of solute to one side, to form the solution, lowers the fugacity of the solvent

by dilution, but an increase of pressure on the resultant solution can increase the fugacity to its

original value. The free-energy changes caused by addition of the solute and by the change of

pressure will be

G1 G1

dG = dn + dP

n 2 P n2

1 2

P

and the sum of these terms must be zero, to maintain equilibrium with the pure solvent phase.

The free-energy values should be understood to be the effective, or partial molal, free energies in

these equations. Substitution of equation 7a into the first term and equation 22 of Chapter 2 into

the second, representing the volume of the solvent by its partial molal value, V 1 , gives

RTd ln f1

dN2 + V1dP = 0 (30)

dN2

( N 2 0) d ln f1 dN

dN 2 = 2 = dN 2 (31)

dN 2 N1

and therefore

RTdN 2 + V1 dP = 0

or

RT

dP = dN2

V1

Integration from N2 = 0 to N2 = N2 (a very small value) gives the expression for the osmotic

pressure,

(N2 0) P =

RT

N2 (32)

V1

The pressure produced can be quite large, even for dilute solutions. The molar volume of

water at 25oC is 18 x 10-6 m3 and RT is 8.314 x 298 = 2.48 kJ/molK. Thus if N2, the mole

7/10/07 3- 74

fraction of impurity in the water, is only 10 -3, the osmotic pressure is 1.38 x 105 Pa = 1.36 atm or

1032 torr. The effectiveness of osmotic processes is often limited by the poor selectivity of

available membranes, usually based on size differences between solute and solvent molecules.

Equation 32 can be easily remembered by its similarity to the ideal-gas law.

(P)V1 = N2 RT looks like PV = nRT. Note, however, that the volume, V 1 , refers to the

solvent, whereas N2 is the number of solute molecules in that volume. 6

Osmosis may be considered to be simply a diffusion of solvent molecules from a more

concentrated (in solvent) solution to a less concentrated (in solvent) solution. It is of great

importance to life processes. The direction of diffusion of water can be reversed by exposure of

plant or animal cells to solutions more concentrated in solute than are the cell fluids (e.g., by

over-fertilization). Reverse osmosis has been applied to the problem of producing fresh water

from salt water. When the salt water is compressed beyond the osmotic pressure, water flows

through a membrane, leaving the salt behind.

CHANGE OF BOILING POINT OR FREEZING POINT. Addition of sugar to water will raise the boiling

point but lower the freezing point of the water. Addition of gasoline to water will lower the

boiling point but leave the freezing point essentially unchanged. Addition of gold to silver will

raise the freezing point of the silver, although addition of silver to gold lowers the freezing point

of the gold. These effects, which may seem to have no consistent pattern, are all predictable by a

single equation, knowing only certain properties of the pure substances and the mutual

solubilities.

An impurity added to a substance at a phase transition point will usually go preferentially into

one phase or the other. This lowers the fugacity of the major component in the phase that has

become impure and upsets the equilibrium.

Solvent is present in both phases and it is a necessary condition for the equilibrium that the

free energy of the solvent (as well as solute) should be the same in the two phases, both before

and after addition of solute. After addition of solute to one phase, if equilibrium is re-established

by changing the temperature of the two phases, the condition for final equilibrium is that the sum

of concentration and temperature effects on the free energy of the solvent in the impure phase

should equal the temperature effect on the free energy of the solvent in the pure phase.

dG1 = dG1o

Substituting fugacities

(equation 7a), ln f 1 ln f 1 ln f 1o

dN 2 + dT = dT

N 2 T T N 2 T N2

6

A pseudo-derivation is as follows. If P1o V1 = N 1o RT for pure solvent, P1V1 = N 1 RT for

the solution, and V1 can be assumed equal for both, then

(P1o P1 )V1 = (N1o N1 )RT or PV1 = N2 RT . (But of course the ideal-gas law is not really

applicable to solutions.)

7/10/07 3- 75

For example, if sugar is added to water at the boiling point, the change in fugacity of the liquid

water is given by the left-hand side and the change in fugacity of the pure (that is, sugar-free)

water vapor is given by the right-hand side. From equation 31 the first term is just - dN 2, and

from the exact Clausius-Clapeyron equation (12),

d ln f 1 H * H d ln f 1o H 1 * H 1o

= 1 2 1 and =

dT RT dT RT 2

in which H1* is the enthalpy of the solvent vapor at very low pressure, H1 is the (partial molal)

enthalpy of the solvent in the impure phase at the pressure of the equilibrium, and H 1o is the

(partial molal) enthalpy of the solvent in the pure phase in equilibrium with the impure phase.

Substitution of these expressions gives

H 1 * H 1 H 1 * H 1o

dN 2 + =

RT 2 RT 2

dN2 =

(

H1 * H1 H1 * H1o

dT

)

RT 2

Ho H

= 1 2 1 dT

RT

This relates the change in temperature, from the normal equilibrium temperature for the pure

substance, to the change in mole fraction of impurity in the substance (in one phase only).

Because N2 = N2 - 0 = N2, the equation may be rewritten

H 1o H 1

(N 2 0) N2 = T (33)

RT 2

It is clear that T, which is the change in boiling point or freezing point, must have the same sign

as H1o - H1, which is the enthalpy for the solvent going from the impure phase to the pure phase.7

For example, if a solution of sugar and water is boiled, the pure phase is the water vapor and

thus H1o is the enthalpy of water vapor at the prevailing pressure; the impure phase is the liquid

solution and so H1 is the (partial molal) enthalpy of the water in the sugar solution; and H1 o - H1 is

therefore the heat of vaporization of water, which is positive. It follows that the boiling point of a

sugar-in-water solution must be higher than the boiling point of pure water, at the same pressure.

7

As a mnemonic device one may remember that scientists, and indeed all moral

individuals, strive for greater purity. Thus H is the thermal energy absorbed in going to the

purer phase.

7/10/07 3- 76

If the solution of sugar and water is cooled to the freezing pint, pure ice will separate out. Then

the pure phase is the ice and so H1o is the enthalpy of the ice, H1 is the partial molal enthalpy of

the water in solution, H1o - H1 is the heat of freezing (- 334 J/g), and T will be negative.

If CCl4 is mixed with water it will not dissolve, but the vapors mix. Then N2 will be the mole

fraction of CCl4 in the water vapor and H1 o - H1 will be the enthalpy of the (pure) liquid water

minus the enthalpy of water vapor; this H is negative and the boiling point of the water is

accordingly decreased. The boiling point of CCl 4, or of any other liquid immiscible with water,

will be similarly depressed by the addition of water, a phenomenon known as steam distillation.

An alternative expression is

H 1 T

N 1 = (34)

RT 2

where N1 is the difference in mole fraction of the major component (N1A - N1B ) and H1 is the

difference in enthalpy of the major component (H 1A - H 1B).

THE IMPORTANCE OF COLLIGATIVE PROPERTIES. The equations for lowering of vapor pressure

of the solvent (Raoults law), for osmotic pressure, and for change of boiling point or freezing

point, share a common characteristic. Each of these expressions involves the mole fraction of the

solute or, equivalently, the mole fraction of the solvent, and is totally independent of any of the

individual properties of the solute. Within the range of dilute-solution laws, the effects calculated

for any given solvent depend solely on the properties of that solvent and on the total number of

molecules of solute added, even if there is a mixture of several kinds of solute molecules. That is

why the quantities measured (vapor pressure lowering, osmotic pressure, and change of boiling or

freezing point) are called colligative properties.

Measurement of a freezing point lowering, for example, will permit calculation of the number

of moles of solute, so that, knowing the number of grams of solute added, an average molar mass

can be found. This is an effective means of showing whether a solute dissociates, and into how

many parts. The colligative properties are also very important for determining molar masses in

polymeric materials.

The limitation to very dilute solutions is not a severe handicap in practice. Measurements

can be made at several concentrations and the values extrapolated to zero concentration. The

dilute-solution laws provide assurance that the extrapolation will be a straight line at the low

concentration end. Also, in many applications the important question is whether the solute is or is

not dimerized, or dissociated. An approximate value, at moderate concentrations, can provide the

answer.

Phase Diagrams

The dilute-solution equations provide important information concerning behaviors of both

solvents and solutes when solutions approach infinite dilution, but they lack information that may

be required. They do not predict actual melting points or boiling points of pure materials, nor do

they predict values of the Henrys law constants. Only very general characteristics are predicted

7/10/07 3- 77

for concentrated solutions. Such information is usually best presented in graphical form. Only a

brief introduction is possible here, but it will provide a guide to the meaning of phase diagrams

and how to interpret them.

By a phase we will mean any generally homogeneous region, whether vapor, liquid, or solid.

Because vapors always mix, there can be only one vapor phase. Some liquids are miscible, others

only partially so, and some are essentially immiscible. Solids generally do not mix significantly,

although some solid solutions are known.

GIBBS PHASE RULE. You probably recall the general axiom from mathematics for solution of

equations in more than one unknown. If there are n variables, or unknowns, there can be a

unique solution if and only if there are n conditions, or equations. Two unknowns require two

equations, and so forth. More than two (independent) equations give no possible solutions.

Fewer conditions give an infinite number of possible solutions. The number of conditions

permitted but unspecified is called the number of degrees of freedom.

For example, if a salt may have three distinct hydrate forms (each with a different number of

water molecules incorporated into the crystal structure), then only a certain number of these may

co-exist in equilibrium. Fewer hydrates present imply one or more degrees of freedom, whereas

more hydrates than the allowed number will cause some of the forms to disappear as water

molecules are exchanged between them.

Let v represent the number of variables and e the number of equations relating them. Then

the number of degrees of freedom, f, is

f=v-e (35)

except that it is sufficient to know c - 1 concentrations in each phase. Thus

v = p(c - 1) + 2

Each component must have the same free energy, or fugacity, in each pair of phases, giving

c(p - 1) equations, or conditions. Therefore the number of degrees of freedom (remaining) is

8

Usually the number of components is simply the number of things you would mix

together. Occasionally there is possible uncertainty. You might, for example, mix ammonia gas

and hydrogenchloride to form NH4Cl. Then, because there may be excess NH3 or HCl (but not

both), there would be two components. However, if you began with NH4Cl, the ratio of HCl to

NH3 is predetermined and there is only one component.

7/10/07 3- 78

f = p(c - 1) + 2 - c(p - 1)

=c-p+2 (36)

corresponds to a single

phase. The lines are the

common borders, and

thus represent two phases

in equilibrium (or three

phases at a point)..

You will recall from experience with drawing graphs that a point (or any finite number of

points) corresponds to no degrees of freedom. A line (or a finite number of lines) represents one

degree of freedom; setting one variable determines the other. Two degrees of freedom yield an

area (or more than one area).

freedom may vary from zero to two.

(c = 1) f=c-p+2=3-p (37)

A single phase (vapor, liquid, or solid) is therefore represented by an area. Two phases (solid-

liquid, solid-vapor, or vapor-liquid) are restricted to a line. Three phases yield a single point,

called the triple point (solid + liquid + vapor). The phase diagram (with T on the vertical axis, to

match following diagrams) is shown in Figure 5.

You can calculate the slopes of the three lines from the Clapeyron and Clausius-Clapeyron

equations, knowing the heats of fusion and of vaporization or sublimation and the densities of the

phases. The upper end of the liquid-vapor line simply stops above the critical point the

distinction between liquid and vapor disappears.

phase with two components on a two-dimensional page if we kept both temperature and pressure

as external variables. We consider here the restricted example where pressure is maintained

constant (e.g., at atmospheric pressure). Then Gibbs phase rule tells us the degrees of freedom

are, again, with c = 2,

It follows that wherever there is a single phase present, that phase must be represented by an area

(two degrees of freedom). If there are two phases present, the compositions are restricted to a

line (or sometimes more than one line, but still one degree of freedom). Three phases can coexist

7/10/07 3- 79

only at a point, or a set of

points, with no remaining

degrees of freedom.

Accordingly, an area can

represent only a region in

which there is a single phase,

of variable composition.

There are two apparent

exceptions. First, the

solubility of one solid in

another is typically so

states. b) Phase diagram. The area between the curved lines is not part of the equilibrium phase diagram.

There can be no phase of such temperature and composition.

small that the area of a pure solid will look like a single, vertical line. Second, when two

phases, solid or liquid, are in equilibrium, those two phases will have different compositions and

therefore different areas, bordered by lines that are separated from each other, as in the benzene-

toluene diagram of Figure 6. Each line is simply the border of its respective area. If the overall

composition falls between those lines, or areas, the material will split into variable amounts of the

left and right areas (phases). The region between phases has been given the unfortunate label of a

two phase region; a better description is a forbidden area. There can be no phase present with

a composition falling in such a forbidden area. The relative amounts of the left phase and right

phase are given by the lever-arm rule. If C L and C R are the compositions (as percentages of either

phase say the left-hand phase) and C is the overall composition of the mix at some point, the

relative amounts (masses) of the left-hand and right-hand phases are given by

m1 (C - CL ) = m2 (CR - C) (39)

Similar behavior is shown by two immiscible solids or two immiscible liquids. Carbon

tetrachloride and water liquids split into two layers, with very little solubility of either liquid in the

other. At higher temperatures, however, the vapors mix freely. Thus the basic phase diagram is

as shown in Figure 7a. There are three possible phases: the vapor, at higher temperatures, liquid

CCl4 at room temperature and below, and liquid water. The two liquid phases can co-exist, but

there is no liquid phase with composition falling in the general range of 95% CCl 4/5% water to

95% water/5% CCl4 (where the numbers are illustrative only, and depend somewhat on

temperature). Figure 7a is somewhat difficult to interpret, so it is customary to add a horizontal

line as a marker, to dramatize the lowest vapor temperature of the mixture, as in Figure 7b.

(There can be no equilibrium across a horizontal line, which would connect points at different

temperatures.) Also, if the diagram represents solid-liquid equilibrium, as for silver and copper in

Figure 7c, it was recognized long before Gibbs work of the late 19 th century that when the liquid

7/10/07 3- 80

solution is cooled, either silver or copper will precipitate out first (depending on whether the

composition lies to the left or right of the low point, called the eutectic). The composition of the

remaining liquid accordingly moves toward the eutectic composition. In the last stage of

precipitation, or freezing, the mixture that comes down is a fine mix of two phases, silver and

copper, with the overall composition of the eutectic. Accordingly, a vertical line was drawn

below the eutectic point to represent this eutectic mixture two distinct phases, but with a

distinctive appearance. Over decades, the vertical line was changed to a dotted line (to

a b c

Figure 3.7. a) Bare-bones phase diagram for two immiscible phases with miscible high-

temperature phase (e.g., CCl4 and H2O, liquid-vapor, or Silver-Copper, solid-liquid). b) The

horizontal line guides the eye. c) Early diagrams showed the eutectic mixture as if it were a

separate phase, or (later) as a dotted line.

indicate there is no phase with composition falling in this broad forbidden region) and more

recently the vertical line is largely omitted.

Examining a large number of such phase diagrams, the two patterns shown here will be

recognized as appearing in combination. Often a solid compound forms, so the diagram can

conceptually be divided in two, element one plus compound on the left and compound plus

element two on the right. There may be regions of solubility, resembling the benzene-toluene

diagram, within a larger phase diagram. Some compounds may spontaneously decompose as the

temperature rises, yielding separate phases. The variety is seemingly endless. But almost all can

be recognized as relatively simple combinations of these two basic patterns.

Problems

1. For the transformation of graphite to diamond at 25 oC, G = 2.9 kJ/mole. The densities are

2.25 and 3.51 g/cm3. What is the minimum pressure required to make diamond

thermodynamically stable at this temperature?

2. At 1114oC the vapor pressure of Ni was observed to be 7.50 x 10-8 torr and at 1142o C it was

14.33 x 10-8 torr. What is the heat of vaporization of nickel in this range?

3. Is the fugacity of ice increased or decreased by exerting pressure on the ice? Which will show

the greatest change in fugacity for a pressure increase of 10 atm: ice, or liquid water? Explain.

4. The vapor pressure of a liquid compound, Y, obeys the equation ln P = a + bT -1, with P the

pressure in atm and T in kelvin.

7/10/07 3- 81

a. What is the boiling point of Y?

b. What is the heat of vaporization at the normal boiling point?

5. Find the mole fractions of the several components if 24 g of methane, CH 4, is mixed with 7 g

of CO, 14 g of N2, and 8 g of He.

6. A saturated solution of benzoic acid, C6H5COOH, contains 0.32 g in 100 g of water. The

density of the solution is 1.3 g/cm3. What is the molarity of the solution?

7. Find the mole fraction, molarity, and molality of iodine when 0.10 g of iodine is dissolved in

100 g of CCl4 (density 1.59 g/cm3).

8. a. What is the molarity of water in pure water?

b. What is the molality of water in pure water?

c. What is the molarity of CCl4 in pure CCl4 (density 1.59 g/cm 3)?

d. What is the molality of CCl4 in pure CCl4?

e. What is the molarity of an ideal gas at 1 atm and 25 oC?

9. A solution contains, by weight, 40% water, 35% ethanol (C 2H5OH), and 25% acetone

(CH3COCH3).

a. Find the mole fraction of each component.

b. Find the molality of the ethanol and acetone if water is considered to be the solvent.

c. Find the molality of the water and acetone if the ethanol is considered to be the solvent.

10. The solubility of CCl4 in water at room temperature is about 0.9 g/L and the vapor pressure

of CCl4 is about 100 torr. What would be the equilibrium vapor pressure of CCl4 above a beaker

containing CCl4 covered with a layer of water?

11. Water in equilibrium with air (20.9% O2, 79.1% N2 by pressure, volume, or mole fraction) at

0oC contains 1.28 x 10-3 mole of air per liter, of which 34.91% is O 2. Calculate the Henrys law

constant

a. for O2

b. for N2

12. Is the Henrys law constant for benzene in water large or small?

13. The distribution coefficient for mercuric bromide, HgBr 2, between water and benzene is 0.90.

That is, with concentrations expressed as molarities, C(HgBr2 /H 2 O) = 0.90.

C(HgBr2 /C 6 H 6 )

An aqueous solution contains 0.010 M HgBr2. 50 ml of this solution is to be extracted with 150

ml of benzene.

a. What fraction of the HgBr2 is left in the aqueous phase if the extraction is made with one

150 ml portion of benzene?

b. What fraction is left if the extraction is made with three successive 50 ml portions of

benzene?

14. Over a certain range of concentrations, the volume of a solution containing m moles of NaCl

in 1 kg water has been found to be, in ml,

V = 1002.935 + 16.670 m + 1.636 m3/2 + 0.170 m2

Find the partial molal volume of

a. NaCl in a 2 m solution

b. water in a 2 m NaCl solution

c. pure NaCl (density 2.165 g/cm3)

7/10/07 3- 82

15. The vapor pressures of benzene and toluene, at 27 oC, are 120 and 40 torr. Assuming an ideal

solution, what is the composition of the vapor above a solution containing 100 g of benzene

(C6H6) and 150 g of toluene (C6H5CH3 )?

16. In your work for Adulterated Chemicals, Inc., you have isolated a new antibiotic through a

lengthy series of extractions, biological tests, and so forth. A few milligrams are available, and by

the ultra-centrifuge method it has been found that the molar mass is 10,000. It is desired to check

this by another method. For a 1% by weight solution of the substance in water, calculate

a. the freezing-point depression

b. the boiling-point elevation

c. the change in vapor pressure at 25oC

d. the osmotic pressure, at 25oC, in cm H2O. (The density of mercury is 13.6 g/cm3 .)

Which method would you recommend?

17. Boiling occurs in a solution when the sum of the vapor pressures of the components is equal

to the atmospheric pressure (or the applied pressure), but these vapor pressures are lower than for

the pure materials (cf. Raoults law, equation 29c). If two liquids are immiscible, each exhibits its

own vapor pressure (in each phase), and steam distillation occurs when the sum of the vapor

pressures is equal to the atmospheric pressure.

a. Calculate the vapor pressure of pure water at 99 oC.

b. What vapor pressure must a compound, immiscible with water, have to steam distill at

o

99 C when the atmospheric pressure is 745 torr?

c. What would be the composition of the vapor in such a steam distillation?

18. A solution of 3.795 g of sulfur in 100 g of CS2 boils at 46.66oC. The boiling point of pure

CS2 is 46.30oC and the heat of vaporization of CS2 is 26.8 kJ/mol. From this experimental result,

what is the probable formula of the sulfur molecule in the solution?

19. Show that if two phases (A and B) in equilibrium are both slightly impure, the resultant

change in temperature (change in melting point or boiling point, relative to pure phases), T, is

given by

H 1T

N 1 =

RT 2

where N1 is the difference in mole fraction of the major component (N1 = N1 A - N1 B ) and H1 is

the enthalpy of transition ( H 1 = H 1A H 1B ) .

7/10/07 3- 83

4 Chemical Equilibrium

Chemical equilibrium is one of the most important applications of thermodynamics. The

theory follows very simply from the equations already derived. Setting up the necessary

equations in practice requires only an understanding of the meaning of a chemical equation. Most

mistakes arise in the elementary process of counting the molecules or moles of reactants and

products.

For some systems the solution of the mathematical equations requires some skill and,

especially, some understanding of the physical implications so that reasonable assumptions and

approximations can be made. For the types of problems considered here, the primary requirement

is to follow a simple, methodical procedure in finding the appropriate equations, and then to insert

numerical values into these equations. Solution of the equations is then quite easy.

A completely general chemical reaction may be represented in the form

aA + bB -----6 cC + dD

This should be interpreted as follows: Under certain conditions of overall temperature, pressure,

and concentrations of A, B, C, and D (not yet specified here), a moles of substance A react with b

moles of substance B to form c moles of substance C and d moles of substance D. Although

some of the reactants (A and B and perhaps others) are consumed and some products (C and D

and perhaps others) are formed, it is assumed that there is no change in temperature, in pressure,

or in concentrations of any of the substances as a consequence of the chemical reaction.

The free-energy change, if the reaction proceeds as written, will be

G = n G

products

i i n G

reactants

j j

The values of the partial molal, or effective, free energies on the right-hand side depend on the

states of these compounds, including the temperature, the pressure, and the individual

concentrations. Thus G may have any value, depending on the states of reactants and products.

Remember that, for purposes of the calculation, the states of reactants and products are

unchanged by the reaction. The temperature, pressure, and concentration of each substance is the

same before and after the reaction. The reaction may involve a negligible fraction of the

substances present, or reactants may be added and products removed as the reaction proceeds.

Tables give G = Go for the reaction occurring with all reactants and products in their

standard states.

Go = cGCo + dGDo aGAo bGBo (2)

7/10/07 4- 84

Subtraction of equation 2 from equation 1 gives

( ) ( ) ( ) (

G Go = c GC GCo + d GD GDo a GA GAo b GB GBo ) (3)

At this point it is convenient to substitute the fugacities (equation 7a, Chapter 3) for the free-

energy terms.

G i = RT ln f i + B i (T )

and G i o = RT ln f i o + B i (T )

Therefore,

fi

Gi Gio = RTln (4)

fi o

f f f f

G Go = RT c ln Co + d ln Do a ln Ao b ln Bo

fC fD fA fB

The ratio of the fugacity of any substance, f i, to the fugacity of the same substance in its standard

state, fio, is called the activity, ai .

fi

ai = (5)

f io

It follows from the definition that activity is always dimensionless and without units. Substitution

of activity for the ratio of fugacities and replacement of n ln x by ln x n gives

(

G G o = RT ln a Cc + ln a Dd ln a Aa ln a Bb )

which can be further simplified to the form

aCc a Dd

G = G + RT ln a b

o

(6)

a A aB

It will be convenient to write this in the form

G = G o + RT ln Q (a ) (7)

defining Q (a) to be

aCc aDd

Q(a) = (8)

a Aa aBb

7/10/07 4- 85

or the corresponding form appropriate to the particular reaction.

Equation 6 is a very important result with obvious physical interpretation. If all substances

(reactants and products) are in their standard states, all activities are, by definition, equal to 1.

Then Q (a) = 1, ln Q (a) = 0, and G = Go. The correction term depends on the value of Q (a),

which depends on the individual activities and therefore on the fugacities, or on the pressure and

concentration of each substance at the given temperature.

Standard States

The choice of standard states affects the value of G o as it appears in tables, and determines

the relationship between the state of a compound and its activity. There are certain conventions

that are customarily followed, so that it is generally considered unnecessary to explain in detail

the choice of standard states that has been made. Unless the conventions are understood,

therefore, it may not be possible to apply thermodynamic values found in the literature. Standard

states are chosen to give a convenient form for the activity.

GASES. For an ideal gas, fugacity is equal to pressure. We choose the standard state to be 1 atm

pressure. Then f = P, fo = Po = 1 atm:

f P(atm)

a= o

= = P(atm) (9)

f 1 atm

That is, the activity, which is a dimensionless ratio, is equal to the numerical value of the pressure,

with the pressure expressed in atmospheres. This simple relationship can be extended to cover

real gases by the introduction of an activity coefficient, (Greek gamma), that will equal 1 if the

gas is ideal, and will differ from 1 as the gas deviates from ideality.

a = P (10)

The activity coefficient defined in this way has units of atm -1. Equation 10 is applicable to any

gas, real or ideal.1 If the gas is non-ideal, it is necessary to know the value of .

LIQUIDS AND SOLUTIONS. The major component of an ideal solution has a fugacity given by

Raoults law

1

More generally, the standard state of any gas is taken as the ideal gas at 1 atm pressure;

that is, it is a fictitious state with properties obtained from the properties of the actual gas, at

sufficiently low pressures that the gas is ideal, extrapolated to 1 atm pressure using the equations

for behavior of an ideal gas. The numerical value of the activity coefficient is the ratio of the

fugacity of the real gas to that of the idealized gas. The dimensions are reciprocal pressure.

7/10/07 4- 86

f1 = f1o N1

in which f1o is the fugacity of the pure solvent. We choose the pure solvent as the standard

state so that f1o is the fugacity in the standard state. Then

f1

a1 = = N1 (11)

f1o

Thus the activity of the solvent is equal to its mole fraction, in the ideal solution, and the activity

of any pure liquid is 1. Not all solutions are ideal, so it is convenient to allow for deviations from

Raoults law by introducing an activity coefficient, as for gases, defined by the equation

a1 = 1 N 1 (12)

This activity coefficient is dimensionless. It will be 1 for a pure liquid, for a solvent in an infinitely

dilute solution, or for a component of an ideal solution. It may differ appreciably from 1 when the

fugacity of the liquid in solution deviates from Raoults law.

If a solute obeys Henrys law, the fugacity is proportional to concentration and the standard

state of the solute may be chosen such that f 2o = k, the Henrys law constant (even though such a

standard state may be physically unattainable). Then

f2 f2

a2 = = = c2 (13)

f 2o k

with |c2| representing the numerical value of c2 . For any particular concentration, the value of the

activity depends on the units chosen for expressing concentration. Common choices are molarity,

molality, or sometimes mole fraction (especially when the choice between solute and solvent is

ambiguous). Activity is dimensionless but the activity coefficient has dimensions of inverse

concentration. For example, if c2 is in mole per liter, 2 has units of liter per mole. In any case,

a2 = 2 c2

subsequent discussions we will assume the concentration of solute is expressed as molarity. For

dilute water solutions the difference between molarity and molality is negligible.

Concentrated solutions may show large deviations from Henrys law, as a consequence of

large intermolecular forces. This may also occur with uncharged solutes, leading, for example, to

a maximum-boiling or minimum-boiling solution, known as an azeotrope. It is also expected for

multiply charged ions (which typically form complex ions of smaller charge). In dilute solutions,

activity coefficients of ions are less than 1, approaching 1 at infinite dilution. Activity coefficients

of ions in concentrated solutions (on the order of 1 M) may increase and become greater than 1.

Strong electrolytes fully dissociate in aqueous solution, so the concentration of undissociated

electrolyte may be assumed to be vanishingly small. We can eliminate consideration of the

undissociated electrolyte by defining its activity to be equal to the product of the activities of the

ions into which it dissociates. Then the equilibrium constant for the dissociation is 1, G o for the

7/10/07 4- 87

dissociation is zero, and the irrelevant quantities disappear from the calculations.

SOLIDS. The fugacity of a solid is very nearly constant, at a given temperature, independent of

the applied pressure (except for extreme pressures). We choose this normal value of the fugacity

as f o, so the solid has an activity of 1. Appreciable deviations from unit activity for a solid may

be expected only under very high pressures, when impurities are present (as in mercury-metal

amalgams), when the solid is severely strained, or when the solid exists as extremely small

particles for which surface effects cannot be neglected.

VARIATIONS AND LIMITATION. Other choices of standard states are possible and may be

convenient for special circumstances. For example, the standard state of a gas may be taken as a

concentration of 1 mol/L rather than at 1 atm. Such a choice seldom, if ever, appears in tables of

standard free energies, but may occasionally be found, especially in introductory discussions, for

applications to chemical equilibria.

There is an important distinction between the choices of standard states for enthalpy and for

free energy. Both are commonly taken for 1 atm pressure and for the most stable phase under the

standard conditions. However, enthalpies are given for a fixed temperature, usually 25 oC (but

sometimes 18oC). Corrections for other temperatures are made by calculations involving the heat

capacity.

H (T2 ) = H (T1 ) + C P dT

T2

T1

On the other hand, the temperature dependence of the free energy is given by equation 23,

Chapter 2,

G

= S

T P

We have defined entropy only through S, and therefore subject to an arbitrary additive constant.

The change in free energy with temperature is thus also subject to an arbitrary additive constant,

and therefore is unknown.2 It is therefore necessary to choose the standard state for the

specification of free energy to be at the temperature of interest.

CALCULATIONS. We are now prepared to calculate free-energy changes for specific chemical

reactions for particular choices of conditions. Consider first the reaction for the synthesis of

ammonia at 25oC when each of the three gases is present at a partial pressure of 5 atm. The

standard free-energy change, Go, is - 16.64 J/mol (NH 3). Assume the gases are ideal.

2

It is possible to assign an arbitrary absolute value for entropy, but such methods always

omit some parts of S, and thus should be regarded as indeterminate. Note, however, that this

limitation does not apply to finding the change in G (as, for example, in finding the change in

Greaction) with change in temperature. This change depends on S, which can be measured. The

temperature dependence of fugacity can also be found.

7/10/07 4- 88

N2 + 3/2 H2 ------6 NH3

a NH 3

G = G o + RT ln

(a ) (a )

N2

1/ 2

H2

3/ 2

PNH 3 5

= G o + RT ln = 16 ,640 + 2, 478 ln

(P ) (P )

N2

1/ 2

H2

3/ 2

25

= 20 .62 kJ/mol (NH 3 )

The free-energy change for Ag2O in air (20% O2) will be slightly different:

Ag2O ------6 2 Ag + O2

(a ) (a ) 2 1/ 2

G = G + RT ln

o Ag O2

aAg2O

Activities of the solids are 1 and the activity of the oxygen is 0.20 (equal to the pressure in

atmospheres).

= 8.846 kJ/mol

The free-energy change for the dissolution of CaF 2 in water at 25 oC, containing 0.001 M NaF

and 0.0001 M CaCl2 may be calculated as follows. The standard free energies of solid CaF2 and

of CaF2 as a solute are -1,162 and -1,106 kJ/mol. Thus Go for the dissolution process is 55.90

kJ/mol.

(

G = 55900 + 8.314 298 ln 10 4 10 3 )( ) 2

= 55900 + 2478 ln10 10

= - 1.150 kJ/mol

The dissolution of HCl gas, at a pressure of 0.10 atm, is somewhat less spontaneous if the

water contains 0.50 M HCl. The standard free energies of HCl(g) and HCl(aq) are - 95.27 and

- 131.2 kJ/mol, so Go = - 131.2 - (- 95.27) = - 35.9 kJ/mol, and (by chosen convention) a HCl(aq)

= aH+ aCl-.

7/10/07 4- 89

a H + aCl

G = G o + RT ln

a HCl ( g )

(0.50)(0.50)

0.10

= 33.6 J/mol

Equilibrium Constants

At equilibrium, under constant temperature and pressure, the free-energy change is zero and

equation 6 becomes

ac ad

0 = G o + RT ln Ca Db = G o + RT ln Q (a )eq

a AaB eq

or

ac ad

G o = RT ln Ca Db (15)

a AaB eq

For any given reaction, the left-hand side, G o, is a constant, obtainable from handbook tables. It

depends only on (1) the choice of standard states, and (2) the temperature. Therefore, at any

given temperature the right-hand side of equation 15 and therefore Q (a) eq must also be a

constant, which is called the equilibrium constant, K (or K eq).

a Cc a Dd

Q (a )eq = a b = K

(16)

a AaB eq

This equation is really quite a remarkable result, and one that students are often unwilling to

accept in its full implications. It says that, despite changes of pressure, concentrations of

reactants or products, or the presence of other substances, the particular function of activities

represented by Q (a) can assume only one value at equilibrium, for a given temperature and

choice of standard states by which the activities are defined. 3 The value of Q (a) at equilibrium is

determined by equation 15, which can be rewritten as

3

Undoubtedly part of the difficulty (whether cause or consequence of the confusion) is

that many textbooks state that the equilibrium constant depends on pressure or on the presence of

other substances, but this is because they are not talking about the equilibrium constant but rather

the value of Q (c) at equilibrium, which is not necessarily a constant. The changes in the

equilibrium constant referred to are really changes in the activity coefficients, or changes in the

deviations from ideality. The true equilibrium constant (or thermodynamic equilibrium

constant) is rigorously constant!

7/10/07 4- 90

Go = - RT ln K (17)

This equation was derived without benefit of arbitrary assumptions, so it must be satisfied for all

chemical equilibria.

There is a strong tendency to misinterpret equation 17. The left-hand side refers to standard

state conditions, the right-hand side to equilibrium conditions, but these are not the same. It may

be helpful to think of the equation in an expanded form:

Now we recognize that (G)std st = Go, (G)equil = 0, Q std st = 1 and ln 1 = 0, and Q equil = K.

Therefore the equation may be written as

Go - 0 = 0 - RT ln K

which may be interpreted as saying that G o is a measure of how far the standard-state

concentrations (or activities) differ from an equilibrium point, and the equilibrium constant is a

measure of how much the equilibrium concentrations (or activities) differ from their standard-

state values (activities equal to 1). The minus sign shows that the left-hand (standard state) side

deviation from equilibrium is equal and opposite to the right-hand (equilibrium) side deviation

from standard states.

Application of the equilibrium constant is straightforward if each step is taken in turn.

Consider, for example, the problem of finding the equilibrium pressures of N 2 and H 2 formed by

decomposition of ammonia, initially at 2 atm, at 25 oC.

(a ) (a ) 1/ 2 3/2

K =

N2 H2

a NH 3

G o = 16 , 640 J/mol = RT ln K

K = 1 . 2 x 10 - 3

In a gaseous system, activities are equal to pressures in atm (assuming ideal gas behavior).

The pressures, in turn, are proportional to the numbers of moles so, for a given volume and

temperature, it is convenient to think of the chemical reaction in terms of pressures (rather than

just moles). Thus, if the initial pressure of NH 3 is 2 atm and x atm decomposes, the chemical

equation states that x/2 atm of N2 and 3x/2 atm of H2 will be produced, with 2 - x atm of NH3

remaining. The equilibrium condition requires that

(2 x )

7/10/07 4- 91

This is a quadratic equation, with the solution x = 0.0428 atm. The equilibrium condition may

now be more explicitly interpreted for this example. If 2 atm of ammonia comes to equilibrium

with its decomposition products, the equilibrium state will be 1.9572 atm of NH 3, together with

0.0214 atm of N2 and 0.0642 atm of H2. Slight further decomposition, at these concentrations,

would cause no change in free energy; there is no tendency for further decomposition because the

system is now at equilibrium. An equilibrium constant for a reaction involving gases, in which

pressures appear as an approximation for activities, is often written K P (and, because pressures

are substituted for dimensionless activities, K P may have apparent dimensions of powers of

pressure).

Consider now the problem of finding the equilibrium pressure of oxygen above Ag 2O at

o

25 C.

Ag2O ------6 2 Ag + O2

(a ) (a )

2 1/ 2

K=

Ag O2

a Ag2O

Go = 10,840 = RT ln K

K = 0.0125= PO2 ( ) 1/ 2

Thus silver oxide, placed in an evacuated system, should decompose until the oxygen pressure

reaches 0.119 torr. In an atmosphere containing 20% oxygen the reaction would be driven in the

other direction, so that silver should react with oxygen to form silver oxide. The slow rate of this

reaction (in either direction) is attested by the durability of silver goods. An equilibrium constant

for dissociation of a compound is often written K diss or, when the dissociation is into ions, Kionization.

For the solubility of CaF2 in water at 25oC,

(a )(a )

Ca+ + F

2

K=

aCaF2

Go = 55900= RT ln K

K = 1.78 x 10-10

The equilibrium constant for dissolution of a slightly soluble salt in water is called the solubility

product constant, or Ksp.

The activity of solid CaF2 is 1. Assume that activities of the ions are numerically equal to

concentrations. From the dissociation equation we find that if the concentration of Ca ++ is s, the

concentration of F- will be 2s, so long as there is no other source of these ions than CaF 2.

Inserting these symbols into the equation above gives

7/10/07 4- 92

1.78 x 10-10 = s(2s)2

s = 3.5 x 10-4 M

This is the solubility of CaF2, because each mole of CaF2 going into solution gives one mole of

Ca++ ions. Introduction of activity coefficients would probably change the calculated value by

something on the order of 20%, which is often negligible in determining solubilities. (Reported

experimental values differ by much more than this for some compounds, but such accuracies are

entirely adequate for some applications.)

To find the solubility of CaF2 in 0.5 M NaCl the deviation of activity coefficients from 1

should not be neglected. The equations may be written

= Q ()Q (c)

Experimental measurements indicate that Q (), the correction factor, is on the order of 0.1 for

such a solution. Solving for the concentrations as before gives

1 . 78 x 10 -10

4s =3

0 .1

s = 7 . 6 x 10 - 4 M

The increase in solubility when the other ions (Na + and Cl -) are added is called the salt effect. The

added salt lowers the activity coefficients of all ions present.

The solubility of CaF2 in 0.5 M NaF will be smaller because of the common-ion effect. This

is apparent when we substitute numbers into the equations obtained above.

Now the concentration of fluoride is no longer equal to twice the concentration of calcium ion,

but is 0.5 + 2s when the Ca++ has the concentration s. The correction term may be assumed the

same as for NaCl. Then

1 .78 x 10 -10

s=

0 .1 x 0.5

= 3 .5 x 10 -9 M

This answer confirms the assumption that taking s negligible with respect to 0.5 gives a self-

consistent, and therefore mathematically valid, solution to the problem.

An orderly procedure in working problems of chemical equilibrium will greatly decrease the

7/10/07 4- 93

opportunity for mistakes. The recommended steps are as follows:

1. Write the chemical reaction, even though it is a familiar one.

2. Write out the equilibrium constant expression, Q (a), in terms of activities and set this

equal to Keq.

3. Determine the equilibrium constant for the reaction as written, either from the constant

given or from standard-state free energies. Note that reversing a reaction inverts the equilibrium

constant, and that multiplication of the equation by an integer raises the equilibrium constant to

that power.

4. Make the appropriate substitutions of symbols (that is: concentrations, pressures, mole

fractions, or unity) for each of the activities. Include activity coefficient if necessary (either

numerically or symbolically).

5. Determine, from information given and the stoichiometry of the chemical reaction, what is

known about concentrations or pressures.

6. Solve the algebraic equation.

7. Examine the solution to be sure that the answer found is the answer to the question asked

and is a reasonable value in terms of the physical problem as stated and the approximations made

in the solution of the problem.

Consider, for example, the decomposition of the gas phosphine, PH 3 (G o = 18.24 kJ/mol at

o

25 C), to give white phosphorus (solid) and hydrogen gas. If 5 atm of PH 3 in a closed vessel

comes to equilibrium with its decomposition products, what will be the final pressure of PH 3?

The specific steps of the solution, as described above, are:

1. 2 PH3W 2 P + 3 H2

a P2 a H3 2

2. K eq = 2

a PH 3

K = 2.51 x 106

6

a H3 2

4. aP = 1; 2.51 x 10 = 2

a PH 3

5. 2 PH3 -----6 2 P + 3 H2

Because Keq is large, the reaction must be shifted well to the right, so x will be nearly equal to 5/2,

and 5 - 2x will be very sensitive to x. Therefore, as a first approximation, let x = 5/2 on the right-

hand side and find (5 - 2x):

7/10/07 4- 94

(5 - 2x)2 = 27(5/2)3/2.51 x 106 = 1.68 x 10-4

x = 2.49

This calculated value is in excellent agreement with the value assumed, so the calculation is self-

consistent.

7. The final pressure of PH3 is 5 - 2x = 0.013 atm and of H2, 3x = 7.48 atm. This is a

reasonable answer for the problem given, because G o(PH 3) = 18.24 J/mol indicates that PH3 is

quite unstable.

The equilibrium constant does vary with temperature. From equation 17, ln K = - G o/RT,

so we can find the temperature dependence. Take the derivative with respect to temperature

(holding the pressure constant at its standard value), employing equation 30 of Chapter 2.

d ln K

=

d G o 1 d G o

=

( )

G o d T 1 ( )

dT dT RT RT dT R dT

S o G o TS o + G o

= + =

RT RT 2 RT 2

and therefore

d ln K H o

= (18)

dT RT 2

The last equation can be integrated, assuming H o is constant with temperature, to give

K2 H o T

ln = (19)

K1 RT1T2

constant at T1, Ho is the enthalpy change for the reaction with all reactants and products in their

standard states, and T = T2-T1.

The similarity of equation 19 to the Clausius-Clapeyron equation (equation 6, Chapter 3) is

not accidental. Equations for solubility, for reaction rate constants, and for other quantities, have

equivalent forms. This form is to be expected because all of these physical properties depend on

the system surmounting an energy barrier (corresponding to the heat of reaction, the heat of

vaporization, the heat of solution, or some other such energy, or enthalpy, term) and therefore

they depend, in a fundamental way, on the Boltzmann distribution law, which is an exponential

expression relating numbers of molecules, energy states, and temperature, and which therefore

gives rise to a logarithmic temperature dependence.

7/10/07 4- 95

Electrochemistry

The best method of directly measuring the free-energy change of a chemical reaction is often

to carry out the reaction in an electrochemical cell. The free-energy change, at constant

temperature and pressure, is (eqn. 26, Chapter 2)

or

G = Wrev (20)

where Wrev is the electrical work. Electrical power, P, is I 2R = EI and electrical work is power

multiplied by time, or potential multiplied by charge:

Wrev = Pt = EI t = Eq

The potential, E, is in volts, the current I in amperes, the time t in seconds, the resistance, R, in

ohms, the charge q, in coulombs, and power, P, in watts, and the work w in joules. A convenient

unit of charge is a mole of electrons (6 x 10 23 electrons), called a faraday. One faraday, F, is

96,487 coulomb. If n mol of electrons (or n equivalents) are transferred at a potential

difference E the work done is Wrev = Eq = E(nF) and the free-energy change is

G = - nFE (21)

For example, we will find that the standard cell potential (all reactants and products present

at unit activity) for the reaction that transfers 2 electrons from copper to ferric iron (Fe +++) is

1.100 V. The standard free energy (per mol Cu 6 Cu++) is therefore

Go = - nFE = - 2 x 96,487 x 1.100 = - 21,230 J/mol

Substitution of equation 21 into equation 7 gives

and therefore

ln Q (a )

RT

E = Eo (22)

nF

This is now commonly called the Nernst equation. Similarly, by combining equation 21 with

equation 17 we obtain

RT

E o

= ln K (23)

nF

7/10/07 4- 96

Writing

ai = i ci

for each of the reactants and products, the function Q factors to give

Q(a) = Q()Q(c)

and thus

ln Q ( ) ln Q (c )

RT RT

E = Eo

nF nF

( i = 1) E = Eo

RT

lnQ (c ) (24)

nF

The potential depends on the actual activities, or concentrations, of the reactants and products.

Not only G and equilibrium constants can be determined electrochemically, but also H and

S. From equation 21 and equation 30 of Chapter 2,

G E

S = = nF (25)

T P T P

and therefore, from H = G + TS, we obtain

E

H = nFE + nFT (26)

T P

chemical reaction in which electrons are transferred from one substance to another. Such

reactions are called oxidation-reduction reactions, or simply redox reactions. Removal of

electrons, as in Fe --6 Fe+3 + 3e, or 2 I- --6 I 2 + 2e, is called oxidation; addition of electrons is

called reduction.

Electrons enter or leave a device through a conductor called an electrode. The cathode

(from the Greek down way) is the electrode at which electrons enter any device; the anode

(from the Greek up way) is the electrode at which electrons leave any device. To push

electrons through a vacuum tube or electroplating cell, the cathode must be made negative. On

the other hand, the electrode at which an electrochemical cell releases electrons is called negative

(Figure 1) and this is, by definition, the anode.

It is not possible to measure half a reaction. Only complete reactions (cathode reaction +

anode reaction) can be measured. Nevertheless, it is convenient to consider the electrochemical

7/10/07 4- 97

potential of a reaction as a sum of the potentials of

two half reactions, each defined from equation 21

in terms of the free-electron changes. Let G A be

the free-energy change for the anode reaction

(electrons leaving, hence oxidation), G C be the

free-energy change for the cathode reaction

(electrons entering, hence reduction), and G be

the free-energy change for the total reaction.

Free-energy changes are additive, so

E = EA + E C (27)

thus independent of the amount of reaction! That

is, the potential of a half-reaction such as

M++ + e -----6 M

reaction

M++ + 2 e -----6 M

small additional term that should be included on

the right-hand side of equation 27, arising from the

contact between dissimilar solutions. Like E A and

EC , these junction potentials cannot be

measured, nor can they be calculated by

thermodynamics. They can, however, be

electrochemical cell, oxidation, occurring at the

anode, with release of electrons, and reduction,

occurring at the cathode, with removal of electrons

from the circuit, produces a potential difference

between anode and cathode that drives charges

around the circuit. Charge is conserved. There is

no source of charge, or source of current.

estimated, based on theories involving diffusion rates, and are usually sufficiently small in practice

7/10/07 4- 98

that they can be ignored for present purposes.

Although it is not possible to measure EA or EC separately, it is possible to measure total cell

potentials. Then, by choosing an arbitrary value for some half-cell potential as a reference level,

other half-reaction potentials can be determined relative to this arbitrary reference. The half-

reaction chosen as the reference for this purpose is

2 e + 2 H+ -----6 H2

for which Eo (the potential with all reactants and products at unit activity) is arbitrarily assigned

the value zero. Then, for example, because the standard potential of the cell reaction

Zn + 2 H+ -----6 H2 + Zn++

Reaction Eo (volt) Reaction Eo (volt)

Li+ + e ----6 Li -3.0401 Cu + e ----6 Cu+

++

0.153

K+ + e ----6 K -2.931 SO4= + 4 H+ + 2e ----6

Na+ + e ----6 Na -2.71 H2SO3 + H2O 0.172

Mg++ + 2e ----6 Mg -2.372 AgCl + e ----6 Ag + Cl- 0.22233

Al+++ + 3e ----6 Al -1.662 Cu++ + 2e ----6 Cu 0.3419

Mn(OH)2 + 2e ----6 Cu+ + e ----6 Cu 0.521

Mn + 2 OH- -1.5 I2 + 2e ----6 2 I- 0.5355

Cr++ + 2e ----6 Cr -0.913 MnO4- + e ----6 MnO4= 0.558

Zn++ + 2e ----6 Zn -0.7628 MnO4- + 2 H2O + 3e

2 CO2(g) + 2 H+ + 2 e ----6 MnO2 + 4 OH- 0.595

----6 H2C2O4(aq) -0.49 O2 + 2 H+ + 2e ----6 H2O2 0.695

Fe++ + 2e ----6 Fe -0.447 Fe+++ + e ----6 Fe++ 0.771

Cr+++ + 2e ----6 Cr++ -0.407 Hg2++ + 2e ----6 2 Hg 0.7973

Cd++ + 2e ----6 Cd -0.4030 Ag+ + e ----6 Ag 0.7996

AgI + e ----6 Ag + I- -0.15224 Hg++ + 2e ----6 Hg2++ 0.851

Sn++ + 2e ----6 Sn -0.1375 2 Hg++ + 2e ----6 Hg2++ 0.920

Pb++ + 2e ----6 Pb -0.1262 NO3- + 4 H+ + 3e ----6

O2 + H2O + 2e NO + 2 H2O 0.957

----6 HO2- + OH- -0.076 Cr2O7= + 14 H+ + 6e

Cu(NH3)4++ + 2e ----6 2 Cr+++ + 7 H2O 1.350

----6 Cu + 4 NH3 -0.05 Cl2 + 2e ----6 2 Cl- 1.35827

Fe+++ + 3e ----6 Fe -0.037 MnO4- + 8 H+ + 5e ----6

2 H+ + 2e ----6 H2 0.0000 Mn++ + 4 H2O 1.507

AgBr + e ----6 Ag + Br- 0.07133 Cr++++ + e ----6 Ce+++ 1.72

Hg2Br2 + 2e ----6 MnO4= + 4 H+ + 3e ----6

2 Hg + 2 Br- 0.13923 ----6 MnO2 + 2 H2O 1.679

Sn++++ + 2 e ----6 Sn++ 0.151 H2O2 + 2 H+ + 2e ----6 2 H2O 1.776

has been found to be 0.763 V, it follows that the standard potential for the half reaction

Zn -----6 Zn++ + 2 e

7/10/07 4- 99

must be 0.763 V. In turn, from the measured Eo for the reaction

2 e + Cu++ -----6 Cu

the standard potential is Eo = 0.337 V. We can proceed in this fashion to find the potential for

any half reaction on this arbitrary scale. Reversal of a cell reaction changes the sign of a

potential.4 The more positive a half-reaction potential, the greater the tendency of that half

reaction to proceed as written. (But it should be kept in mind that the reaction may be too slow

to observe or that some other spontaneous reaction may occur instead.)

Some standard potentials for reduction half-reactions are given in Table 1. According to the

Stockholm Convention, such standard reduction potentials are called standard electrode

potentials. If the reaction is written in reverse order, E o will have the opposite sign and is called

the standard oxidation potential. Tabulations of half-reaction potentials are often given for

oxidation half-reactions.5

CALCULATIONS OF CELL POTENTIALS. A few examples will illustrate the applications of standard

potentials of half reactions. Consider the cell reaction

Cu -----6 Cu++ + 2 e

The standard potential for the first is taken directly from Table 1, that for the second is obtained

from the table simply by changing the sign (because the reaction is the reverse of that given in the

4

An electric potential difference is the work required, per unit of charge, to move a charge

between two points, just as a gravitational potential difference is the work required, per unit of

mass, to move a mass between two points. The gravitational potential difference for a well is

positive if the top is measured with respect to the bottom, or negative if the bottom is measured

with respect to the top, and an electric potential that is positive if the cathode is measured with

respect to the anode will be negative if the reaction is reversed. (The standard electrode

potential includes a choice of sign in the definition, but standard potential simply means that

the reactants and products are in their standard states.)

5

For more half-reaction potentials see especially W. Latimer, Oxidation Potentials, 2nd

ed., Prentice-Hall, Englewood Cliffs, N.J., 1952.

7/10/07 4- 100

table). Thus

The positive cell potential indicates that the original reaction will proceed as written, with

substances at unit activity.

The cell reaction shown in Figure 2 is

The potential, at 25oC, may be found as follows. From Table 1,

Eo = 0.763 + 0.337 = 1.100 V

RT a Cu a Zn + +

E = Eo ln

nF a Zn a Cu + +

8 . 314 J/mol K x 298 K 0 . 01

= 1 . 130 V ln

2 equiv/mol x 96,487 C/equiv 0 .1

= 1 . 130 V

assuming the solid metals, Zn and Cu, are at unit activity (pure

and not seriously strained). The activities of the ions have been

approximated by their concentrations.

The concentration correction factor, (RT/nF) ln Q (a),

appears sufficiently often that it is helpful to carry out a partial

evaluation. At room temperature, 25oC, we may write

RT 8.314 x 298.15 V

nF n x 96487

RT 0.05915

(25 o C) (28)

nF n

(25 C)o

E = Eo

0.05915

n

logQ (a) (28a)

The Nernst equation may also be applied to half-reaction potentials. For example, the

potential of the reduction half-reaction

Zn++ + 2 e -----6 Zn

would be

7/10/07 4- 101

RT a

E = Eo ln Zn

nF a Zn + +

or, at 25oC,

0 .05915 a

E = 0 .763 log Zn

2 a Zn + +

(The electrons should, in principle, also appear in this expression, but the activity of the

electrons is unknown, and when this reduction half-reaction is combined with an oxidation half-

reaction, the electron terms will drop out.) Similarly, for the oxidation half-reaction

Zn -----6 Zn++ + 2 e

the potential, at 25oC, would be

0 . 05915 a ++

E = 0 . 763 log Zn

2 a Zn

Although space does not permit an adequate discussion of the problem of reversibility, it

should be pointed out that not all chemical reactions can be carried out in electrochemical cells,

and even many that can will not be reversed by a change of potential. The first requirement for a

well-behaved electrochemical cell must be that the reaction will proceed as desired and be capable

of reversal. To achieve quantitative agreement with the equations of thermodynamics, however,

the requirements are more stringent. The chemical reaction must be thermodynamically

reversible, so that an infinitesimal change of potential is sufficient to reverse the flow of current

and the direction of chemical reaction. Discussions of the problems encountered in irreversible

electrochemical systems may be found in more advanced works under the listings of

overvoltage, polarization, and junction potentials.

CELL NOTATION. A very convenient shorthand notation has been developed for writing

electrochemical cells. The cell shown in Figure 2 can be represented by

Zn/ZnSO4(0.01 M)//CuSO4 (0.1 M)/Cu

A cell in which the reaction is the displacement of hydrogen by zinc can be written

Zn/Zn++//H+/H2,Pt

The platinum serves as the electrical contact to the solution, with hydrogen gas bubbled around

the platinum. Although there are minor differences among authors concerning separating

components with commas and shilling marks, generally one of these marks will separate

substances in direct contact. The // indicates a junction between two different solutions, which

are commonly connected by a salt bridge, such as a U tube containing concentrated KCl

7/10/07 4- 102

solution and dipping into the two solutions.

The direction of the cell reaction is determined by the convention that the electrode on the

left is the anode.6

physical chemistry, analytical chemistry, descriptive inorganic chemistry, preparative inorganic

and organic chemistry, biochemistry, and metallurgy. Electrochemical measurements provide an

accurate means of obtaining the thermodynamic properties of a reaction, including H, S, and

G. These thermodynamic properties depend, in turn, on the exact nature of the reaction,

including the charges on the ions participating. Because the potentials depend on concentrations,

information is available on the concentrations of individual ions in solution for analytical purposes

or for determining solubilities.

Electrode potentials are often more convenient than free energies for prediction of which

reactions will be spontaneous. For example, oxidizing agents can be put in order of oxidizing

powers by reference to the standard potentials for the corresponding reactions. Often an

oxidizing agent can be found that is just strong enough to do the job desired and not so strong

that it will oxidize other substances present in the mixture. Electrode potentials are the basis of

studies of corrosion and electro-refining of metals.

Problems

1. The standard free energies of NO2 and N2O4 at 25oC are 51.3 and 99.8 J/mol. Find the

equilibrium constant for the reaction

2. For each of the following reactions, set up the equilibrium constant expression, in terms of

activities, and make the appropriate substitutions of symbols (concentrations, pressures, mole

fractions, or one) for the activities:

a. Cu++ + H2S(aq) ----- CuS + 2 H+

b. 2 HgO ----- 2 Hg + O2

c. NaHCO3 + HCl ----- CO2 (g) + H2 O + NaCl

H 2O

(ethyl acetate) (acetic acid) (ethanol)

6

There are very few conventions that need to be memorized, although these few can be

expressed in a bewildering variety of forms. One convention is that the anode (where the

electrons leave the cell) in on the left in these condensed cell descriptions. A mnemonic for

remembering this is a partial acrostic based on the word always: Anode ... Left ...W ...A ...Y

...S. Another convention is that the term standard electrode potential means the same as

standard reduction potential. A third is that a positive potential for a cell corresponds to a

spontaneous reaction, as implied by equation 2.

7/10/07 4- 103

3. The standard free energies of benzene and cyclohexane are 124.5 and 28.5 J/mol at 25 oC. Find

the equilibrium constant for the reduction of benzene with hydrogen at 25 oC.

If equilibrium is reached with 5 atm H 2 gas present, what is the mole fraction of benzene left in the

cyclohexane liquid produced?

4. What effect will the addition of an inert gas have on the equilibrium point of the gas-phase

reaction

N2O4 ----- 2 NO2

if the volume is maintained constant?

5. What effect will the addition of an inert gas have on the equilibrium point of the gas-phase

reaction

N2O4 ----- 2 NO2

if the total pressure is maintained constant?

6. For the reaction

CO + 2 H2 ----- CH3OH

Go = -13.5 J at 700 K. Find the percentage decomposition of methanol, at this temperature and

constant volume, if the initial pressure of pure methanol is 5 atm.

7. Water and solid sulfur can react to form SO 2 and H2S according to the equation

The standard free energies are, for H 2O (gas), -228.6, for H2S (gas) -33.4, and for SO2 (gas), -

300.1 J/mol, at 25oC.

a. Find the equilibrium constant for the reaction as written.

b. Calculate the pressures of SO2 and H2S to be expected in equilibrium with solid sulfur and

moist air (vapor pressure of water = 23.8 torr) at 25 oC, assuming gases to be ideal.

8. The reaction

2 SO2 + O2 ----- 2 SO3

fixed volume, find the equilibrium pressure of SO 3 and hence the percentage dissociation.

9. The standard free energy of HI at 250oC is -10.8 J/mol.

a. Find Go and the equilibrium constant for the reaction at 250o C,

H2 + I2 ----- HI

b. Find Go and the equilibrium constant for the reaction, at 250o C,

H2 + I2 ----- 2 HI

7/10/07 4- 104

How does this K compare with the K from part a?

c. If 1 atm of HI at 250oC is placed in a vessel and allowed to reach equilibrium with its

decomposition products at this temperature, what will be the final pressure of HI?

10. The solubility product constant, Ksp , for MgF2 at room temperature is 7.1 x 10 -9. Assuming

activity coefficients are unity, find the solubility of MgF 2

a. in water

b. in 0.01 M NaF solution

Addition of ions to a dilute solution will decrease the values of activity coefficients. Would the

addition of Na2SO4 increase or decrease the solubility of MgF2 ?

11. Find Go for the process of dissolving MgF2 in water. Is this positive or negative? Explain

why, in terms of what will happen when MgF2 is added to water.

12. The solubility products for barium oxalate at 18 oC are given below.

(B) BaC2O4 H2O Ksp = 2.2 x 10-7

a. Assuming only (A) is present in the solid phase, find the concentration of Ba ++ ion in

aqueous solution in equilibrium with this solid.

b. Assuming only (B) is present in the solid phase, find the concentration of Ba ++ ion in

aqueous solution in equilibrium with this solid.

c. Describe what will happen if 1 g of (A) and 1 g of (B) are added to 100 ml of water at

o

18 C under 1 atm pressure.

d. How many phases will be present at equilibrium? What are they?

13. The dissociation constant of H2S in water solution is 9.1 x 10 -8.

(The second dissociation, to give S=, can be ignored here.) Find the concentration of hydrogen

ion in 0.1 M H2S solution.

14. The dissociation constant of benzoic acid is 6.30 x 10 -5 at 25 oC. Find the concentration of

hydrogen ion

a. in 0.001 M benzoic acid solution

b. in solution containing 0.001 M benzoic acid plus 0.01 M sodium benzoate. (Benzoic acid

dissociates to give one hydrogen ion, BH ----- B- + H+.)

15. For the cell

Zn/Zn++(a = 0.01)//Ag+(a = 0.5)/Ag

b. What is E o?

c. What is E ?

d. Is the reaction spontaneous?

16. Find the equilibrium constant for the reaction, at 25 oC,

7/10/07 4- 105

2 Fe++ + Hg2++ ----- 2 Hg + 2 Fe+++

is 0.464 V at 25oC.

a. Will the potential be increased or decreased by adding NaCl to a concentration of 0.10 M?

b. Will the potential be increased or decreased by alloying the silver with gold?

c. Is the silver the anode or cathode?

d. As the cell is written, will electrons in the external circuit flow from left to right or from

right to left?

18. The Weston normal cell is Cd-Hg/CdSO4/Hg2SO4/Hg, for which the potential is E = 1.0183

[1 - 4.06 x 10-5(t - 20) - 9.5 x 10-7(t - 20)2 + 1 x 10-8 (t - 20)3 ] V at to C. Find H for this cell at

20oC.

19. The cadmium-calomel cell

has been found to have a potential that varies with temperature according to the equation

with T in kelvin and E o in V. For the cell reaction at 40o C, calculate

a. Go b. Ho c. So

20. For the cell

Pt, H2(1 atm)/HCl/AgCl/Ag

in which the electrolyte also contained 0.001 M NaCl, the measured potential, at 25 oC, was found

to be 0.724 V. What is the pH of the solution, assuming activities equal to concentrations?

21. Write the reaction to be expected if a block of Mg is attached to a steel ship hull. Will the

ship be oxidized or protected from oxidation?

22. Find an oxidizing agent capable of oxidizing Hg to Hg2++ without appreciable formation of

Hg++.

23. Predict the products of the following reaction:

a. HNO3 + Hg -----

b. HNO3 + Hg2++ -----

c. Hg + Hg++ -----

24. In deriving equation 27 it was emphasized that electrochemical potentials are independent of

the amount of reaction. (Holding down the button on a flashlight does not increase voltage.) Yet

the Nernst equation (see equation 28a) contains n explicitly. How can you reconcile these

seemingly contradictory facts?

[Answer: 24. Q(a) contains powers of activities proportional to n. Dividing log Q(a) by n

removes this apparent dependence on n from the correction term for E. ]

7/10/07 4- 106

5 Heat Engines and Absolute Zero

Many innovations of thought and technology contributed to the Industrial Revolution, but

certainly a major factor in its development was the replacement of human and animal power by

the power of the steam engine and, later, by power from the internal combustion engine.

Thermodynamics, too, owes much of its early development to these engines that convert thermal

energy to mechanical energy (heat to work). It was through his studies of heat engines in the

early 19th century that the young Frenchman Sadi Carnot discovered the principle now best

described in terms of entropy, and even today the heat engine is considered important as a means

of demonstrating the principles of classical thermodynamics. But the principles of the heat engine

are also of great practical importance in modern technology and in current research. New devices

are constantly being sought to convert thermal energy into electrical power. One way of stating

the second law is that mechanical energy (as work) can be totally converted to thermal energy (or

heat) but thermal energy cannot be totally converted to work (i.e., mechanical energy) in a

cyclic process. Thermodynamics provides an understanding of the possible effectiveness, and the

inherent limitations, of all devices to convert thermal energy into mechanical energy. The theory

of heat engines is also important to a discussion of absolute zero and the third law of

thermodynamics.

The essential ingredients of a steam engine are a boiler and a source of heat for it; a cylinder

into which the steam from the boiler can expand fitted with a piston against which the gas

will push, performing work (and thereby losing energy and becoming cooled); and means for

further cooling and/or venting the expanded steam so that the piston can be returned to its initial

position. In the operation of the engine, heat is put into the engine at some elevated temperature,

the engine itself does work on its surroundings (transmitted by the shaft of the piston), and a

portion of the thermal energy taken in is discharged, as heat, at a lower temperature (into the

cooling water). The energy transfers are represented in Figure 1.

Figure 5.1. A heat engine takes thermal energy from a reservoir at a higher temperature,

TH, does work on the surroundings, and dumps excess thermal energy at TC .

7/10/07 5- 107

Theoretical heat engines always operate on a completely reversible, closed cycle. Real heat

engines seldom, if ever, operate on a fully closed cycle. Expanded steam, for example, is typically

at least partially released to the atmosphere, rather than being condensed to liquid and recycled.

That has little effect on the overall efficiency, so we retain the cyclic model.

The efficiency of a heat engine is defined to be the output, (-) W, divided by the input, Q U,

which is the thermal energy put into the engine at the upper temperature, T U .

output - W

efficiency= = (1)

input QU

For a complete cycle, QU + QL + W = E = 0, and QU is positive, QL, which is the thermal energy

(or heat) absorbed by the engine at the lower temperature, is negative, and W, the work done on

the heat engine, is negative. Thus, in terms of all positive values

(-W) = QU - (- QL)

or

|W| = |QU | - |QL |

Therefore QU > (- W) and the efficiency is less than one (or less than 100%).

CARNOTS THEOREM. Between 1698 and 1782, a series of British inventors designed steam

engines, originally to remove water that flooded the coal mines but eventually to initiate the

Industrial Revolution that was largely responsible for the creation of the British Empire. Toward

the end of the century, Lazare Carnot, a French mathematician, engineer, general, and

administrator under Napoleon, studied the design of steam engines and concluded that efficiency

was decreased by any jerkiness (sudden acceleration) of the engine. His son, Sadi, followed in

his footsteps as an officer, until his career was terminated by Napoleons collapse. Sadi then

retired, at half pay, at the age of 24 (in 1820) to study physics, economics, and steam engines. In

1824 he wrote a small pamphlet, Reflections on the Motive Power of Fire, that laid out the theory

of heat engines, including a derivation of the maximum possible efficiency of any such device.

Consider two heat engines, A and B, operating between the same two temperatures. We

wish to avoid any jerkiness in their operation, so we may imagine that engine B, at least, operates

reversibly. We put no restrictions on engine A, so we may start with the trial assumption that the

efficiency of A is greater than that of B. The two engines can then be coupled together as shown

in Figure 2. Engine A drives engine B in reverse, and because (-W)/Q U is greater for engine A, we

set (QU)A = - (QU)B (by adjusting the length of the stroke). Then (W)B > (-W)A , so there is more

than enough mechanical energy available to drive engine B. By allowing some input of energy at

the lower temperature, from the cooling water, we now have a pair of engines that will give us

perpetual motion (of the second kind). Engine A drives engine B with excess work available to

carry out some other task. But we know this is impossible, both from long experience and from

our understanding of the second law of thermodynamics.

The conclusion of this thought experiment is that the efficiency of engine A cannot exceed the

efficiency of any reversible heat engine, such as B. This conclusion, reached by Sadi Carnot, is

known as Carnots theorem:

7/10/07 5- 108

Figure 5.2. Two heat engines may be coupled, such that the reversible engine (left)

provides thermal energy at the higher temperature to the other engine, which in turn

provides the work to drive the first engine.

The efficiencies of any two reversible heat engines, operating between the same

two temperatures, are the same, and this is the maximum efficiency

for any heat engine operating between these two temperatures.

From Carnots theorem we can see that the nature of the working fluid whether steam,

ideal gas, mercury, or any other vapor, liquid, or vapor-liquid combination cannot change the

efficiency, nor can the nature of the cyclic process alter the efficiency, so long as the steps are

reversible and thermal energy transfers occur only at the upper and lower temperatures. The

efficiency will, in fact, be decreased by non-reversible heat transfers or transfers at intermediate

temperatures and, to a lesser extent, by friction, as we will see below, but these are differences

associated with the departure from reversibility.

It is sufficient, therefore, to choose a very simple cyclic process, operating with an ideal gas.

The result will be applicable to any real device, apart from corrections for irreversibility.

CARNOTS CYCLE. The cycle most conveniently treated is called the Carnot cycle. It consists

of an isothermal reversible expansion at the upper temperature, an adiabatic reversible expansion

from the upper temperature to the lower temperature, an isothermal reversible compression at the

lower temperature, and an adiabatic reversible compression from the lower to the upper

temperature. More briefly, it alternates isothermal and adiabatic steps, with every step reversible.

The important equations of the Carnot cycle are obtained quite easily for an ideal gas.

Step 1: at T1, E1 = 0; V1 6 V2:

V2

W1 = Q1 = nRT1 ln (2a)

V1

and in more detail,

dEa = nCV dT= wa = - PdV= - nRT dV/V so CV ln T2 /T1 = - R ln V3 /V2

7/10/07 5- 109

Step 3: at T2, E2 = 0; V3 6 V4:

V4

W2 = Q2 = nRT2 ln (2c)

V3

and in more detail,

dEb = nCV dT= wb = - PdV= - nRT dV/V so CV ln T1 /T2 = - R ln V1 /V4

Then, because ln T1/T2 = - ln T2/T1, it follows that ln V3 /V2 = - ln V1 /V4 and thus

V2 /V1 = V3/V4, so

Q1 Q

= 2 (3)

T1 T2

and

= nR (T 2 T 1 ) ln

V2

W = W i

V1

The efficiency is

output W T1 T2 T

= = = (4)

input Q1 T1 T1

SHORTCUT: We may ignore the details of the ideal-gas expansions and compressions and, in fact,

remove the restriction to an ideal gas, by emphasizing the changes in entropy.

In the initial reversible isothermal step at T 1, E 1 = 0 and

- W1 = Q1 = T1 S1

For the reversible adiabatic step (T 1 to T2), Q is zero and therefore S is zero. In the reversible

isothermal step at T2, E2 = 0 and

W2 = - Q2 = - T2 S2

and in the reversible adiabatic step returning from T 2 to T 1, Q is zero and S is zero.

Now we note that for the over-all process,

S = S1 + S2 = 0

7/10/07 5- 110

S1 = - S2

- W = Q = Q1 + Q2 = (T1 - T2) S1

Let S1 be represented by the symbol (Greek kappa). The important equations are then

Q1 = T1 (5a)

Q2 = - T2 (5b)

- W = (T1 - T2) = T (5c)

with Q1 the amount of thermal energy transferred to the engine at T1 , Q2 the amount transferred to

the engine at T2, and W the total amount of work done on the engine in a complete cycle. These

three equations must apply to any reversible heat engine. Only the value of will vary from one

engine to another, for a given choice of T1 and T2.

APPLICATIONS OF HEAT ENGINES AND HEAT PUMPS. The maximum possible efficiency for a heat

engine producing net work ( > 0, W < 0) is that of a reversible engine. From equation 4 this is

-W T

efficiency = = (4a)

Q1 T1

For example, a steam engine operating between 100 oC and 20oC has a maximum possible

efficiency of

-W T 80

eff = = = = 21 . 4 %

Q1 T1 373

Steam engines can be designed to operate with superheated steam, with a resultant improvement

in possible performance. Operating between 600 oC (a typical federal limit) and 30o C, the

maximum possible efficiency would be

570

eff = = 0 . 65 = 65 %

873

which still represents a loss of more than a third of the energy, and even this value is too

optimistic.

PRACTICAL LIMITATION OF CURZON AND AHLBORN. It has always been apparent that the Carnot

cycle puts an unrealistic demand on the system, because it assumes thermal energy transfer at T 1

and at T2. Such a transfer, without a thermal gradient, would be infinitely slow. Although such

an arrangement would give maximum efficiency, it would give zero power output because it could

7/10/07 5- 111

never finish its first cycle.

Curzon and Ahlborn have shown that optimum power output occurs when the demands of

rate of thermal energy transfer are balanced against the engine efficiency. When this limitation is

included, the actual best efficiency becomes

T1 T2 W

eff = = (6)

T1 Q1

This is a substantially lower efficiency than predicted by Carnot, but it agrees quite well with the

actual efficiencies obtained from real heat engines. (This shows that friction, usually blamed for

poor performance, is relatively inconsequential in well-designed heat engines.)

By the Curzon and Ahlborn formula, the efficiency of an engine operating between 20 oC and

100oC would drop to 1 - %(293/373) = 11%. Moving to the higher temperatures of 600o C and

30oC would give an efficiency of 1 - %(303/873) = 41%.

REVERSING A HEAT ENGINE. Our proof of Carnots theorem relied on the assumption that it is

possible to reverse a heat engine, which would mean taking in thermal energy at a low

temperature from the surroundings (e.g., the cooling water or from outdoors) and releasing high-

temperature thermal energy to the surroundings, as a consequence of our having done work on

the engine. Under these circumstances, our efficiency becomes the amount of thermal energy

transferred (at T1 or at T2, depending on our intent) divided by the amount of work we must do on

the engine.

To transfer thermal energy to the reservoir at T 1,

output - Q1 T

efficiency (warming) = = = 1 (7)

input W T

whereas the efficiency for removing thermal energy from the reservoir at T 2 would be

output Q2 T

efficiency (cooling) = = = 2 (7a)

input W T

Suppose, for example, we wish to move thermal energy from outside, where it is freezing

(0 C) to inside where it is 25o C. Then the calculated efficiency is 298/25 = 11.92 = 1192%.

o

Whereas we could buy 1 kWh of electrical energy and get 1 kWh of thermal energy put into the

room from an electric heater (which is necessarily 100% efficient), if we could put that same

power into a reversible Carnot engine we could get 11.92 kWh of thermal energy into the room,

most of it (10.92 kWh ) coming from the 0oC air outside. Is this possible?

The answer has to be yes and no. Yes, we can build reversible heat engines, which for the

application described would be called heat pumps. Yes, the heat pumps would extract thermal

energy from outside and dump large amounts of thermal energy inside. The same type of reversed

heat engine can also pull thermal energy from the inside of a freezer or refrigerator and dump it

7/10/07 5- 112

into the room. But no, for the same reasons discussed by Curzon and Ahlborn, we cannot get

very close to 1100% efficiency. Actual measured efficiencies typically range between 3 and 5 (or

300% and 500%), which is still quite good, but not as spectacular as Carnot would indicate.

Many people believe an efficiency should inherently be less than, or at most equal to,

100%. The output/input (i.e., efficiency > 1) of a heat pump or refrigerator is therefore typically

labeled as a coefficient of performance.

As we have seen, the first law of thermodynamics deals with the conservation of energy as it

is transformed and transferred between the system and surroundings. Although temperature is

important in measuring energy changes, it enters only as temperature differences, for which the

scale is quite arbitrary. The second law of thermodynamics predicts which of the many

conceivable transformations and transferrals of energy can actually occur, given sufficient time.

In the definition of the entropy function, an absolute temperature appears, which recurs in the

equations for phase equilibrium, in the expressions for the efficiencies of heat engines, and in

other applications of the second law. The third law of thermodynamics is comparatively recent,

having been proposed early in the 20th century. Several forms have been suggested for this

additional postulate, but all are intimately involved with the absolute temperature scale, and

particularly with the absolute zero of temperature.

DETERMINATION OF THE ABSOLUTE TEMPERATURE SCALE. It has not been possible to achieve

the absolute zero of temperature and there is good reason to believe that it cannot be reached,

although temperatures routinely achieved are now in the general range of nanokelvin, 10 -9K.

Measurements at very low temperatures are important, but identification of absolute zero is

critical to studies even at room temperature.

For example, embedded in Carnots equations is a definition of thermodynamic temperature,

measured in terms of thermal energy transfer. From equation 3,

T1 Q1

= (3a)

T2 Q 2

If we compare measurements at the freezing point of water and the boiling point of water, the

measured value of this ratio is 1.366, from which we find T 2 = 2.73 T and T1 = 3.73 T. Then if

we define T to be 100 K, we establish the kelvin scale with T 2 = 273 K and T1 = 373 K.

Alternatively, it is found preferable to set one fixed point, taken as the triple point of water at

273.16 K. The boiling point is then measured to be 100 K above the freezing point of water.

NERNSTS HEAT THEOREM. The entropy change for a chemical reaction at a temperature T 2 can

be found if the entropy change at some other temperature, T 1, is known and the heat capacities of

reactants and products are known. The procedure is analogous to Kirchhoffs law (equation 17,

Chapter 1). For a constant pressure,

7/10/07 5- 113

CP (reactants)

T1 T2 C (products

)

S2 = dT + S1 + P dT (8)

T2 T T1 T

measurements of heat capacities over a range of temperatures, Nernst observed that calculated

entropies of reaction seemed to go to zero as the temperature approached zero. This observation

provided the basis for a generalization known as the third law of thermodynamics.

There are several ways of stating the third law, and many of the implications are best

understood from the standpoint of quantum statistical mechanics. For present purposes the

following statement will suffice:

Every substance in its lowest energy state, at absolute zero, has the same entropy.

An equivalent statement would be

the entropy change for every process (chemical or physical change) becomes zero when the

process occurs between substances in their lowest equilibrium states at absolute zero.

We cannot demonstrate this by carrying out reactions at 0 K. In the first place it is impossible to

achieve absolute zero, and in the second place, the rates of chemical reactions and other processes

decrease so rapidly with decreasing temperature that few, if any, chemical reactions could proceed

at temperatures even near 0 K. It is necessary, therefore, to rely on calculated entropies of

reaction. It is now known that such calculated values include many apparent exceptions to the

third law, which generally prove to be the best supporting argument for the law.

From a knowledge of the structure of a substance, together with an understanding of

statistical mechanics, it is possible to predict which substances are likely to be apparent

exceptions to the third law and to calculate the exact amount of the discrepancy to be expected.

The excellent agreement obtained between theory and experiment on the exceptions is evidence

of the validity of the original postulate.

Assume, for example, that a substance has an energy state that differs only slightly in energy

(or enthalpy) from the lowest energy state, but that this upper energy state has an appreciable

entropy difference from the lowest state. Labeling the upper state with an asterisk and the lowest

state with a subscript zero, H* - Ho is positive but very small, whereas S* - So is positive and not

vanishingly small. Then, at a temperature greater than 0 K, T(S* - S o) may be greater than H* -

Ho, so the free-energy change for the transition to the upper state will be negative and the system

will exist predominantly in the upper state. Only for vanishingly small temperatures will the

enthalpy term be able to overcome the entropy term and make the lowest energy state most

stable, but at such low temperatures the time required for the change of state may be so great that

the lowest energy state is never achieved experimentally.

Entropy is a measure of disorder in a system and its evaluation depends upon a counting

operation, so the entropy differences between states are often expressible as a function of small

integers. Energies, however, may be arbitrarily close. Energy states that are very close together

are said to be degenerate or nearly degenerate. An example of near degeneracy of energy

levels is provided by carbon monoxide, CO, which can pack in a solid crystal in the perfectly

ordered arrangement CO CO CO or in disordered arrangements, such as CO CO OC CO, in

which some molecules are turned around. Although these have only slightly different energies,

7/10/07 5- 114

there are so many possible disordered states that the equilibrium entropy at temperatures slightly

above zero is1 R ln 2 = 5.76 J/molK above the ground state. This disorder remains, frozen in,

as the temperature is lowered toward zero.

Another form of degeneracy arises from the presence of small magnetic effects of the nuclei

(associated with nuclear spins). The magnetic field of the Earth is so weak that the nuclear

magnets are not well aligned with each other. This has a negligible effect on the energy, but again

a very appreciable effect on the entropy. However, the nuclei are unchanged in a chemical

reaction, so there is no entropy change in a chemical reaction arising from these nuclear magnetic

effects. The nuclear effects therefore do not cause an apparent exception to the third law.

Because the spin state does not change, it may be called a frozen metastable equilibrium state,

or a pseudoequilibrium state.

The third law may be restated, explicitly recognizing the existence of nonequilibrium states,

as follows:

Lim S = 0 (9)

T0

for any isothermal process involving only phases in internal equilibrium or involving any phase in a

pseudoequilibrium state, provided the process does not disturb this pseudoequilibrium.

The importance of the third law, for classical thermodynamics, is that it provides a natural

reference level2 from which entropies can be measured and tabulated. These absolute entropies

are available in handbooks, based on measurements of heat capacities from low temperatures. A

few such values are given in Table 1. Tabulated entropies can be added or subtracted to find

entropies of reaction, which can be combined with enthalpies of reaction to calculate free energies

of reaction, and hence equilibrium constants. Entropies can also be calculated, employing

equations of statistical mechanics, if the molecular properties are known from spectroscopic

measurements.

Table 1 STANDARD ENTROPIES, 25oC

Compound State So (J/molK) Compound State So (J/molK)

Al c 28.3 NO g 210.8

AlCl3 c 109.3 NO2 g 240.1

AlF3 c 66.5 N2O g 220.0

Al2O3 c () 50.9 N2O4 lq 209.2

1

The entropy depends on the number of possible molecular arrangements that the

equilibrium state comprises. For each CO molecule there are two possible positions, so for N

molecules, there are (2)N possibilities. The entropy is k ln 2N = Nk ln 2 = R ln 2 = 5.76 J/molK

if N is taken as Avogadros number.

2

This reference level is often called zero entropy, but that name is somewhat misleading.

No absolute value for entropy can be predicted from classical thermodynamics, and there is no

way in which an absolute value of entropy could be meaningfully employed The so-called zero

of entropy is usually not the lowest entropy state attainable, for it ignores the spin effects

mentioned above.

7/10/07 5- 115

Br2 lq 152.2 g 304.4

g 245.47 HNO3 g 266.9

C graphite 5.74 NH3 g 192.7

C diamond 2.4 Na c 51.3

CO g 197.66 NaCl c 72.1

CO2 g 213.78 NaOH c 64.5

CS2 g 237.8 O2 g 205.15

Cl2 g 223.1 O3 g 238.9

F2 g 202.8 P red 22.8

H2 g 130.68 white 41.1

HBr g 198.70 PH3 g 210.2

HCl g 186.90 S rhombic 32.05

HF g 173.78 SF6 g 291.5

HI g 206.6 SO2 g 248.2

H2O g 188.83 CBr4 g 358.1

H2O2 g 232.7 CCl4 g 309.4

H2S g 205.8 lq 214.4

I2 c 116.1 CF4 g 261.6

g 260.6 CH4 g 186.3

K c 64.7 C2H2 g 200.9

KCl c 82.6 C2H4 g 219.3

KOH c 78.9 C2H6 g 229.2

Mg c 32.7 CH3OH g 281.6

MgO c 27.0 lq 160.7

MgCl2 c 89.6 C2H5OH g 281.6

MgF2 c 57.2 lq 160.7

N2 g 191.01 C6H6 lq 173.4

ATTAINMENT OF ABSOLUTE ZERO.3 As we have seen, the most efficient refrigeration system is a

reversible heat pump. The work required to withdraw an amount of heat Q = - Q 2 from a low-

temperature reservoir at T2 is, from equation 7a, W = (T/T2 )Q2 . As T2 goes to zero, therefore,

the amount of work required to remove a given amount of thermal energy from any substance at

the temperature T2 will become infinite. It thus appears that the second law prohibits us from

reaching the absolute zero.

A more meaningful equation for our purposes is obtained by finding the work required for a

given change in temperature. Replacing q2 with CP dT, the differential form of equation 7a

becomes

CP

w= TdT (10)

T2

in which w is the amount of work required to change the temperature of a substance, with heat

capacity CP, from the temperature T2 to the temperature T2 - dT, and T is the difference in

3

See E.M. Loebl, J. Chem. Ed. 37, 361-363 (1960), and R. Fowler and E.A.

Guggenheim, Statistical Thermodynamics, Cambridge, 1939, pp. 224-227.

7/10/07 5- 116

temperature between the substance and the surroundings. If the ratio C P/T 2 becomes infinite, as

might be expected, when T2 goes to zero, the amount of work required for any given temperature

change of the substance would indeed be infinite. It has been found, experimentally, however,

that CP also goes to zero as the temperature approaches 0 K, and in fact the ratio CP /T2 becomes

zero, rather than infinite. Therefore, we cannot argue that the second law prohibits us from

reaching absolute zero.

If CP/T2 does go to zero as T2 goes to zero, as observed experimentally and predicted from

theory, then equation 8 can be applied to find entropies at the absolute zero. (The integral is not

defined unless CP/T remains finite.) Then it becomes possible to show that the third law of

thermodynamics prohibits us from reaching absolute zero.

The proof is as follows. Let A and B represent any two phases that differ in some respect but

which may be interconverted. For example, A and B might represent reactants and products for a

chemical reaction, or they might represent two different crystalline modifications of a given

chemical substance. Then the entropy of A at T 1 may be related to the entropy at absolute zero by

the equation

(T 1 ) = ( A ) dT

T1

+

o

S A S A C P

0 T

and similarly, for phase B, the entropy at any temperature T 2 is

S B (T2 ) = S Bo + C P (B )

T2 dT

0 T

For every temperature, T2, of phase B there must be a temperature, T1 , of phase A such that SA (T1 )

= SB(T2):

T1 dT o T2 dT

0 T 0 T

Rearranging, we obtain

S Bo S Ao = CP ( A) C P (B)

T1 dT T2 dT

0 T 0 T

We may assume T1 $ T2; if this is not satisfied we need only relabel the phases A and B to make it

so.

Because the transformation from A, at T 1, to B, at T2, is isentropic (no entropy change), it

should be possible, in principle, to achieve an adiabatic, reversible transformation,

We are free to choose either T1 or T2; we choose to let T2 = 0. Then either T1 > 0 or T1 = 0. If T1

> 0, then

CP ( A)

T1 dT

0 T

> 0 and SBo > SAo

7/10/07 5- 117

but this would be a violation of the third law, which says that A and B must have the same entropy

at absolute zero.

The only other possibility is that T1 = 0. That is, the transition

A(T1) -----6 B(0)

can occur only if T1 is zero; one cannot reach absolute zero from a non-zero temperature. The

same argument may be turned around. If SBo were greater than SAo, then T1 would be greater than

zero and it would be possible to reach absolute zero. If T 1 must be zero, then it follows that SA o =

SBo.

Therefore, the following statement may be considered as an alternative form for the third law

of thermodynamics:

It is impossible by any procedure, no matter how idealized,

to reduce any system to the absolute zero in a finite number of operations.

7/10/07 5- 118

Appendix

Basic Operations of Calculus

mathematics developed by Isaac Newton and by Gottfried Wilhelm Leibniz. Many problems of

physics, chemistry, and engineering require an understanding not only of the operations of

calculus but also of the justification and the limitations for these operations. Such questions are

properly treated in mathematics texts. This appendix is in no way a substitute for such a rigorous

development of calculus. It is, rather, a temporary expedient to allow the student who has not yet

reached some of these operations in his mathematics studies or has forgotten some details to

apply those particularly simple operations that are required in elementary thermodynamics.

What makes calculus different from ordinary algebra is that it looks at the limiting values of

quantities, including infinite1 numbers of quantities or steps. Provided the mathematical

expressions are well behaved, the resulting equations are no more difficult than algebra.

Whenever the value of one quantity, or variable, depends on the value of some other

quantity, or variable, the first variable is said to be a function of the second. This is often written

y = f (x), read as y equals f of x, to indicate that the value of x determines the value of y. 2 For

example, the area, A, of a circle is a function of the radius, r. We write this A = f (r), where f (r)

= r2. The symbol f ( ) may be considered a mold into which the variable is placed. That is, if

f (r) = r2, then f (x) = x2, f (z) = z2 , and f (a) = a2 . If f (x) = 3x2 - 2x + 5, then f (z) = 3z2 -

2z + 5.

Note that we often build in mnemonic devices. For example, even though area may be

considered as a variable in a particular problem, and would therefore usually be represented by a

symbol near the end of the alphabet, we represent area by A. Furthermore, we let such symbols

do double duty by labeling functions in the same way. Thus we may write

A = A(r) = r2

letting A represent both the variable area and the function whose value gives the area.

1

We represent infinity by 4, but it is not a definite number. Infinity is a symbol, or

name, for any very large quantity that is larger than any number you (or someone else) may select

beforehand.

2

We are assuming at present that f (x) = y is a single-valued function of x; that is, for

each value of x, there is just one value of y = f (x). However, there are many situations where one

value of x may correspond to more than one value of f (x), or the same value of f (x) may arise

from more than one value of x.

7/10/07 A- 119

A.2 Theory of Limits

Zeno posed the problem of Achilles and the tortoise. Achilles could run ten times as fast as

the tortoise. If the tortoise was initially 100 m from Achilles, then when Achilles has run 100 m,

the tortoise has moved only 10 m. When Achilles has run 10 m, the tortoise has moved 1 m.

Each time Achilles runs the distance to where the tortoise had been, the tortoise will have moved

to a new location, ahead of Achilles. Will Achilles ever catch the tortoise?

What bothered Zeno and his friends was that it would require an infinite number of

mathematical steps of the type initially described. Could Achilles ever complete an infinite

number of such steps?

The problem, or paradox, posed by Zeno deals with limiting values, taking smaller and

smaller intervals. We can solve Zenos problem with algebra by requiring that Achilles and the

tortoise be at the same point at some time, t. The position of Achilles, at any time t, is

xA = x0 A + vA t

and the position of the tortoise is

xT = x0 T + vT t

and the initial positions differ by

x0T = x0A + 100

and because

vA = 10 vT

we find, by setting x0T = x0A, with this substitution for vA ,

9 vT t = 100 m

from which we can find when and where Achilles will catch the tortoise if we know v T (or v A).

Because each step is 1/10 as great as the previous step, the steps become infinitesimal and require

shorter and shorter times. Newton and others recognized this did not represent a real difficulty in

finding the sum of steps.

A quite different sort of question is the value of (x 2 - 4)/(x - 2) at the point x = 2. When x =

2

2, x - 4 = 0 and x - 2 = 0, so the ratio is 0/0, which is an indeterminate form. However, the

function is well-behaved; it approaches the same value, from above or from below.

6

2

0 1.75 3.5

x = 2, it approaches the value x + 2 = 4 as x approaches 2 from

below or from above.

7/10/07 A- 120

In the following discussion, we can assume that the limits discussed are all well behaved. In

most instances, no difficulty arises at the specific values of interest. Even if a few of them are not

readily evaluated at a particular point, provided they appear well behaved on approaching that

point from below and from above, we will be justified in evaluating the limits by standard

methods.

An equation usually relates two or more variables, showing the values assumed by one

quantity as the other variable, or variables, take on different possible values. For example, the

pressure, volume, and temperature of an ideal gas are related by the equation

PV = nRT (A1)

in which n is the number of moles of gas, R is a universal constant (8.3144 J/molK, independent

of which real gas is being considered, to the approximation that the real gas follows this

equation), and the temperature is an absolute temperature, usually on the Kelvin scale.

Derivatives. One of the important questions that can be answered from such an equation

concerns the rate at which one variable changes with changes in another. For example, we may

ask how the volume changes with changes in temperature, for a fixed pressure. We can write

nR (A2a)

V1 = T1

P

(A2b)

nR

V2 = T2

P

and therefore

(A3)

nR nR

V = V 2 V1 = (T2 T1 ) = T

P P

or

V nR

= (A4)

T P

It can be seen from Figure A2 that this ratio is the slope of the line of volume plotted against

temperature.

Now suppose we are interested, instead, in how volume changes with pressure, at a fixed

temperature. The curve is a hyperbola, shown in Figure A3. Clearly the slope is no longer

constant. Proceeding as before, we may write

7/10/07 A- 121

V1 = nRT (1/P1) (A5a)

V2 = nRT (1/P2) (A5b)

temperature for an ideal

gas. The slope of the line

is V/T = nR/P.

[Vertical axis V;

horizontal axis T.]

1 1 nRT (P1 P2 ) -P

V = V 2 V1 = nRT = = nRT (A6)

P2 P1 P1 P2 P1 P2

or

V nRT

= (A7)

P P1 P2

This calculated value is not the slope of the curve at either P 1,V 1, or P 2 ,V 2 ; it is the slope of the

chord connecting these two points (b-d, Figure A3). Thus the slope depends not only on where

we start (P1,V1) but also on how far we go. If we want the slope at the point P1 ,V1 that is, the

slope of the line tangent to (touching) the curve at this point we can take P 2 closer and closer

to P1. If P2 is sufficiently close to P1 , we can write the

equation in the form

V nRT

= 2

P P = P1 = P2 P

(A8)

This says that the slope of the line tangent to the curve at

P1,V1 depends on P1, as it should by inspection of the

curve, but not on any other pressure value, which is also

quite reasonable.

7/10/07 A- 122

Figure A3. Volume against pressure for an ideal gas.

The slope of the chord, bd, is V/P = - nRT/P1P2.

The slope of the tangent at b, ac, is dV/dP = - nRT/P 12.

The slope of the line tangent to a curve is called the derivative of the curve, and is written in

the form dy/dx (or in this example, dV/dP). When we need to be more explicit (which is not very

often) we write

dy y (A9)

= Lim

dx x0 x

That is, dy/dx is the ratio of y/x as x becomes vanishingly small.

The two derivatives we have already met would thus be written

dV nR

= (A10)

dT P

and

dV nRT

= 2 (A11)

dP P

Derivatives cannot always be found as easily as for the two examples considered above, but for

present purposes only a very few formulas are required, and these few are given in Table A1.

From these few basic expressions it is possible to obtain many others. A few of these are listed in

Table A2. You should check each of these yourself, by applying the formulas from Table A1, to

be sure you see how the process works.

One word of warning. If you want the derivative at a particular point or for specific values

of the variables, do not substitute values of the variables first. Find the derivative, in terms of the

symbols, then substitute numbers for the symbols, as required.

Function Derivative

y=u+v dy/dx = du/dx + dv/dx

y = xn dy/dx = nxn-1

7/10/07 A- 123

y = ln x dy/dx = 1/x

y = ev dy/dx = ev dv/dx

y = a (constant) dy/dx = 0

Leibniz, the short-hand notation of Newton is often preferred. Time derivatives are indicated by

the dot above; derivatives with respect to position by a prime. Thus

dy dy (A12)

y& = y' =

dt dx

&y& = = ; y" = = (A13)

dt dt 2 dx dx 2

Function Derivative

y = ax dy/dx = a

-(n+1)

y = ax-n dy/dx = -nax

= (1/v2)[ v du/dx - u dv/dx]

ax ax

y=e dy/dx = a e

y = x ln x dy/dx = ln x + 1

E = mv2 dE/dv = mv

7/10/07 A- 124

f = q1q2 /r2 df/dr = - 2q1q2 /r3

v f = vo2 + 2 ax (

dy / dx = 1 / 2 vo2 + 2 ax ) (2a )

1 / 2

= a / vo2 + 2 ax

Differentials. Although the derivatives are defined as the limiting value of a ratio, as the

bottom, and therefore the top, approach zero, it is also possible to interpret derivatives as a ratio

of two infinitesimal quantities -- that is, two quantities each of which is smaller than any number

you may select beforehand. When interpreted in this way, dy and dx are called differentials.

(A14)

(P constant ) dV =

nR

dT

P

(T constant ) dV =

- nRT

dP (A15)

P2

dA = 2 r dr (A16)

dy (A17)

dy = dx

dx

Division is a basic operation, learned in elementary school. The division of a by b, a/b, is

equivalent to asking how many times we can subtract b from a (or, equivalently, by what quantity

must we multiply b to get a; b x ? = a). Thus 0/2 is well defined the answer is zero. But 2/0 is

undefined. You could remove zero from 2 all day long, and still have 2. Nor is there any definite

number c such that 0 x c = 2. We describe 2/0 as infinite, meaning that the answer is larger than

any number you might select beforehand.

Theory of Limits. Less easily analyzed is a division that is equivalent to 0/0. Is the answer 0?

Is the answer infinite, 4 ? Or can we obtain some meaningful value between zero and infinity?

You may be aware of proofs such as 2 = 1 that rely on a hidden division by zero. An important

segment of mathematics deals with the analysis of quantities that appear to be of the form of 0/0,

but can, on closer inspection, be assigned meaningful values.

Consider a similar problem of the theory of limits. As x becomes small, 1 + x approaches 1,

and 1 raised to any power (i.e., 1 multiplied by itself any number of times) would still give 1. But

1/x, as x becomes small, becomes very large, and any number greater than 1 raised to a

7/10/07 A- 125

sufficiently high power should give a large answer. What happens, then, to

(1 + x )1/ x

as x approaches zero? As you can show for yourself by substituting small values of x, the limiting

value of the expression is approximately 2.718, which we label as e.

Lim (1 + x)1/ x = e x60

x60

This quantity appears frequently, and quite naturally, in mathematical and physical problems. In

particular, it often appears as the base of an exponential expression or, equivalently, as a base of

logarithms. The number is irrational (like the familiar ), so it cannot be represented exactly in

decimal form; to 10 places it is e = 2.7182818285 ...

Logarithms. A logarithm is another name for an exponent. For example, we know that 10 3

= 1000. Therefore the logarithm of 1000, to base 10, is 3. The logarithm of 100, to base 10, is 2.

Choosing e as the base of logarithms, if

ez = w

then

lne w = ln w = z

ln uw = ln u + ln w (A18)

so

ln wn = n ln w

and

ln e = 1

where we choose the usual physicists notation

x6 0

ln e = ln (1 + x)1/ x = 1/x ln (1 + x) = 1 x6 0

so

7/10/07 A- 126

Often we need to add together a large number of small changes in a variable or in some

expression involving variables. The summation process may be approached from either of two

viewpoints. One method, which we consider first, is represented geometrically by an area. The

second method may be called an antiderivative.

Area. In section A.3 we looked at the equation for an ideal gas to find how one quantity

changes as another quantity changes. That gave us the derivative, which may also be rewritten as

a ratio of differentials. Differentials may be equated, telling us more directly the infinitesimal

change in one quantity as some other quantity undergoes an infinitesimal change. A derivative, or

ratio of differentials, may always be interpreted as a slope.

For example, we found the derivative, dV/dT, when PV = nRT (and P is constant), to be

dV nR

= (A21)

dT P

and therefore

nR

( P constant) dV = dT (A22)

P

The right-hand side is a product of nR/P and the infinitesimal quantity, dT. Such a product may

be represented as in Figure A4. The ordinate is nR/P and dT is an infinitesimal change in the

abscissa. The product is an area the area of a vertical strip of infinitesimal width, as roughly

represented in the figure.

the area of the jth rectangle. The sum

of all these rectangles (vertical slabs)

is the total volume change for T =

T1 to T2.

As the temperature changes, the location of the vertical strip changes, moving from left to

right for an increase in T. The quantity we seek is the sum of all these changes,

N

nR

P T

i

i (Ti 0, N )

7/10/07 A- 127

which is simply the area of the rectangle, between T 1 and T 2 . Because nR/P is constant (we

assumed constant pressure), the area is easily found. It is

nR

(T 2 T1 )

P

N

V = dV = Vi = V2 V1 (Vi 0, N ) (A23)

i

Therefore

V = V 2 V1 =

nR

(T 2 T1 ) = nR T (A24)

P P

Perhaps the analysis appears fussier than necessary, but the same method may now be

applied to a less obvious problem. We found if we hold temperature constant,

is the area of the jth rectangle. The

sum of these approximates the area

under the curve between P1 and P2.

dV nRT

= (A25)

dP P2

or

dP

dV = nRT (A26)

P2

As shown in Figure A5, the summation procedure gives (for T constant),

7/10/07 A- 128

N N

Pi

V = Vi = nRT ( Vi , Pi 0; N ) (A27)

i i Pi 2

We can evaluate the right-hand side easily enough with a computer or a programmable hand

calculator. For the initial value, P = P1, calculate V1 = nRT/P1. Pick some arbitrary, small value

for P. Then for P = P1 + P, calculate a new V = V, and from this V = V - V1 . Continue

adding P to find P = P + P, then V and hence V = V - V, and so forth. The result, as

depicted in Figure A5, gives V as the area under the curve of nRT/P 2 vs. P.

The accuracy of the answer will depend, in general, on the size of the P we choose. A

smaller value of P will give a more accurate result, but may take a little more computer time. In

principle, we could also find the area, and thus V, by cutting out the shaded area and weighing

it, comparing the weight to a rectangle of the same paper of known area.

Antiderivative. It is often (but not always) possible to find a formula to express the answer

to summation problems such as those just considered. A clue is offered by the last sum, which

can be written as a sum of infinitesimal terms of the form

nRT

d (V ) = d

dP

= nRT 2 (A28)

P P

The sum of small changes is the total change. Writing the sum (G, Greek S) with a stylized S, I,

to represent the sum over an infinite number of infinitesimal quantities, we can express the

problem in the form

dP nRT

dV = nRT P2

= d P

(A29)

and therefore, just as summing up all the small changes in V gives V, summing up all the small

changes in nRT/P gives (nRT/P), so

nRT

V = (A30)

P

dP nRT

nRT = d (A31)

P2 P

7/10/07 A- 129

That is, we recognize where - nRT/P2 came from, which is precisely the reverse problem of

finding the differential (or the derivative) in the first place. Therefore this process has been called

taking the antiderivative.

We call IdV and I-nRT dP/P2 and I (nR/P) dT integrals. The expression following the

integration sign, I, is called the integrand. The approximation errors of numerical integration

depend on the size of the steps, and can therefore generally be made negligible. An analytical

solution fits the curve at each point of the curve, so there is no error of approximation.

To evaluate an integral we ask, What function could we take the differential of to obtain

this integrand? Some basic integrals we typically learn to remember. Extensive tables are

available to help us with more complex integrations. A few examples are given in Table A3.

Definite and Indefinite Integrals. Every physical problem is subject to boundary conditions,

meaning in this instance that we find the sum, or integral, or total change, between a definite

initial state and a definite final state. We express this by noting the limiting values in writing the

integral and in evaluating the result. Thus we would write

nRT dP nRT 2

P

V2 P2

V1

dV =

P1 P2

=

P P1 (A32)

which gives

1 1

V 2 V1 = nRT (A33)

P

2 P1

7/10/07 A- 130

There are times, however, when we are more interested in finding the function from which

the integrand came (i.e., finding the antiderivative) than in finding the actual change. Then we

must recognize that the derivative of a constant is zero, so any arbitrary constant added to the

integral vanishes in finding the integrand. Thus we may write

dP nRT

nRT P 2

=

P

+c (A34)

7/10/07 A- 131

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