PREFACE
object of the present book is to provide an introduction to the and applications of thermodynamics for students of chemistry and chemical engineering. All too often it appears that such students tend to regard the subject as an academic and burdensome discipline, only to discover at a later date that it is a highly important tool of great practical value. The writer's purpose has been to explain the general structure of thermodynamics, and to give some indication of how it may be used to yield results having a direct bearing on the work of the chemist. More than one hundred illustrative numerical problems are worked out in the text, and a total of about three hundred and sixty exercises of a variety of types have been included for solution by the reader. In the
principles
The
hope of imparting the whole subject with an aspect of reality, much of the material for this purpose has been taken from the chemical literature, to which references are given. In order to economize 'space, and at the same time to test the reader's grasp of thermodynamics, the derivations of
To this extent, of interesting results have been set as exercises. at least, the exercises are to be considered as part of the text, although their solution should in any event be regarded as essential to any adequate course in chemical thermodynamics. In treating the various topics in this book the particular method employed has been determined in each case by considerations of simplicity, In some instances the classical, hisusefulness and logical development. torical approach has been preferred, but in others the discussion follows more modern lines. Whenever feasible the generalized procedures, involving reduced temperatures and pressures, which have been evolved in recent years chiefly by chemical engineers, are introduced. As regards statistical methods, the author feels that the time has come for them to take their place as an essential part of chemical thermodynamics. Consequently, the applications of partition functions to the determination of heat capacia number
equilibrium constants, etc., have been introduced into the text in the appropriate places where it is hoped their value will be appreciated. The symbols and nomenclature are essentially those which have been widely adopted in the American chemical literature; however, for reasons given in the text, and in accordance with a modern trend, the Gibbs symbol M and the shorter term "chemical potential" are employed for the partial molar free energy. Because atmospheric pressure is postulated for the conventional standard state of a liquid, some confusion has resulted from the use of the same symbol for the standard state as for the liquid at an arbitrary pressure. Hence, the former state is indicated in the text in
ties, entropies, free energies,
VI
PREFAOB
the usual manner, by a zero (or circle), but the latter is distinguished by a small square as superscript. The writer would like to take this opportunity to acknowledge his indebtedness to certain books, namely, F. H. Macdougall, "Thermodynamics and Chemistry"; L. E. Steiner, "Introduction to Chemical Thermodynamics"; B. F. Dodge, "Chemical Engineering Thermodynamics"; and, in
particular, G. N. Lewis and M. Randall, "Thermodynamics and the Free Energy of Chemical Substances." He is also sincerely grateful to Dr. Allen E. Steam, University of Missouri, and Dr. Roy F. Newton, Purdue
I diversity, for reading the manuscript of this book and for making numerous suggestions which have helped materially to clarify and improve the treatment. Finally, the author wishes to express his thanks to his wife for reading the proofs, and for her continued aid and encouragement.
SAMUEL GLASSTONE
BERKELEY, CALJF. November 1946
CONTENTS
CHAPTER
PACE
PREFACE
I.
v
1
HEAT,
1.
WORK AND ENERGY
Introduction, 1;
5.
2.
Temperature,
2;
3.
Work, Energy and
Heat,
II.
PROPERTIES OF THERMODYNAMIC SYSTEMS
4.
14
18.
Thermodynamic Systems,
14;
5.
Equations of State,
HI.
THE
6.
FIRST LAW OF THERMODYNAMICS The Conservation of Energy, 33; 7. Energy and Heat Changes,
Thermodynamic
Processes, 41.
33
36; 8. Reversible
IV.
HEAT CHANGES AND HEAT CAPACITIES
9.
47
11.
The Heat Content,
47;
10.
Adiabatic Processes, 55;
The
JouleThomson
Effect, 60.
V. THERMOCHEMISTRY
12.
68
68;
13.
Heat Changes in Chemical Reactions,
plosion Temperatures, 84; 89.
14. Calculation of
Flame and ExHeat of Reaction,
VI. CALCULATION OF
15. Classical
ENERGY AND HEAT CAPACITY
16.
95
Theory
of
Theory, 95;
99;
17.
Quantum
Statistical
Heat Capacity,
Heat Capacity
of Solids, 120.
VTtrTHE SECOND LAW OF THERMODYNAMICS
18.
129
Entropy, 141.
Conversion of Heat into Work, 129;
19.
VIII.
ENTROPY RELATIONSHIPS AND APPLICATIONS
Temperature and Pressure Relationships, 154; 21. Knergy and Heat Capacity Relationships, 163; 22. The JouleThomson
20.
Effect, 171.
154
IX. ENTROPY DETERMINATION AXD SIGNIFICANCE 23. The Third Law of Thermodynamics, 178;
Treatment of Entropy,
183.
178
24. Statistical
X. FREE ENERGY
25.
201
Functions, 201;
26.
The Free Energy and Work
Chemical
Potential, 213.
XI. PHASE EQUILIBRIA 27. Systems of One Component, One Component, 237.
vii
222
222: 28. Systems of
More Than
Viii
CONSENTS
PAGE
CBAPTBB
XII. FUOACITT AND Acnvri Y
.
260
30. Mixtures of Gases, 261;
29. Fugacity of a Single Gas, 250; 31. Liquid Mixtures, 268.
XIII.
FREE ENERGY AND CHEMICAL REACTIONS
32.
273
The Equilibrium Constant,
273;
33.
Free Energy Change in
Chemical Reactions; 282.
XIV. THE PROPERTIES OP SOLUTIONS
'
317
_
34. Ideal Solutions, 317; lute Solutions, 337.
35.
Nonideal Solutions, 330; 36. Di
XV. ACTIVITIES AND ACTIVITY COEFFICIENTS
37.
360
Activities, 356.
Standard States. 350; 38. Determination of
XVI. SOLUTIONS OF ELECTROLYTES
39. Activities
378
and Activity
Coefficients, 378.
XVII. THE DEBYEHttcKEL THEORY
40. Ionic Interaction in Solution, 407; DebyeHttckel Equation, 412.
41. Applications of the
407
XVIII. PAKTIAL
12.
MOLAR PROPERTIES
,
427
Determination of Partial Molar Properties, 427; 43. Partial Molar Volumes, 433; 44. Partial Molar Thermal Properties, 437.
XIX. E.M.F.'s AND THE THERMODYNAMICS OP IONS
45. E.M.F.'e
462
and Electrode
Potentials, 462; 46.
Thermodynamics
of Ions in Solution, 186.
APPENDIX:
Table Table Table Table Table
1.
2,
3.
4.
5.
501 Constants and Conversion Factors 502 Properties of Gases and Liquids 503 Heat Capacities of Gases 504 Heat Capacities of Solids Standard Free Energies and Heats of Formation,
Integral Heats of Solution of Salts
and Entropies
Table
6.
505 506 509
INDEX
CHAPTER
HEAT,
I
WORK AND ENERGY
1.
INTRODUCTION
1
The subject matter of Scope and Limitations of Thermodynamics. thermodynamics is based essentially on two fundamental postulates (or laws) which summarize actual experience with regard to the interconversion of These are called the first and second laws of different forms of energy. thermodynamics. There is also another postulate dealing with certain aspects of the second of these laws; it is often referred to as the third law of thermodynamics, but its use is more restricted than is that of the other laws. By the application of relatively simple and well established mathematical procedures to the two basic laws, it has been possible to derive results which have proved of fundamental importance to chemistry, physics and engineerFor example, equations have been developed giving the variation with ing. temperature and pressure of certain physical properties of substances. Of more direct interest to the chemist, however, is the derivation of the exact conditions for spontaneous chemical reaction and for chemical equilibrium. Although the great practical value of thermodynamics is undeniable, as will be shown in the subsequent pages, there are certain limitations that must be borne in mind. The methods of thermodynamics are independent of atomic and molecular structure, and also of reaction mechanism. Consequently, the results throw no direct light on problems related to these subThe conclusions of thermodynamics may be correlated with those jects. of the kinetic theory of matter, for example, but the distinction between the two approaches to the study of physical problems must be clearly understood. Thus, the observable thermodynamic property of a body known as its "temperature" may be regarded as being determined by the average kinetic energy of the molecules. However, the concept of temperature as used in thermodynamics is independent of any theories concerning the existence of molecules. As will be seen shortly, temperature, like other thermodynamic variables of state, is based oil experimental, macroscopic observation of the body as a whole. One aspect of thermodynamics is the prediction of relationships between various quantities that are directly observable or which can be derived from observable properties, but thermodynamics alone cannot give any indication
la.
'
In order to obtain the information possible to invoke certain procedures, such as the kinetic theory of matter, statistical mechanics and the DebyeHlickel theory, which really
of the actual values of these quantities.
it is
1
P.
W. Bridgman, "The Nature
of
Thermodynamics/' 1911.
2
lie
HEAT,
WOHK AND
IONBRGY
outside the scope of thermodynamics. Nevertheless, because such methods and theories provide a means for the calculation of thermodynamic properties, they may be regarded as complementary to thermodynamics. They are, however, not essential, for the observable quantities under consideration can usually be obtained by experimental methods without recourse
to theory. As far as chemical reactions are concerned, thermodynamics can indicate whether a particular process is possible or not, under a given set of circumstances, e.g., temperature and concentrations of reactants and products However, no information can be obtained from pure thermodynamics as to the rate at which the reaction will take place. For example, it can be shown by means of thermodynamics that hydrogen and oxygen gases should combine to form liquid water at ordinary temperatures and pressures, but it is not possible to state whether the reaction will be fast or slow. Actually, in the absence of a catalyst, the combination is so slow as to be undetectable in many years. In effect, thermodynamics deals quantitatively with equilibrium conditions, that is, conditions which do not change with time, and 2 it does not take into account the rate of approach to the equilibrium state.
2.
TEMPERATURE
2a. The Concept of Temperature. Since the laws of thermodynamics deal with the interconversion of energy, it is necessary to consider the sigBefore nificance of energy, and of the related quantities, heat and work. doing so, however, it is desirable to examine the concept of temperature. The ability to distinguish broadly between hot and cold is a familiar faculty of the human senses. substance which is hot is said to have a higher temIf a hot body, such as a piece of metal, is perature than one which is cold. in with similar a but colder body, then after a short time the contact placed senses show that one is neither hotter nor colder than the other. That is to
A
two bodies have attained a state of thermal (or temperature) equiand they are both said to be at the same temperature. The body which was originally hot will now feel colder to the touch, whereas the colder one will now feel hotter. The temperature of the hot body has consequently decreased while that of the cold body has been raised until at equilibrium the two temperatures are the same. It would appear, therefore, that something actually energy is transferred from the hotter to the colder body until the two bodies have equal temperatures; that which is apparently transferred in this manner is called "heat." Thus, heat may be defined as that which to one another solely as the result of a difference in temperature. passes from body The quantity of heat transferred in this manner depends, in the first place, on the change of temperature of each body. Another factor, namely the
say, the librium,
heat capacity, will be considered later. Although the human senses can detect temperature differences to some extent, they are obviously not adequate for precise measurement; neither
1
8. Glaustone,
K.
J. Laidler
and H. Eyring, "The Theory
of
Rate Processes," 1941.
2b
TEMPERATURE
3
can they be used to associate a definite number with each temperature. For these purposes it is necessary to have an instrument or device known as " The principle of the thermometer is based on the fact a "thermometer. certain that properties, such as volume or electrical resistance, vary with temperature. In the ordinary mercury thermometer, for example, use is made of the change in volume of mercury with temperature; in this case, however, the volume changes are observed by the alteration in length of the column of mercury in a narrow glass tube. Suppose such a thermometer is placed in contact with a body until thermal equilibrium is attained; the position of the mercury in the glass tube is then said to represent an arbiIt has been found experimentally, in trary temperature of t degrees (t). agreement with expectation, that if two bodies are each in thermal equilibrium
with a third, they are in thermal equilibrium with one another. This fact renders possible the use of the thermometer as an indicator of temperature. It means that whenever the mercury reaches a certain point the temperature of any body is always t, provided thermal equilibrium is attained between the body and the thermometer.
2b. Thermometric Scales: The Centigrade Scale. In order to use a thermometer for the quantitative expression of temperature and of temperature differences, two things are necessary. First, a zero point of the temperature scale must be chosen, absolutely or arbitrarily, and second, the size of the unit, i.e., the degree, must be defined. On the centigrade temperature scale the zero is taken as the "ice point/' that is, the freezing point of water in contact with air at standard atmospheric pressure (76.00 cm. of mercury).* The size of the degree is then defined by postulating that the "steam point," that is, the boiling point of water at standard atmospheric pressure, shall be taken as exactly 100. If represents any physical property which varies with temperature, and 100, respectively, on the centigrade and XIQO are the values at XQ is then the X"o) in the scale; degree represented by the change rJir(^ioo is the value of the property at any temperature f the given property. If magnitude of that temperature is then t, as given by
X
X
is the length of a mercury column in In the common mercury thermometer a glass tube, and the distance between the positions representing XQ and Xioo is divided into one hundred equal parts, in order to facilitate evaluation of the temperature in accordance with equation (2.1). * It should be noted that and hence saturated, with air at
X
C
1
is taken as the freezing point of water in equilibrium, atm. pressure, and not that of pure water; the freezing
0.0023 C. point of the latter is t By the expression "the value of the property at any temperature" is implied the value of the property of the thermometfic substance when it is in thermal equilibrium with a body at the given temperature.
+
4
HEAT,
WORK AND ENERGY
2c
of different thermometric substances, or the differSince the property ent fchermoirietric properties of a given substance, do not vary in an identical manner with temperature, various thermometers, all of which have been and 100 C, may indicate different temperatures when in standardized at thermal equilibrium with the same body at an intermediate point. mercury thermometer and a toluene thermometer, for example, which agree at and 100 C, would differ by several degrees in the vicinity of 50 C. Even mercury thermometers in tubes made of various types of glass indicate
X
A
Gases have frequently been used as thermometric substances; thus may represent the volume of a given mass of gas at constant pressure, or the pressure at constant volume. However, here again, the variation with temperature of the volume (or pressure) of a gas depends somewhat on the nature of the gas. For gases, such as hydrogen and helium, which do not depart greatly from ideal behavior ( 5c) under ordinary conditions, the temperatures recorded do not differ very appreciably, and the differences become less marked as the pressure of the gases is decreased. It appears, from experimental observation, that at sufficiently low pressures or, better, if the results are extrapolated to zero pressure, the temperature of a given body as recorded by a gas thermometer would always be the same irrespective of the nature of the gas. 4 It follows, therefore, that when gases approximate to ideal behavior, i.e., at very low pressures, the differences in their thermometric properties disappear. This fact presents the possibility of devising a temperature scale which shall be independent of the thermometric substance, the latter being a hypothetical "ideal gas." Such a scale is the socalled "absolute ideal gas scale," in which the (absolute) temperature is taken as directly proportional to the volume of a definite mass of an ideal gas at constant pressure, or to the pressure at constant volume. For convenience, the magnitude of the degree on the absolute scale is usually taken to be the same as on the centigrade scale ( 2b), so that the absolute temperature T on the ideal gas scale is given by
3 slightly different temperatures. 2c. The Absolute Ideal Gas Scale.
X
r
v
,
,
(2.2)
Fo)
where V is the volume of the ideal gas at this temperature, and Fioo and Fo are the corresponding volumes at the steam point and ice point, respectively, all the volumes being determined at the same pressure. The value of the ice point To on the absolute scale may be determined by setting F equal to Fo in equation (2.2), so that
O

(23)
By making measurements on
8 4
various gases, at constant pressures, and
International Critical Tables, VoL I, p. 55. , Wensel, /. Res. Nat. Bur. Stand., 22, 375 (1039).
a
as defined above. i.16 K. This is sometimes called the Kelvin scale. Stand. 0. The addition of 273. 1. melting point of silver. Practical Temperature Scale. 6 3.16 C. thermometer. consequently a number of fixed points have been chosen by international agreement which can be used for the determination of experimental temperatures on the centigrade scale. using the 459.e. It will be noted from equation ice point taken as (2.e. the thermodynamic scale can be shown to be identical with the absolute ideal gas scale. temperatures on the latter.16 then gives the corresponding absolute temperatures. as well as the former. expressed in appropriate units.00 C. and others of which determine various intermediate temperatures. The ice point is consequently 273. some of which extend the scale to 3400 C. all at standard atmospheric pressure. Res.00 C. WORK. Fahrenheit degree. application of of the force and I is the of its of displacement point magnitude application...1)]. based on the second law of thermodynamics.5 C. Lord Kelvin (William Thomson). the lowest limit of temperature. The following temperatures are taken as primary standards: boiling point of oxygen. 444. It may be noted. 100. in honor of its originator. boiling point of sulfur. A number of subsidiary fixed points. Roeser and Wensel. that the thermodynamic derivation of the absolute temperature scale provides a more definite interpretation of the absolute zero. ice point. J. 1063 C. Bur. have also been proposed. . than is possible by means of the ideal gas . steam point. Mechanical work is done whenever the point of a If F is the force is displaced in tJie direction of the force. then the mechanical work done is In addition to equal to the product F X I.3a WORK.16 to the temperature of the ideal gas thermometer on the ordinary centigrade scale. 273.2) that on the absolute scale the volume of an ideal gas should become This hypothetical point.60 C. 247 * Work and + (1935).97 C. Nat. i.3).16. and melting point of gold. is known as the absolute zero of temperature. Temperatures on the absolute ideal gas scale are thus obtained by adding 273.005 of it have been realized. ibid.* For practical purposes gas thermom2d. in the direction in which the force acts. eters are not satisfactory. 960. it has been found that the ice point 5P as given by equation (2. it should be presumably represents the lowest conceivable temperature. the temperature is then given by J(F) 6 Burgess. ENERGY AND HEAT 5 extrapolating the results to zero pressure. .. is 273.. It will be seen in Chapter VII ( 18k) that it is possible to develop an absolute temperature scale.182. with the C [equation (2. which zero at a temperature of zero degrees. also independent of the nature of the thermometric substance. 3a. There are reasons for believing that the absolute zero is unattainable ( 18j). 635 (1928). scale are represented by the symbol K. ENERGY AND HEAT Energy.69 R. Actually. 14. although temperatures within less than 0. Engineers frequently express temperatures on the Rankine (absolute) scale. incidentally. hence.
The standard meter is. because heat. but each can be expressed as the product of an intensity factor and a capacity factor. respectively. other forms of work are possible. because of the connection between work and energy. as defined in 2a.e. sometimes referred to as the intensity factor. was originally defined as 10~ times the length of the earth's quadrant.e. The meter.028 cc. 3b. i. the capacity factor. follows historical tradition.. i.). the one used here is somewhat simpler when the problems of dimensions and units of energy come up for consideration. Washington. the E. system is the erg. i. but is actually 1000. is not significant.. however. The standard kilogram. near Paris. mechanical force is equal to the product of mass and acceleration. and the generalized dis placement is the quantity of electricity. The derivation of the concept of energy through those of force and work. constituting what is known as the c. and a generalized displacemert. it was meant to be 1000 cc.). passing through Paris.. length and time usually employed in scientific work are the gram (g. work itself. There are thus various manifestations of energy.. which is a form of energy.s. kept at Sevres.. including heat itself. produces in it a velocity of motion of 1 cm. the distance between two marks on a bar at C. * of Standards.e. . e. multiplied by length.. The work done is thus equal to the product of the applied E. Exact duplicates of the standard meter and kilogram are kept at the National Eureau D. and the cc. By Newton's laws of motion. as represented by the different forms of work.) and second (sec. pressure.00 grams. ence between the ml. on a mass of 1 g.g.* It was intended to be equal to the weight of exactly 1000 cc. however. electrical work. hence force has 2 2 the dimensions of mass Since work is equal to force length/ (time) . for example. but in each case the work done is equal to the product of a generalized force. Further. the differis exactly onethousandth part of a liter. centimeter (cm. The units of mass.F. the generalized force is the socalled electromotive force. The unit of energy in the c.e. Dimensions and Units of Energy. Because of this discrepancy it is becoming the practice to express volumes of liquids and gases in terms of the milliliter (ml. all forms of the latter can be expressed in work units. Although this approach to the subject of energy has some advantages. i. also at Sevres.g.. The liter is the volume occupied by 1 kilogram of water at 4 C and 1 atm. from north pole to equator.g. mlt~ as stated the dimensiona of work are ml2 t~2 and all above. In electrical work. The second is defined as 1/86.. . including. as given above. is taken as the mass of a lump of platinum. which For most purposes. cannot be completely converted into work. or 100. it is the work done when a force of 1 dyne acts through a distance of 1 cm.400 part of a mean solar day.6 HEAT. of course. 1000. the latter being the average interval between successive transits of the sun across the meridian at any given place.000 cm.. but there is actually a small difference. 4 C. per X .F. and the quantity of electricity which is passed. C. However. 7 system. WORK AND ENERGY 3b mechanical work. some writers prefer to describe energy as that which can be transformed into heat.s. of pure water at its temperature of maximum density.). Energy is defined as any property which can be produced from or converted into work. forms of energy must consequently have these dimensions. the dyne being the force which acting for 1 sec.M.M.
The int.P. 6 Birge. and the capacity factor is the heat capacity ( 3d).F.. which can be stated in ergs if required ( 3e). 7 7 In view of the definitions of energy given above.11800 milligrams of silver in the electrolysis of a solution of silver nitrate under certain specified condiThe (international) volt is defined in terms of the E. substance for that matter. as the result of a difference of temperature.3d sec. is equal to the product of the quantity of electricity and the applied potential difference. so that X 10 ergs. and heat can be. is defined as 10 ergs. converted Heat is produced from mechanical work. joules. joules.0002 Energy expenditure to four significant figures. it is the form in which energy is transferred from one body to another. joule is equal to 1. the joule. 3d. viz. Energy expenditure  26.. 1 amperesecond. a subsidiary unit.45 X 2.432 = 107 64. which is taken to be exactly 1.0002 X = 64. confusion has arisen because of the necessity for distinguishing between the absolute joule as thus defined. 6 Problem: A quantity of 26. Since the former is given in int. or of any other.e.M. of 1 (international) volt. (b) ergs.e. i. thus.33 int. Bur. is a measure of the heat energy transferred. at least partially. and the international joule. a certain amount of heat can be converted into work. heat is expressed in terms of a unit known as the (15) calorie. WORK. for instance. 33. In evaluating the quantity of heat energy that has passed to a given body. Rev. of electricity flows under the influence of a potenThe (international) coulomb is the tial. . that must be supplied to raise the temperature of a given amount of warter. i. and electrical work is transformed into heat by the passage of On the other hand. 13. by means into work. Nat. 235 (1944). On this basis. Calculate the energy expenditure in (a) international joules. Heat and Energy.0002 abs. the energy expended. /. coulomb. the international joule is apparently equal to 1.e.. coulombs and the latter in int. machine. and hence to 1. quantity of electricity which will cause the deposition of 1. i. either by direct contact or by means of radiation. joules. Res. which is defined as the quantity of heat required to raise the temperature of 1 gram of water by 1 in the vicinity The actual temperature is specified because the quantity of heat of 15 C. = 64. since most forms of work can be readily converted into heat. The electrical work done. Mod. E.34 X 10 ergs. Phys. standard cell. the product of these two quantities. Stand. heat must be regarded as a form of energy. As a general rule. Heat Capacity. ENERGY AND HEAT 7 7 Since the erg is so small. volts. From the standpoint of thermodynamics. heat is energy in transit. 233 U941>: Curtis.0002 absolute joules.0183 (international) volts at 20 C. 3c. by 1 depends to some extent on the temperature itself.. of the Weston tions.. by means of a suitable electricity through a resistance..M. Unfortunately.432 volts. based on The latter is the work done when 1 (international) electrical measurements.45 coulombs of electricity flows through a conductor under the influence of a fall of potential of 2.33 X 1.. the result will be in int. of friction. a heat engine. the intensity factor is the change of temperature.
the molecular (or formula) weight in grams.e. The two most important are constant pressure and constant volume. From the standpoint of the chemist. l 1 . The heat capacity is a property which is proportional to the quantity of matter present. cal. Thus.. C(2'. (3. The heat capacity is frequently referred to 1 gram of material. the term "mole" will refer to the simple formula weight in grams. is equal to 1 (15) caloric. Unless otherwise stated.g. the mole of acetic acid is 60. if the temperature !T 2 T\ is represented by AT the true heat capacity is given by the expression 7 make . in spite of the fact that a large proportion of s)* * molecules may be present. It is necessary to indicate. It will be seen later ( 9b) that the heat capacity of a substance can have a definite value only under certain specified conditions.~ g. e. From the definition of the calorie given above.  TO. if the temperature of the body is raised from TI to 7*2 by the passage to it of an amount of heat Q.* The quantity of heat is then known as the molar heat capacity. the particular conditions under which heat is transferred to or from the given substance. . it is evident that the heat capacity of 1 gram of water. and this must consequently be stated. C= T 2>Tl Hm^. Two particular quantities are commonly employed. deg. deg. Thus. it is then called the specific heat.05 g. &T 7 (3.3) Since the quantity of heat Q is usually stated in calories and AT in degrees. WORK AND ENERGY 3d The heat capacity of a body is the property which multiplied by the temperature change gives the quantity of energy which has entered or left the body as heat when it is brought jnto contact with another body having a different temperature. the heat capacity C of the body is given by Q = According to this equation. the specific heat of water is exactly 1 calorie per degree per gram in the region of 15 C.. in the vicinity of 15 C. a more useful form of the heat capacity is that referred to 1 mole. thus. calories per degree per gram (or per mole). As already indicated. it is evident that the dimensions of heat capacity are calorics/degrees for the 1 l given amount of material. i. therefore. thus. In (3. the heat capacity of a body or substance usually The heat capacity as defined by equation varies with the temperature.8 HEAT." or cal.2) is thus the mean value for the temperature range from T\ to TV order to define the heat capacity at a given temperature it is necessary to increase the temperature interval as small as possible."" mole~ that is.1) C = > (32) so that the heat capacity is sometimes defined as the quantity of heat required to raise the temperature of a body by 1..
544 C. gives 1 int. usually water. there is such an exact connection is really an aspect of the first law of thermodynamics ( 6a). Heat quantities are usually measured by means of a calorimeter." . X R in int.M. From the resistance. ampere is the current which flawing for 1 sec. joules per degree. joules. calculate the heat capacity of the calorimeter. but the foregoing description indicates the fundamental principle involved in modern calorimetric work.43 is X 185 int.43 ohms contained in a calorimeter. Problem: A current of 0. and the int. (0.M. and passing a definite current for a The accompanying increase of temperature of the calorimeter is specified time. can be Similarly. then determined by means of a thermometer placed in the liquid. it Since the rise of temperature of the calorimeter 0. . the heat capacity of the calorimeter can be determined in int. which will be tacitly assumed for the present. the value of any quantity as the result of a chemical reaction. and which contains a calorimetric liquid.P. it is necessary to know the relationship between joules and calories. In its simplest form this consists of a vessel. of about t\vo parts in 10. Heat generated = (0. The Measurement of Heat: The Defined Calorie.565 amp. joules. X of the calorimeter is known. the change in temperature of the substance must also be known.. Because of a slight uncertainty. and since the latter is given by / X t. coulomb of elecand an int. it is seen that If / is in int. electrical work. joule ( 3b). ohm is the resistance of a conductor through which passes 1 int. it follows that Electrical Work = 72 X R X t. for example. In the present case. stance can be found from the amount of heat it transfers to a calorimeter. where / is the current and R the resistance. volt is when applied. and the quantity of electricity. the heat capacity of any subreadily determined by equation (3.000. int. through a coil of The rise of temperature is obresistance 15. ohms * and t in sec.1).544 C. the fall of potential (or E. is passed for 3 min. current and time the amount of electrical energy expended can be If it is assumed that this energy is completely calculated in terms of int. to / By Ohm's law. 5 sec. served to be 0.F. taking the heat generated as equal to the joules.. therefore.36 WORK. as defined in 3d. follows that Heat capacity = Once the heat capacity it. ENERGY AND HEAT 9 3e. ampere int. In actual practice various devices are used to improve the accuracy of the results.43 1675 int. of heat transferred to * An 1 tricity. where t is the time for which the current is passed. concerning the relationship between the standard (15) calorie. In order to convert the results obtained by the electrical heating method into That calories. The heat capacity of the calorimeter and its contents is determined by placing an electrical conductor of known resistance in the liquid.565) 2 X 2 15.) across the resistance coil is equal R. the work will be given in int. a defined calorie. joules 185/0. which is insulated as well as possible in order to prevent loss or gain of heat.565) X 15. transferred from the conductor to the calorimetric liquid in the form of heat. Assuming that no heat is lost to the surroundings. amps.544 1 deg. The electrical work is equal to the product of the E.
Consider any substance. which may be gaseous. Work of Expansion* terest to the chemist. 12. joules 1675/4.1833 int. Calculate the heat in defined calories evolved in the reaction. for 185 sec..183 = 400. and is equal to the specific heat of water at about 17 C. For this reason. P X a. heat cannot be completely transformed into work without leaving some change in the system or its surroundings. in the reaction is here exactly equal to that obtained it from Hence.. It will be seen in Chapter VII that heat differs other forms of energy in one highly significant respect. and the work done upon or i In most processes of in3g.e. I (1944). * It is assumed that the piston is weightless and moves without friction. i.43 ohms.. that of the atmosphere. Whereas all other forms of energy are completely convertible into work. . Phys. i from it. Am. Nat. WORK AND ENERQY 7 3f This differs to a very small equivalent to 4. J. The heat produced the electric current. extent from the standard calorie. mechanical. from the preceding problem in the reaction follows that Heat evolved = = 1675 int. Suppose the substance in expansion the cylinder expands.. is equal to the force P X a multiplied by the 7 " * Rossini.. /. part of the heat taken up at a particular temperature is converted into work.10 HEAT. and the remainder is given out at a lower temperature (see Chapter VII). 407 (1939). loss in energy of a body may thus be defined in terms of the 3f. electrical. itself. This is frequently referred to as work of expansion. due to a temperature difference. Mueller and Rossini. In the continuous conversion of heat into work. from all heat transferred to or . e." of which various The gain or types. The latter i^ usually considered under the general description of "work. Res.. by means of a heat engine. through a heating coil of resistance 15. joules has been proposed. Heat and Work. In order to obtain the same increase of temperature it was necessary to pass a current of 0.4 calories. and as a result the piston is raised through a distance h. upon is i FIG Work of f orce acting on the piston then the product of the pressure and the area. liquid or solid. fitted with a piston the is exerted a constant total which pressure P. e. that is. the only work involved is that due to a change of volume against an external pressure. so that no work is lost in the actual motion of the piston.e. tiur. etc. 22. surface.565 amp. for example. The work done against the external pressure.g. are possible. the work of expansion. Stand.. at least in principle. Problem: A chemical reaction was allowed to take place in a calorimeter and the rise of temperature was observed.g... 1). contained in a ^cylinder * of crosssectional area a (Fig. i. and energy that is transferred in other ways. it is convenient in the thermodynamic treatment to distinguish between the energy that enters or leaves a body as heat.
0132 5 X 10 6 dynes cm. The results X 10 2 int.0133 X 10 9 ergs = 1. point of application in the direction of the force ( 3a). equal to F 2 Fi. the work will be obtained in ergs. and this can be readily converted into abs. of mercury.0131 ergs. therefore." 2 is the acceleration due to gravity. the density of which is 13.028 cc. Fi) (3.66 cm. where the factor 980.0131 X defined calorie is 4. The quantity a Work of expansion = P(F 2 = PAF. = = 76. all quantities in this procedure is of diminishing the risk of error is to express 3b) before undertaking any calculations. 3 so that the product is in dynes cm. (c) The int. One way ( units . atm. are frequently expressed in various units. is the increase of volume against the external pressure P. i. joules. joules. if required.e. and The 1.. the pressure must be expressed in dynes cm.. confusion is liable to ensue unless all quantities are labelled correctly and completely by the appropriate units. (c) int. = 1.1833 = 24.2 .. so that the work of expansion is literatm. at sea level and a latitude of ] 45.e. cm. 1 atm.5) as 1. (d) defined calories.595 To at C. is equivalent to exactly 76 cm. that P X a X h. energy. joule is equal to 1 .5) where AF.0133 10* ergs is thus equivalent to 1.0131 3h.218 def. The treatment can often c.g.e.. BNERfty AND HEAT 11 i.4) or (3. sec.000 X 13. joules.0002 abs. where V\ is the initial volume and F 2 is the final volume. X 107 is X X (d) The 1. (6) and the volume of 1 obtain the value in ergs. (a) 1 In this case P is . cal. 1 atm. to five Since liter is significant figures. The units employed for expressing pressure and volume determine the units in which the work of expansion is obtained from equation (3. and this may be replaced by F 2 Fi. joules ( 3b). and the volume change AF in liters. 10 7 ergs.g. the work is then in literatm.. If P is given in dynes per sq. equal to 1000. pressure P in atmospheres. the work of expansion is given by 3 6 equation (3.s.3h displacement h of its WORK.0132 6 X 10 X 1. e. but sometimes unnecessarily tedious. hence. and F is in cc. 1.218 defined cal. units. ( 3b).. and For some purposes.1833 int. It follows.5). joules..e. hence to 1. it is convenient to express the calories. Problem: A substance expands by 1 liter against a constant pressure of 1 atm. Calculate the work done in (a) literatm. joules may be summarized: = 24." 2 A pressure in cm. which is supposed to remain constant throughout the expansion. 1 literatm.~2 1.4) (3. and so the work of expansion 10 2 /4. ergs.66 dynes cm. and AF is 1 litar. .595 X 980. i. Because quantities having the same dimen sions. (b) ergs.0002 102 int. Conversion Factors.000028 X 10 i.0133 X 10 ergs. X h represents the increase in volume in the expansion process.
... Calculate the heat generated in (i) joules.. When an electric current was passed through a heating coil of resistance 16. When a piece of metal weighing 19.287 C." of a calorimeter.205 X 10~*2). at the ice point. 8. is to convert them into a dimensionless form. 24.45 to 23. Evaluate the heat capacity of the calorimeter in (defined) cal. deg.12 HEAT.00 C. At a certain temperature the volume has increased by 22. deg. The application of the foregoing ideas will be illustrated in subsequent portions of the book.954 volts. 7.? 6.8146 X 10<* + 9. A mercuryinglass thermometer is standardized at and 100 C. by 24. Neglecting loss of heat by radiation. as seen above.4 cal. the fall of potential across the coil was 3. the temperature of the latter was found to rise from 22. A number of be considerably simplified derived in the problem in conversion factors which will be required from time to time are collected in Table 1 of the Appendix at the end of the book.0591 (defined) Determine the cal.4 (defined) cal.243 amp. deg.18 ohms.50 C. 3. liter" 1 atm. In applying these factors.1 4.g. WORK AND ENERGY 3h by employing conversion factors. previously heated to 100.e. F. corrected to ideal behavior.." . The volume of a gas. The change of volume of mercury between these temperatures is represented by vt = t. i. and that similar units cancel one another if they appear in the numerator and denominator of a fraction. determine the rate of increase of temperature.500 g. . ./literatm. sec. The heat capacity of a calorimeter was found to be 218. without dimensions.6 ml. For example.46 g. where v* is the volume at the correct centigrade temperature t.49 ohms. joules. was dropped into the calorimeter. hence. a useful device which avoids the possibility of error in the less simple cases. in 1 1 deg.. total heat evolved in (i) ergs. (l + 1. through a resistance of 20. is passed for 15 min. is equivalent to 24. is 442. private communication. Neglecting the expansion of the glass. What is the mean heat capacity of the metal in cal. Newton. It is then permissible to multiply one side of an expression by . 8 unity and the other side . of a metal of mean heat capacity 0. deg. The heat generated in the preceding exercise is liberated in a calorimeter.218 cal. etc. (ii) ergs. 45 sec.218 cal. deg.218 cal. . what temperature will the thermometer read at exactly 50 C? 2. R. at constant What is the temperature on the centigrade scale? pressure.with a heat capacity of 125. absolute temperatures on the Rankine scale are equal to t 1 1 F 1 + 459. (ii) abs.. 5. Justify the statement in the text that if the degree is taken as that on the Fahrenheit scale. and the temperature rises by 0. and by utilizing the fact that various units can be multiplied and divided. EXERCISES 1. A current of 1.." 1 is equal to unity.* at 23 C.'1 g. liter"1 atm.""1 The subsequent cancellation of identical units with opposite exponents makes conversion from one set of units to another a relatively simple matter..218 cal. 1 literatm. 24.42 ml."" 1 is cooled from the steam point to the ice point. such as those 3g. A quantity of 2.69.
"1 faraday"1 is dimensionless and equal to unity. Using the expression in Exercise 1.500 coulombs per g. (iii) abs. volt"1 g.070 cal.""1 . volt"1 g.. (ii) literatm. (iv) int."1 and that the quantity 23.595 g. accompanying the fusion of 1 mole of acetic acid at atmospheric pressure. cc.. equiv." . 10: Calculate the work done against a constant pressure of 740. the specific volume of water is 1 1 approximately 1 cc.070 cal. show that it is also equal to 23. what proportion of the total amount of heat supplied to the mercury is the work of expansion? 12. joules. Express the results in (i) ergs. equiv. The density of mercury at C and 1 atm. pressure. 11. . pressure is 13.. (v) defined cal.""1 . deg. . equiv. in defined cal.0330 cal.1595 cc. The faraday is usually given as 96. g." at 1 atm. Given that the mean specific heat in this range is 0. pressure." and that of the vapor is 1720 cc. when 1 mole of water evaporates completely at 100 C. g."1 g.EXERCISES 13 9. Determine the work of expansion. determine the work of expansion in ergs when the temperature of 100 g. of mercury is raised from to 100 C at 1 atm. joules. The specific volume of liquid acetic acid exceeds that of the solid at the 1 melting point by 0.0 mm. g.
Types of System. The thermodynamic properties thus serve to define a system completely." 2nd cd. it usually consists of a A definite amount (or amounts) of a specific substance (or substances).* by a real or imaginary boundary through which energy may pass. THERMODYNAMIC SYSTEMS will In order to develop the consequences of the laws be considered shortly. of a system can be defined completely by four observable properties or "variables of state". State of a System. viscosity. Glasstone. or of two or more solids. it then consists of two or more phases which are separated from one another by definite bounding surfaces. or of two immiscible (or partially miscible) liquids. 1946. 4b. such as mass. density. etc. a thermostat. The thermodynamic or macroscopic state or. the composition is. There are. which consist. completely uniform throughout. S. pressure. are examples of heterogeneous systems. of course. and hence the state of the system depends on the pressure. or a pure liquid or solid.g. If these properties are specified. of course. surface. gravitational and similar effects are neglected. in brief. refractive index. or a liquid or solid When a system is not uniform throughout it is said to be heterosolution. In actual practice it is not necessary to state the pressure. volume and temperature only.. of A an isolated system. * 1 X f Electrical. the state. 1 4a. dielectric constant. either as heat or as some form of work. all other physical properties. numerous other kinds of heterogeneous systems. The combination of a system and its surroundings is sometimes referred to as system effect.CHAPTER II PROPERTIES OF THERMODYNAMIC SYSTEMS 4. such as a gas or a mixture of gases. ume and "Textbook of Physical Chemistry. in the remainder of the universe. A system consisting of a liquid and its vapor.. and XI.. that is. Chapters V. voltemperature. For thermodynamic purposes the "surroundings" are usually restricted to a limited portion of the universe. fixed. system may be homogeneous. are thereby definitely fixed. magnetic. these are the composition. 14 . geneous. which may be separated from its surroundings. for experiment has shown that these three properties of a simple homogeneous system of definite mass are related to one another. of thermodynamics. as is well known to students of chemical equilibrium and the phase rule. which are not a homogeneous solid solution. it is necessary to define the terms of reference. the volume and the temperature. e. The portion of the universe which is chosen for thermodynamic consideration is called a system.! If the system is homogeneous and consists of a single substance.
4C
THERMODYNAMIC SYSTEMS
of
15
The value
of these properties thus depends on the values of the relationship between them is called an equation of state, but its precise form lies, strictly speaking, outside the province of pure thermodynamics; an equation of state must be derived from molecular (kinetic) theory or from direct experiments on the system under considera= RT, For example, the equation of state for an ideal gas, namely tion. is the volume of 1 mole, T is the absolute is the gas pressure, where is a constant, is based partly on the kinetic theory of temperature, and
any one
other two.
The
PV
P
V
R
gases and partly on experiment.
The van der Waals equation
represents
a modification of the ideal gas equation, derived by means of molecular Other equations of state, particularly those involving several emtheory. pirical constants, are determined from experimental data, although their general form may have a theoretical basis. The derivation of such equations is not possible by means of thermodynamics, but the results of thermodynamics may be applied to them with interesting consequences, as will be evident in the subsequent discussion. In any event, it may be accepted that, in general, the pressure, volume and temperature of a system are not independent variables, and consequently the thermodynamic state of a simple, homogeneous system may be completely defined by specifying two of these
properties.
The results stated above, namely 4r,. Thermodynamic Equilibrium. that only two of the three properties of a system, viz., pressure, volume and temperature, are independently variable, and that a homogeneous system of definite mass and composition is completely defined by these two properties, are based on the tacit assumption that the observable properties of the system are not undergoing any change with time. Such a system is said to be in thermodynamic equilibrium. Actually this term implies three different types of equilibrium which must exist simultaneously. First, there must be thermal equilibrium, so that the temperature is the same throughout the whole system. Second, if the system consists of more than one substance there must also be chemical equilibrium, so that the composition does not vary with time. Finally, the system must be in a state of mechanical equilibrium; in other words, there must be no macroscopic movements within the system itself, or of the system with respect to its surroundings. Disregarding the effect of gravity, mechanical equilibrium implies a uniformity of temperature and pressure throughout the system; if this were not the case, it would, of course, be impossible to describe the system in terms of the pressure, volume and temperature.
Systems in which diffusion or chemical reaction is taking place at an appreciable rate are not in thermodynamic equilibrium, and consequently their state cannot be completely specified in a simple manner. Certain systems which are
not in true equilibrium may nevertheless be treated by thermodynamic methods, provided the approach to equilibrium is so slow as to be undetectable over a considerable period of time. An instance of this type is represented by a mixture of hydrogen and oxygen gases under normal conditions of temperature and pressure. As mentioned earlier, reaction should take place with the formation of liquid water.
lt>
PROPERTIES OF THERMODYNAMIC SYSTEMS
4d
so that, the system is not really in chemical equilibrium. However, the reaction so slow that in the absence of a catalyst it behaves as if it were in thermodynamic equilibrium, provided, of course, that thermal and mechanical equilibria are The conditions of chemical equilibrium will, naturally, not apply to established.
is
such a system.
4d. Properties of a System. The physical properties of a system may be divided into two main types. There are first, the extensive properties which depend on the quantity of matter specified in the system. Mass and volume are two simple examples of extensive properties. The total value of an extensive property is equal to the sum of the values for the separate parts into which the system may, for convenience, be divided. It will be seen later that several properties of thermodynamic interest, such as the energy of a system, are extensive in nature. The other group of properties are the intensive properties; these are characteristic of the substance (or substances) present, and are independent
of its (or their) amount. Temperature and pressure are intensive properties, and so also are refractive index, viscosity, density, surface tension, etc. It is because pressure
of the quantity of
and temperature are intensive properties, independent matter in the system, that they are frequently used as
variables to describe the thermodynamic state of the system. It is of interest to note that an extensive property may become an intensive property by specifying unit amount of the substance concerned. Thus, mass and volume are extensive, but density and specific volume, that is, the mass per unit volume and volume per unit mass, respectively, are intensive properties of the substance or system. Similarly, heat capacity is an extensive
property, but specific heat is intensive. The properties of a system in thermodynamic equilibrium depend only on the state, in the sense defined in 4c, and not on the previous history of the system. If this were not the case, the properties would have no significance, for they would be determined not only by the actual temperature and pressure, but also by the temperature and pressure the system may havo had in the past. This is clearly not the case. It follows, therefore, as a consequence that the change in any property due to a change in the thermo
dynamic (equilibrium) state depends only on the initial and final states of system, and not on the path followed in the course of the change.
the
If any 4e. Thermodynamic Properties and Complete Differentials. quantity G, such as a thermodynamic property, is a singlevalued function which completely determine the value of (7, of certain variables x y,z, , that is,
y
.
.
.
<?=/(*,
t/,
z,
.
.
.),
(4.1)
then the change in G resulting from a change in the variables from a/, ?//, in the final state, is given by in the initial state, to #/?, ?//*, 2/?, ., ., ZA,
.
.
.
.
A<?
= G K  GA =
J(XB,
y,
ZB,
.
.
.)
 f(x A
.
yA, ZA,
.
.
.)
(4.2)
48
THBRMODYNAMIC SYSTEMS
it is
17
As a mathematical consequence,
possible to write for a small increase
dO
in the property
(?,
XtV..
where the partial differential symbol, e.g., (dG/dx) v ,. represents the rate of change of G with the variable x, while all the other variables, y, constant. Any differential dG y defined by equation (4.3), zy ., remain of a function G, represented by (4.1), is called a complete differential, or an
.
.
.
.
.
.
exact differential, of that function. As seen above, a thermodynamic property of a homogeneous system of constant composition is completely determined by the three thermodynamic Since only two of these three variables, pressure, volume and temperature. variables are independent, it is possible to write
where
G may be the energy,
from
(4.3) that
fully later.
volume, or other property to be considered more This expression is equivalent to equation (4.1), and hence it
follows
*The
*
1
*
(4  4)
physical significance of this result can be understood from the When the pressure and temperature of the system following considerations. are P and T, respectively, the value of the thermodynamic property under consideration is G, but when the variables are changed to P f dP and T dT, it becomes G dG. Since the value of the property is completely determined by the pressure and temperature, the change dG will be independent of the path between the initial and final states. Hence, any condP and venient method for carrying out the change from P and T to T dT may be chosen for the purpose of calculating dG. Suppose the change is carried out in two stages: (i) in which the temperature remains to constant at T while the pressure is changed from dP, and (ii) in dP and the temperature is which the pressure is held constant at P dT. In stage (i) the rute of change of G with preschanged from T to T constant at the temperature T, is (dG/dP)T, and since the actual pressure,
+
+
P+
+
P
P+
+
+
dP, the change in G for this stage is equal to (dG/dP} T X dP\ be identical with the first term on the righthand side of equaIn stage (ii), the rate of change of G with temperature at the tion (4.4). constant pressure P + dP, which is very close to P, may be written as Since the actual temperature change is dT, the change in G (6G/dT) P for this stage is (dG/dT) P X dT, which corresponds to the second term on the righthand side of equation (4.4). The sum of the two terms just derived gives the total change dG for the given process, in accordance with (4.4). In the foregoing discussion, G has been treated as a singlevalued function It is equally permissible to choose as of the pressure and temperature.
sure change
is
this is seen to
.
18
PROPERTIES OF THERMODYNAMIC SYSTEMS
5a
variables any two of the three thermodynamic properties, pressure, volume and temperature. In some cases it is convenient to take pressure and volume as the independent variables; the complete differential of a thermo
dynamic property
G may
then be written as
Alternatively,
if
the volume and temperature are chosen as the variables,
"Various forms of equations
of
(4 6)

(4.4), (4.5) and (4.6) will be utilized in the treatthermodynamic properties. Another important result, which will be required later, may be derived from the equations given above. Since the volume of a homogeneous system of constant composition is a singlevalued function of the pressure and
ment
temperature,
it is
possible to write
''
If this
value of
dV
is
substituted in equation (4.6), the result
is
For a given infinitesimal change of thermodynamic state, dG must have a 7 definite value, no matter how it is calculated; the coefficients of dP and dT identical. respectively, in equations (4.4) and (4.8) must therefore be
,
Hence,
\
Of J T
/ i /t \
\V
/T
\
Of / T
/
(4.9)
and
x
i/^f
\
/ ^ T/ \
zn \
(4.10)"
5.
EQUATIONS OF STATE
Sa.
The
Ideal
is
Gas Equation.
The
practical value of the results of
frequently greatly enhanced when an equation of state, thermodynamics the pressure, volume and temperature of the system, is available. relating
* Some writers derive equation (4.10) directly from (4.6) by "dividing through by dT," and then imposing the constant pressure condition; this procedure is, however, open to criticism on mathematical grounds.
Sa
EQUATIONS OF STATE
19
satisfactory relationship of this type is known for liquids and solids, but for gaseous systems certain moderately simple equations of state have been All gases actually differ in their behavior, and so the problem is proposed.
No
approached by postulating the properties of an ideal ing deviations from ideal behavior. An ideal gas is one which satisfies the equation
gas,
and then consider
PV = RT
for
1
(5.1)
mole at
all
temperatures and pressures;
the absolute temperature, respectively, V is It will be observed that at constant pressure, (ideal) gas constant. the volume of an ideal gas is directly proportional to its absolute tempera2c. Attention may also be called ture, in agreement with the postulate in to the fact that equation (5.1) implies that Boyle's law and GayLussac's (or Charles's) law are both applicable to an ideal gas. At a given temperature and pressure, the volume of any gas, ideal or not, will be proportional to its mass, or to the number of moles, contained in the system. Since equation (5.1) applies to 1 mole of an ideal gas, it follows that for n moles,
and T are the pressure and the molar volume, and R is the
P
molar
PV =
nRT,
(5.2)
where V is now the total volume occupied by the gas; molar gas constant.
R
is,
however,
still
the
so
is frequently encountered in thermodynamics, and value will be determined. Use is made of the fact, derived by extrapolating experimental data for a number of gases to zero pressure, that 1 mole of an ideal gas occupies 22.414 liters at 1 atm. pressure and a temperaIt follows, therefore, that in equation (5.1), P is 1 atm., ture of 273.16 K. V is 22.414 liters mole 1 and T is 273.16 K; hence,
The gas constant R
its
= "
T
It will
1
X
22.414
273.16
0.082054 literatm. deg." mole1
1
.
be observed that since the product PV has the dimensions of energy, be expressed in energy per degree; since the value of R is invariably 1 1 given for 1 mole of ideal gas, it is stated in terms of energy deg."" moleIn the present case the energy is in literatm. Since 1 liter contains 1000.028 cc., it follows that
R must
.
R =
By
can also be expressed
since
1
82.057 cc.atm. deg. mole"
1
1
.
utilizing the conversion factors in Table 1 (Appendix), the value of in ergs deg.~ l mole 1 and in cul. deg.~ l mole"" 1 . Thus,
R
literatm. is equivalent to 1.0133
X
H)9 ergs,
it is
seen that
R = =
0.082054 X 1.0133 X 109 8.3144 X 107 ergs deg. 1 mole
1 .
20
Finally,
1
PROPERTIES OF THERMODYNAMIC SYSTEMS
literaim, is equivalent to 24.218 (defined) cal., so that
Sb
R 
0.082054 X 24318 1.9872 cal. deg." 1 mole" 1
.
In a mixture of ideal gases, it is to be will each behave that gas independently of the others. If the expected partial pressure pi of any ideal gas in a mixture is defined as the pressure this particular gas would exert if it alone occupied the whole available volume V, then by equation (5.2)
Pi
5b. Mixture of Ideal Gases.
V =
ruRT,
(5.3)
where n is the number of moles of the gas present in the system. Since each gas in the mixture will exert its pressure independently of the others, it follows that the total pressure P is equal to the sum of the partial pressures
of the constituent gases; thus,
P =
Upon
it
PI
+ PZ+
,
. . .
+p*+
,
(5.4)
can be readily derived from
introducing the values of p\, p 2 (5.4) that
etc.,
as given by equation (5.3),
PV =
where n
mixture.
is
(m + = nRT,
n,
+
(5.3)
+n +
t


}RT
the total number of moles of
all
By
combining equations
P*
and
the ideal gases present in the (5.5), it is seen that
(5.6)
= P.
n
The fraction n,/n, that is, the ratio of the number of moles (or molecules) any constituent of a homogeneous mixture gaseous, liquid or solid to the total number of moles (or molecules) is called the mole fraction of that constituent; it is represented by the symbol N so that
of
t,
Mole Fraction N< =
tti

+
^2
+
+
n
t
+
=
'
.
n
(5.7)
mole fraction in conjunction with equation that the partial pressure p of any ideal gas in a mixture is related to the total pressure by (5.8) Pi = N t P.
Utilizing the definition of the
(5.6), it follows
Another expression for the partial pressure can be derived from equation (5.3), based on the fact that Ui/V represents the molar concentration, i.e., moles per unit volume, of the particular gas in the mixture. If this concentration
is
represented by c t equation (5.3) gives
,
Pi
for an
ideal gas.
=
ct
RT
(5.9)
Sc
EQUATIONS OF STATE
21
Sc. Real Gases. According to equation (5.1) or (5.2) the product PV a given mass of an ideal gas, at constant temperature, should be constant Actual gases, however, exhibit considerable deviations at all pressures. from ideal behavior. At low temperatures the value of PV, instead of remaining constant, at first decreases as the pressure is increased; it then passes through a minimum and then increases. As the temperature is increased, the minimum becomes less marked, and at sufficiently high temperatures the value of PV, increases continuously with increasing pressure.
for
2.6
2.2
1.8
PV RT
1.4
1.0
0.6
200
400 600 Pressure in Atm.
800
1000
FIG. 2.
Compressibility of nitrogen gas
The
in Fig. 2,
general nature of the experimental results can be seen from the curves which show the variation with pressure of PV/RT for nitrogen at
a number of temperatures. For an ideal gas, all the curves would fall on the same horizontal line. The actual temperature at which the minimum in the curve disappears varies with the nature of the gas. For the gases which are difficult to liquefy, e.g., hydrogen and helium, there is no sign of the minimum at ordinary temperatures, but for nitrogen it is observed up to about 50 C. For a readily liquefiable gas, such as carbon dioxide, the minimum in the curve persists up to temperatures in the region of 400 C. The equation of state for a real gas must evidently account for the variations of with pressure and temperature, as described above, and also for the different behavior of different gases. 2
PV
PV
J S. Glasstone, ref. 1, Chapter III; see also Beattie (Phys. Soc. London), 7, 105 (1940).
and Stoekmayer, Rep. Prog. Phys.
22
5d.
PROPERTIES OP THBRMODYNAMIC SYSTEMS
5d
The van der Waals Equation. One of the earliest successful atto modify the ideal gas equation so as to make it applicable to real tempts gases is that of J. D. van der Waals (1873), who proposed the equation
for
6)
 RT
(5.10)
The constant a is 1 mole, where a and 6 are constants for a given gas. determined by the attractive forces between the molecules, while b is dependent on their effective volume, which represents a balance between attractive and repulsive forces. By choosing appropriate values for a and 6, the van der Waals equation (5.10) is found to represent moderately well the actual behavior of real gases. There is, however, an important weakness: if the equation is assumed to be exact, a and b are found to vary with the temperature. In spite of its approximate nature, the van der Waals equation is frequently employed, for it lends itself readily to mathematical treatment, and even if the results obtained from it are not exact, they are at least qualitatively correct.
By multiplying out, it can be readily seen that the van der Waals equation is a cubic in F, so that there are, under suitable conditions, three values of V for each pressure, at a given temperature (Fig. 3, curves I and II). The region in which this occurs corresponds to that in which liquefaction of the gas is possible. At higher temperatures, e.g., curve IV, two of the roots are
always imaginary, only one being real. At a certain intermediate temperature (curve III), which should correspond to the
critical temperature, the three values of V should become identical, at the point X. FIG. 3. Van der Waals At this point the PV curve will exhibit a isothermal curves horizontal inflection, so that both the first and second derivatives of the pressure with respect to the volume, at constant temperature, will be equal to zero. Thus, writing the van der Waals equation (5.10), for 1 mole of gas, in the form
RT
V it is
a
b
(5.11)
found that
dP \
)r
and
_
(V
RT +  b)6)
2* V*
(5.12)
2RT
(7
6a

F
4
(5.13)
Sd
EQUATION? OF STATE
critical
23
At the
writing
point
X
Ve
and T, to represent the molar
and ~~
both these expressions are equal to zero; hence, critical volume and temperature,
respectively, it follows that
(V.

'
"
2RTe
(V.
6)'
VI

6)'
F?
From
these
two equations, and
(5.11), it is readily
found that
(i)
V =
e
36;
(ii)
Te
80
.....
a
(5.14)
27Rb'
(Hi)
the values of a and b which make the van der Waals equation represent relationship of a gas at a particular temperature are inserted in equation (5.14), the critical pressure, volume and temperature obtained are only in moderate agreement with the experimental results. This is not unexpected for, as already pointed out, a and b are not strictly constant, if the van der Waals equation is assumed to hold. If the PV data from which a and b are derived are obtained at a temperature that is some distance from the critical, they will clearly not prove satisfactory for the evaluation of In actual practice the procedure adopted is to calculate critical constants. a and b from the observed critical data * by means of the equations (5.14). A number of the results obtained in this manner are given in Table I; if the 1 pressure P of the gas is in atm. and the molar volume V in liter mole"" , a 2 2 2 will be in liter atm. mole~ since a/V must have the same dimensions as P, and b will be in liter mole" 1 since this has the dimensions of V.
If
the
PV
,
TABLE a
liter1
I.
VAN DER WAALS CONSTANTS
b
liter
Gas
atm. mole"*
mole" 1
Gas
Hydrogen chloride Hydrogen cyanide Hydrogen iodide Hydrogen sulfide Methane Methanol Methyl chloride
Nitric oxide
Nitrogen Nitrous oxide
Oxygen
Propane
Propylene
Sulfur dioxide
Water
The values of a and b recorded in Table I may be used to calculate the pressure or volume of a gas, at a specified volume or pressure, respectively,
* For critical temperatures and pressures of a number of substances, see Table 2 at the end of the book.
24
PROPERTIES OF THERMODYNAMIC SYSTEMS
Se
to a moderate degree of accuracy. The results are by no means exact, but they serve as an approximation when no other information is available, especially at high pressures.
equations for
Problem: Compare the pressures given by the ideal gas and van der Waals 1 mole of carbon dioxide occupying a volume of 0.381 liter at 40 C.
The
R as 0.0820 literatm. deg.~
ideal gas equation gives, for 1 mole,
J
P  RT/V
mole"1 and
,
T as 273
+ 40 
;
taking
V
as 0.381
liter,
313 K,
it is
found that
b

Utilizing the
van der Waals equation
0.0820
(0.381
in the
form of
(5.11),
with a
=
3.60
and
4.28
X
10* (Table I),
X 313  0.043)
3.60
(0.381)'
.
1 t J.l
atm.
The experimental value
is
50 atm.
Problem: Compare the volumes given by the ideal gas and van der Waals C. equations for 1 mole of nitrogen at 400 atm. pressure and
According to the ideal gas equation V = RT/P for 1 mole; atm. deg. 1 mole"1 , P is 400 atm., T is 273 K, and hence
R
,
is
0.0820
liter
V
T/
RT
^r
0.0820
X TTTT 4w
273
= AAKAA1 0.0560 liter
.,
mole^1
,
.
In order to determine the volume from the van der Waals equation it is necessary to solve a cubic equation, and this is most simply done by the method of trial. Neglecting a/V* in comparison with P, equation (5.10) reduces to P(V 6) = RT, so that
6 for nitrogen is 0.0392, and for 400 atm. V is 0.0952 liter mole" is found to be 247 If this is inserted in equation (5.11), with a equal to 1.39, is found, to be 891 atm. atm. Similarly, if V is taken as 0.0560 liter mole"1 , Since themolar volume of 0.0560 liter corresponds to a van der Waals pressure of 891 atm., and 0.0952 liter corresponds to 247 atm., it is evident that the correct volume, for 400 atm., is about 0.075 liter. By a series of approximations, the volume is found to be 0.0732 liter. (The experimental value is 0.0703 liter. Although the van der Waals result is not correct, it is very much better than the
From Table
1
I,
.
P
P
ideal gas value.)
5e.
Reduced Equation of
State.
If
perature of
a gas are expressed in terms
i.e.,
the pressure, molar volume and temof the critical pressure, volume and
temperature, respectively,
P . Tp
e.
V.
= ^Ve
and
T  BT
e,
(5.15)
and these expressions are introduced into the van der Waals equation
(5.10),
. volume and temperature. a valid one. that it is completely general. although equation (5. Consequently.14). whose PFT behavior may be represented by an expression of the form of the van der Waals equation. and have the same reduced volume 0.16) does not give the correct quantitative relationship between ?r. for it does not involve a and 6. if equimolar amounts of any two gases. Experimental studies have shown that the principle of corresponding states derived above is.17) Neglecting the last term. as a first approximation. which are equal to P/P C V/Ve and T/TC respecthe reduced pressure. corresponding states. '. are called law of corresponding states. (5. are at the same reduced pressure TT. The van der Waals equation is first modified by changing the a/V 2 term to a/ TV 2 thus. It should be pointed out.16) The interesting fact about this equation is is a reduced equation of state.16) is taken as an expression of the The quantities TT. at least approximately. are necessary to obtain an exact equation of state. Upoa multiplying out. Because is not the law corresponding agreement it would that three more than constants appear empirical however. and hence contains no reference to any specific substance. can be and 6. then they must be The two gases are then said to be in at the same reduced temperature 6. such as a and 6. and equation (5. that any equation of state containing two arbitrary constants. and (5. law of with the states. the equation of state proposed by D. by the ideal gas value RT/P.RT + Pb  . however. found that 1) =80. c given by the equations (5. in a/ TV.17) becomes PV . <t> <t> 5f. tively. The Berthelot Equation. in addition to R.1G) and 0. in converted into a relationship involving the reduced quantities IF. since it contains the product of two small quantities. and 0. exact. this becomes PV = R T + Pband replacing V +  (5. Although it is not employed in connection with PVT relationships.Sf EQUATIONS OF STATE 1 25 the result for mole of gas is Upon it is insertion of the values of P Ve and T c. Berthelot has found a number of applications in thermodynamics. equation (5. .
Beattie.RTQ r y^ O (V ( .. 1382 (1930). Am. Once they are known various uses can be made of equation (5. Phys. 50. 8 (5.. Soc. el oZ. 64. 95 (1930). having a partial theoretical basis. Arts Sd. PV .ZV) ( .. 1587. within the limits of applicability of the constants. 62. 59. 53. 33. Beattie and Bridgeman. . C. is that proposed by J.21). is the Berthelot equation. be made of a purely empirical equation which studies. 34.. Am. Aoad. It takes the form The BeattieBridgeman ~ P . Equation. 5h. 61. b and c being arbitrary constants. 229 (1928). Chem. Ind. where AAo/"l + A 9. 544 (1942). Chem. 26 (1939). Chem... Soc. 3.18) R * becomes which 5g. /. 8 The results are useful for interpolation of PVT data. however. based and Consequently. 3133 (1028). Ind. 63. equation (5.. and also for a number of thermodynamic purposes. Soc. these are 5g critical The factors a. Eng. 6 constants.21) factors a. Z. A. 2m (5. Deming and Shupe. the five constants being derived from actual observations. Bridgeman (1927). 52. 1665 (1927).1 2 8 &ir1 diTi The equation thus involves twelve empirical constants. which is capable of relatively easy mathematical manipulation. 52. Ohem. Eng. Maron and Tun&ull. see also.. General Equation of State* Although numerous equations of state have been proposed from time to time. Chem. 6 (1930). Maron and Turabull. Chem. /. 6. A^ y^ . 0. 548 (1942). Phytik. V t R >) . JBo ~V B= B*(l} and C = The chief application of the Beattiea. 1589 (1937). few of these have been used in thermodynamic Mention may. J. but these can be derived from the experimental PVT data without difficulty. c and d are dependent upon the temperature. The values of these constants have been obtained for a number of gases and are recorded in the literature. 4 See. 408 (1941). for example. Beattie and O.RT + aP + bP* + cP + dP*. thus. /. 843 (1931). Bridgeman equation lies in its use to represent the experimental PVT relationships of gases.4 Am. and the variations have been expressed by the relationships The a b c d  + a T. 49.26 PROPERTIES OF THERMODYNAMIC SYSTEMS and R are now replaced by expressions involving the upon experimental results. takes the form of a power series in the pressure. Proc. 93 (1935).+ a !F+ bzT~* + ciT* + c*T' + 1 8 . Am. Another modification of the van der Waals equation.
were available for all gases. much labor could be saved if complete compressibility diagrams. 'if the compressibility factor is plotted against the gas. such as Fig. in fact. therefore. for all van der Waals gases. than f . For n moles of gas. to a less precise extent.25) According to the law of corresponding the reduced pressure * and the reduced temperature 6 have the same value for different gases. their reduced molar volumes </> must be It follows. irrespective of the nature of the In other words. all gases. approximation. Experimental observation has shown that for many substances P V /RTe has. (5. the volume would.. bility factors ic must then also be the same. Since almost the same constant value. it follows that It will be seen from the three relationships of equation (5.23) where K is the compressibility factor in the given state of the gas. which is really a plot of the compressibility factor against the pressure of nitrogen at several temperatures. as a first however.51 EQUATIONS OF STATE 27 Si. although it is more nearly ^ this quantity is constant.24) tha' for ?. the van der Waals equation are useful for solving problems relating to the pressure. and T by OTC . of course. The compressibility factor K of a gas is defined by PV jj?' < where P is the pressure of the gas.22) are replaced by their respective reduced properties. if . therefore. If the pressure.e. that their compressiequal. Except for readily liquefiable gases.25). should be constant. it follows from equation (5. from equation (5. 2. but for a real gas it may be less or greater than unity. where c is a universal constant. as may be seen from Fig. volume and temperature of gases.14) that Pc Ve/RT. and so it is fortunate that the law of corresponding states has permitted the development of a single generalized compressibility diagram which is (approximately) applicable to all gases. states ( 5e). results can be obtained from this diagram which agree with the observed data within a few per cent. be increased nfold. from equation (5. The necessity for a separate diagram for each gas would be a complicating factor. P is replaced by irP V by $V* . Although such analytical expressions as the BeattieBridgeman equation and.22) that for 1 mole of gas PV = uRT. volume and temperature in equation (5. It follows. Compressibility Factors. V is its molar volume and T is the absolute temperature. equal to f. V (5. 2. i. For an ideal gas K would obviously be unity under all circumstances.
28 PROPERTIES OF THERMODYNAMIC SYSTEMS Si s 8 3(2 H o I .
35. 1353 (1932).) Problem: Utilize Fig. for a given reduced temperature. 24..0820 K X 313 381 is MA 4 *' ==67 ' The critical pressure of carbon dioxide 72. Kay. Ind.. 25. Since /* is employed later for another purpose.0703 liter mole" .* From actual experiments on a number of gases.23). thus.. first problem in 5d). 4. with the reduced temperature as parameter. Maron and Turnbull.27. Eng. it follows that _ = P * K RT = ~V 0. but the evaluation of either pressure or temperature is not quite as simple. 725 (1933). Chem. T = 273 + 40 = 313 K.23). 4 to determine the volume of C (cf. Lewis. if the other two variables are given. 513 (1932). the Compressi= 400 atm. Utilizing equation (5.381 liter mole" . pressure . Lewis and Luke.381 liter at 40 C (cf. deg. IT . see Thomson. 257 (1936).P/(Pe + 8) and Cope. the mean observed compressibility factors at various ternperatures and pressures have been derived.. the results for all gases on the same curve.9 atm. and the values of * are plotted against the corresponding reduced pressures. 28. A/V71 0. ibid.." the symbol M being used for the compressibility factor. so that * * = it =  925 * For hydrogen and helium better results are obtained by adding 8 to the critical and temperature when calculating the reduced values. second problem in 5d). ibid.. with it is found that 0. Brown.* The conclusion just reached forms the basis of the generalized. can be achieved directly from Fig. and the critical temperature 126 K. it has been replaced by K here. 23.= x 1. 4 to determine the pressure of carbon dioxide gas when 1 mole occupies 0. for these gases. 4 it is found directly that for these values of TT and 0. volume or temperature of any The determination of the volume gas. Souders and Smith. ibid. V = ic RT =. for a convenient nomograph applicable below the critical point.T/(Te + 8).071 liter ..51 EQUATIONS OF STATE 29 reduced pressure. hence the reduced pressure and temperature are given by From R = bility factor Fig. or reduced. with a fair degree of accuracy. 887 (1931). K is about 1. the value of either the pressure. atm. 1 Substituting the value of V = 0. 24. 28. t Generalized (reduced) compressibility diagrams are often referred to in the literature as 'Vcharts. 4). pressure and 1 mole of nitrogen at 400 is The critical pressure of nitrogen is 33.0820 X 273 = 4UU .0820 literatm.. and R into equation (5. . ibid. 1014 (1936). 34. ibid.27 P X 0. f will fall Problem: Utilize Fig.. ibid.. From these curves it is possible to derive. ibid. 544 (1942). Dodge. Lewis and Weber. 895 (1943).. mole"1 t . 1 (The experimental value is 0..5 atm.1 mole1 and T 273. compressibility curves (Fig.
7 from Fig. at which this line intersects the curve in Fig. it follows that 0. total pressure of A simple modification of the law of partial pressures as applied to ideal gases has been proposed for mixtures of real gases (E. 4. However. liter Problem: A mixture of i mole nitrogen and J mole hydrogen occupies 0.9. The molar volume of the mixture is 0.30 PROPERTIES OF THERMODYNAMIC SYSTEMS 5j The expression * = 0. 6 If P< is the pressure which would be exerted by a constituent of a gas mixture when its molar volume is the same as that of the mixture... (5. 4 cannot be read to this degree of accuracy. where p is the partial pressure and N is the mole fraction of any constituent of the mixture of gases of total pressure P.e. the values of PI. . +   . Cuppk and Tremearne.) The additive pressure law. involving a series of trial solutions. Am. tical with that in the second problem of By equation (5. P.03. i. 313 K. Since e is 72. is useful for Bartlett.1 K. when the volume is known.03 is found to be of T at which the line * = 0. The value temperature 8 corresponding to 40 C. i.P. however. and that for hydrogen is 390 atm.9 = 51 atm.925* is the equation for a straight line passing through the The point representing the system under consideration is that origin of Fig. 4 for the prescribed reduced temperaThe critical temperature of carbon dioxide is 304. then it is suggested that the total pressure P is given by P = N^' + N 2 P. the pressure of nitrogep gas at 50 C for this molar volume is found to be 404 atm. 4. as given by equation the calculation of the approximate pressure exerted by each gas.e. (The  P P X experimental value Sj.0832 liter. Soc. p. 1928). If the total pressure is given.26). and the total pressure. If compressibility data for the individual gases are not available. An alternative approxiVolume Law. provided the molar composition of the gas. 1. The agreement is Fig. /.. The total pressure is thus not equal to ( the sum of the partial pressures defined in the usual manner. 4. (5.8).. Additive (i is X 404) + (J X 390)  394 atm.26) This rule has been found to give results in fair agreement with experiment. can be obtained with the aid of Fig.26). 1276 (1928). The calculation is iden5i. 4 in conjunction with the known critical temperature and pressure of nitrogen and hydrogen (see footnote. P. + + N. and so the reduced ture. because 400 atm.925* intersects the curve for is 0. the evaluation of the volume is somewhat more complicated. The rule that the a mixture of gases is equal to the sum of the pressures exerted by each gas if it alone occupied the whole of the available volume 5b) does not apply to real gases. partly fortuitous. etc. 50. p t = NP. the total pressure is given by P = (The experimental value 5k.0832 at 50 C. Bartlett. by using Fig. is 313/304 = 1. 29). its volume and temperature are known. for some purposes it is convenient to define the partial pressure of a gas in a mixture by means of equation (5. Chem. is 50 atm. Calculate the total pressure. in a mixture of real gases.) Mixtures of Real Gases: Additive Pressure Law.7 72.
carbon dioxide 0. (Fig.0 liters of gas B. 5. (This is the reverse of the problem in 5j . the volume of 1 mole of hydrogen would be 0. assuming ideal behavior. oxygen 23. 3. the mole fraction of each constituent? nitrogen 75. that used in the first problem in By the Amagat law of additive volumes... with negligible traces of other gases. and 50 C.) found from Fig.0 atm. is what 2. 1893. The measured volume of the moist gas is Calculate the volume the dry gas 5. 524 (1923). Leduc. t oc. measured at 0. pressure. are passed into a vessel whose capacity is 15. with a fair degree of accuracy.44 liters. 4. under the same conditions. (The experimental value 0. A. pressure being 23. What is the resulting total pressure. Roy. at the same temperature.25 mole fraction of hydrogen was found to occupy a volume of 71. the total volume should be equal to the sum of the volumes which the constitutent gases would occupy at the total pressure of the mixture... 1898). in each case. it is a simple matter to make use of the additive volume law. Masson. A122. Amagat. phya. Suppose 10. the volume of the given mixture would be It is (i X 0.081 liter. 5 (1898). mole'1 Utilizing the generalized compressibility diagram. see also.28%.0832 liter.. C and 400 atm.8 mm. pressure and 50 C. A liquid mixture consists of equal parts by weight of water and sulfuric acid. Prove that for a mixture of ideal gases the total volume is equal to the sum of the volumes which the constituent gases would occupy at the total pressure of the mixture at the same temperature (Amagat's rule). 4) may For approximate purposes the generalized compressibility diagram be utilized. 283 (1929).5 ml.58%. The method of calculation is. 15. 4 that at 400 atm. pressure a mixture containing 0. Problem: Calculate the volume of a mixture of 1 mole nitrogen and } mole hydrogen at 400 atm. assuming ideal behavior of the gas and of the water vapor.) EXERCISES 1. if the gases behave ideally and the temperature remains The composition of dry air by weight is as follows: constant? gas collected over water at 25 C becomes saturated with water vapor.081) = 0.08%.083) is + (J X 0.50 atm. This rule has been found to hold. its partial .0 mm. Calculate the partial pressure of each of these four gases in air at exactly 1 atm.083 liter. identical with 5i. Ann.5k EXERCISES 31 mate method is available which makes use of the law of additive volumes (. determine whether Amagat's volume rule or Bartlett's partial pressure rule is in better agree* ment with experiment. Leduc. at a total pressure of 752. argon 1.0 liters. A Cf. H. A126. At nitrogen and 0.06%. 248 (1930). at 1.0 liters of gas A.75 mole fraction of 6. and 5. chim. . If complete experimental PVT data for the individual for mixtures of real gases.082 liter. 7 It can be readily shown that for a mixture of ideal gases. 7 et aL Proc. 1 mole of nitrogen would occupy 0.. A103. gases in the mixture are available. would occupy at a pressure of 760 mm.
It has been suggested [Kay. critical + + + + . By means of Amagat's rule and the compressibility chart. are the mole pressure of NiPe i ? fractions of the various gases in the mixture. critical point? pressures given by (i) the ideal gas equation.5. Determine by means of the compressibility chart the weight of gas used up when the pressure in the cylinder has fallen to 50. of oxygen and 77. and 12.) 8. neglect the term ab/V*.8 X 10~ atm. which is small if not large. (ii) the van dei Waals equation. (The experimental values are . 28. 14. Chem. where B tt(w~ b  < van der Waals equation.. 11.2" K and 48. Ind. If G is a function of P. contains methane gas originally at 200 atm. deg. are the critical temP and the critical c2 .) Express B in terms of Te and PC) and compare the result with that given by the Berthelot equation (5. Compare the result with that which would be found if the gases were ideal. 15.9 X lO"4 and 6.32 7. and replace V in a/V by RT/P. Verify the units of the van der Waals a and Table I. calculate the volume occupied by the mixture in Exercise 12 at a total pressure of 500 atm. 1 1 respectively.0 g. and Tcl 7 C 2. PROPERTIES OF THERMODYNAMIC SYSTEMS Show that at moderate and low pressures the van der Waals equation may Mul be written in the form tiply out the PV  RT(l  BP). Compare the result with that for (i) an ideal gas. at 10. (ii) the van der Waals equation. Apply this rule to Exercises 12 and 13. N 2 . What would be the pressure if the gases behaved occupying 155 ml. of nitrogen C. P.08205 literatm. The critical temperature and pressure of ethane are 305. Taking R as 0.0 g.279 liter at 40. and 25 C.0 atm. What would be the approximate molar volume at the the pressure is .0 liters.i. V and T. Eng.19) for hydrogen and oxygen at 25 C. atm. peratures pressures. at C. (ii) a van der Waals gas. (iii) the compressibility diagram. for 1 mole of hydrogen at 50C C.. . prove that . Compare the ideally? 13. A cylinder. 1014 (1936)] that the compressibility factor of a mixture of gases may be determined by treating the mixture as a single gas with a and a critical temperature equal to NiTe i x*Te t N 2 Pc t where NI. 9.fdO \ \dV/ P VdP/r \dPjv b given in and derive an analogous expression for (dG/dT)v16. fdO\ \dPj T fdO\ /dV\ . (iii) the compressibility diagram.1 .8 atm.0 C." mole" determine the van der Waals constants. for 1 mole of ethylene occupying a volume of 0. of capacity 100. Compare the volumes given by (i) the ideal gas equation. determine the total pressure of a mixture consisting of 23. Assuming Bartlett's rule and using the compressibility diagram. .
THH CONSERVATION OF ENERGY The Equivalence of Work and Heat. joules. is. it follows that a standard calorie is equivalent to 4. due to the difference between the standard and defined calories. commenced about 1840 and lasting for nearly forty years. The Mechanical Equivalent from Heat Capacities.1833 int. 6b. Some experiments carried out by H. no matter what its origin. joules.e. and measured the amount of heat thus produced by determining the rise in temperature of a calorimeter of known heat capacity.1858 X 107 ergs. According to the most recent experiments. J. This fact is the basis of the concept of a definite mechanical equivalent of heat. always produced the same quantity of heat. mention may be made of the following: stirring water or mercury by a paddle wheel. It is of interest to mention that while Joule's experiments were in progress.. However. i. Among the methods used for converting work into heat. passage of an electric current through wires of known resistance. work and heat was first clearly seen by Count Rumford (Benjamin Thompson) in 1798. As a result of his observations made on the heat dechanical veloped during the boring of a cannon. the value of which is known in int. but the most important results were those obtained by J. Thus. Assuming that 1 int. joules. R. P. that is. Davy (1799) appeared to indicate the connection between work and heat. one standard (15) calorie is equivalent to 4. of work. 4. As a result of his studies.. and passage of induced current through a coil of wire rotated in a magnetic field. i. forcing water through capillary tubes. at least partly. Joule came to the highly significant conclusion that the expenditure of a given amount of work. Joule in an extended series of observations. 4. compression or expansion of air. it has become the practice by chemists to adopt the relationship between work and heat given in 3e. a defined calorie is equivalent to 4. joule is equivalent to 1. joules.e.1858 abs. he concluded that the heat produced was related to the mechanical work expended in the boring process. irrespective of the source or nature of this work. The difference between this value and the one given above. joules ( 3b).0002 abs.CHAPTER III THE FIRST LAW OF THERMODYNAMICS 6a.1850 int. The relationship between me6. joules. Joule converted known amounts of work into heat. from the specifia heats of air at constant pressure and .1850 int. of a definite and constant ratio between the number of ergs of mechanical work done and the number of calories produced by the conversion of this work into heat. Mayer (1842) calculated. because heat quantities are usually determined at the present time by comparison with the heat produced by electrical work. In a number of carefully planned and executed experiments.
which is not strictly true.16 cc. in other words. This difference is given as 0. the increase in volume of 1 g." * that is. the results of Mayer's calculation are in excellent agreement with the accepted value of the relationship between ergs and calories.0687 cal.2)]. therefore. in the vicinity of 0. By GayLussac's law of the expansion of a gas at constant pressure [cf." see 18d. hence. volume.18 X X 10 ergs. The Conservation of Energy: The First Law of Thermodynamics. of air at C and 1 atm. In the present case.lO z^TZ = *7*7Q A. The fundamental significance of this accepted view was not widely realized until 1847 when H.87 4. 1 atm. is 773. and without itself undergoing any change. an exactly equivalent amount of another kind (or kinds) must be used up. 1 cal. the volume of a gas expands by 1/273. If the pressure is in dynes cm.~* and the volume in cc. Problem: The difference between the heat capacities of 1 g. of air is 773. of air by 1 at constant pressure (1 atm. If modern specific heat data are used. The volume pressure (1 atm. deg. This work should be equivalent to the difference between the heat required to raise the temperature of 1 g. 2.87 X 10* ergs.e. whenever a quantity of one kind of energy is produced. The mechanical equivalent of heat derived in this manner was close to that obtained by Joule in an entirely different manner. No success had attended the many attempts to construct a machine which would produce mechanical work continuously without drawing upon energy from an outside source. of air at constant 1 C. the work done in the expansion against the constant pressure of the 10* atmosphere is equal to the product of the pressure. but its fundamental implication is that although energy may be converted from one form to another.. was not possible has long been accepted by scientists. and the increase of volume. The belief that "perpetual motion of the first kind. the heat change result with the work 6C accompanying the expansion of air.013 4 dynes cm. done against the external pressure.013 X 106 X ^27o.. * For an explanation of "perpetual motion of the second kind.34 constant volume ( and compared the THE FIRST LAW OF THERMODYNAMICS 9b). Assuming the difference in the heat capacities to be entirely due to the work done in the expansion of the air at constant pressure.5)." ( 3f). i. the production of energy of a particular type without the disappearance of an equivalent amount of energy of another form.0687 cai. 107 ergs. or 1. von Helmholtz showed that the failure to achieve perpetual motion and the equivalence of work and heat. described above.) and constant C. = = 2. equation (2. X Work of expansion = 1. This law has been stated in various forms. the work will be expressed in ergs." at of 1 g. it cannot be created or destroyed. thus. calculate the relationship between the erg and the calorie.0687 cal. .) and constant volume is 0. According to equation (3.16 of its volume at C for every 1 rise of temperature.4 cc. 6c..4/273. for 1 increase of temperature. were aspects of a wide generalization which has become known as the law of conservation of energy.
is of great importance. It may be pointed out that the first law of thermodynamics can be regarded as valid as long as perpetual motion of the first kind is found not to be possible. Following historical precedent. The equivalence . The energy liberated ultimately becomes associated with some form of matter. as far as human observation is concerned. However. Energy and Mass. The first law of thermodynamics requires that the total energy of an isolated system must remain constant. the laws of thermodynamics would not be applicable. as will be seen in this and later chapters. the failure is apparent.1). 6e. which have been found to be in complete agreement with actual experience. rather than real. the loss or gain of energy by a body must be accompanied by a corresponding change of mass. that the energy change in a system must be exactly compensated by that of its surroundings. for example. The forms of energy are not necessarily the same. that it may be completely disregarded. According to the theory of relativity there is an equivalence of mass and energy. In certain reactions between atomic nuclei there is a liberation of large amounts of energy without the apparent disappearance of an equivalent quantity of energy of another kind. identical with the principle of conservation of energy. this contingency appears to be so remote. other ways of stating the law will be mentioned later. It is upon the assumption that such experience is universal that the first law of thermodynamics is based. and there is a gain of mass of the latter identical with the loss suffered by the nuclei. or loss. Brief reference may be made here to circumstances under which the principle of the conservation of energy appears to fail. This means that any loss or gain of energy by a system must be exactly equivalent to the gain. the failure to construct a perpetual motion machine and the constancy of the mechanical equivalent of heat. a study of the masses of the nuclei concerned shows that there is a loss of mass which corresponds exactly to the energy set free. the validity of the first law of thermodynamics has here been associated with the impossibility of perpetual motion of the first kind and the constancy of the mechanical equivalent. in another universe or under other circumstances. and it will be applied in later developments. This law is. The conclusion derived from the first law. respectively. for it leads to a wide variety of conclusions. If. Isolated Systems and the First Law.1) where c is the velocity of light. and can consequently be stated in either of the forms given above. as is apparently the case in the universe of which the earth is a part. The change of energy AE is related to the change of mass Aw by the relationship A#  c'Am. but if there is to be a net conservation of energy the amounts must be equivalent. 4a that a 6d. (6. It was stated in combination of a system and its surroundings may be referred to as an isolated system. as required by equation (6.6e THE CONSERVATION OF ENERGY 35 It should be clearly understood that the law of conservation of energy is purely the result of experience. in fact. However. although there may be changes from one form of energy to another. however. the creation of energy were proved to be feasible. The law has nevertheless a much firmer basis. of energy by the surroundings.
g. e. 4e may be applied.. term internal energy can then be used when it is desired to describe the energy associated with the motions. is not included in the thermodynamic energy content. In other words. 5. as stated above. Since nuclear reactions are not considered in chemical thermodynamics. ENERGY AND HEAT CHANGES The energy possessed 7a. vibration. through space. e. that is to say. and not by the manner Volume in which it reached that state. this may 5 on its thermodynamic state. e. Consider any system represented by the state A in Fig. The Energy Content.. magnetic. An increase of temperature at constant volume. the energy of vibration and rotation of the molecules. its energy content. must result in an increase of its energy. that the energy content is a property of the system of the kind that is determined only by the state of the system.36 of THE FIRST LAW OF THERMODYNAMICS mass and energy means that the laws of conservation of mass and energy can both be true.. Energy changes it will be proved that the energy is a singledirect and reverse paths valued function of the thermodynamic variables of It is consequently a property to which the results obtained in (he system. by utilizing the first law of thermodynamics.. is determined by the position of the system in a force field. for example. the problems associated with the relationship between mass and energy will not arise. " The energy content of a system must depend There itself. . e. from the energy due to external factors. but for present purposes it may be The referred to simply as the energy or the energy content of the system. by a system. as distinct from th%*anslational energy resulting from the motion of the molecule as a whole.g. brought about by the transfer of heat to the H system from the surroundings. which. electric or gravitational. so that the state of the system is represented by the * This motion of the molecule is. Suppose the conditions are now altered. to distinguish it tion. It will now be shown. that determine the energy content. in which the coordinates are the observable properties. there is the energy which of the electrons and nuclei..g. 5. within the molecule. of course. etc. but each is a mere corollary of the other. may be regarded as falling into two main categories. the energy which is a characteristic property of the system include the translational energy of the moving molecules. in FIG. pressure and volume. not to be confused with the motion of the system as a whole. and it is only that in the first which is taken into consideraThe latter is sometimes called the internal energy. is first. as well as the energy On the other hand. and by the motion of the system as a whole. 7. along the path I. however.g. rotation. In thermodynamics the energy in this second category is usually ignored.
Since this is confirst law of thermodynamics. that the 7 energy changes in the different paths I. In other words. between the two given states The conclusion to be all be equal to each other. It is clear from these considerations that the energy of a system is a "property" of the system in the sense described in 4e. by path II. 6). I. a t The symbol A as applied to a change in a thermodynamic property accompanying given process represents the algebraic increase in the property. Energy change independent of path state to another. and independent of the path followed. by path I. It is. It is always equal to the . (Fig. I". to that in path II. This statement may be regarded as a form of the first law of thermodynamics. must etc. J". = En . It follows. provided the surroundings remain unchanged.. etc. i. must be numerically equal to that involved in the reverse process B > A. energy would have been created. possible to ascribe a definite value R to the energy or energy content of a particular system in a given sLatc. but there would be a residuum of energy if the surroundings were unchanged. for example. is that the change in energy of a system. etc. It is possible to proceed from A to B by trary to the various paths. without the disappearance of an equivalent amount of another kind. by different processes. must each be numerically equal to that in II. If EA represents the energy in the thermodynamic state A.1) is independent of the path taken in the change of state A > B. and EB that in the state B. depends only on the initial and final states. I".ENERGY AND HtfAT CHANGES 37 point B\ the system is then returned to its exact original state by a series It is then a direct consequence of the of changes indicated by the path II. it is evident that the energy changes in I. As will be seen below. A and /?. then by carrying out the change A > B by path I and the reverse A by path II.e. therefore. it must be concluded that the energy change in the process A B.. of the system. but opposite in sign.EA and * (7. I . In thermodynamics the word "change" is frequently used to imply "change in thermodynamic state". the system would be brought back to its original change B state. the terms "path" or "process" then refer to the means whereby the given change in state is accomplished. argument. if this were not so a perpetual motion machine would be possible. and not on the previous history. returning From the preceding in each case by path II.* first law of thermodynamics that the total energy change of the system in path I must be identical in magnitude. I'. associated with the passage from one Volume FIG. therefore. this value will depend only on the state. I'. therefore. then the increase thermodynamic is of energy AE"\ in passing from A to B is given by . that the increase of energy in path I were greater than the decrease in returning by II. Imagine. a particular change may be achieved by following various different paths. 6. drawn..
taken up by. the E value of &E for any process depends upon the amount of material contained in the system which undergoes the change. and gains energy W. that it gains energy. This equation or. is larger in the initial state. 7c. it is apparent that the energy is an extensive property. if A(? is found to be negative. this must be identical with the increase AE in the energy content of the system. the system. The energy change accompanying the change in thermodynamic state of a system may be due to the per formance of work on or by the system. then by convention is positive if work In other words. of A(7 is. the net gain of energy is Q law of thermodynamics. is taken as loses as when the the result of some form of system energy positive doing is negative if work is done on the system. and may include work of expansion or any other form of mechanical work. on the other hand. Thus. as well as electrical work.88 THE FIRST LAW OF THERMODYNAMICS 7b Since the energy content of a system obviously depends on the quantity of material contained in the system. By the first Q. It should be noted that the conventions for and Q given above are those which are widely adopted in the study of chemical thermodynamics. if confusion is to be avoided. is given up by. alternatively. the difference between the heat absorbed by a system and the total work done by the system may be defined as equal to the increase in a property of the system catted its energy content. Similarly. Q The significance . the property O has a larger value in the final than If A<7 defined in this in the initial state. and also to the transfer of energy to or from the system in the form of heat. etc. Energy Change in Cyclic Process. by the transfer of heat. that is. that is. if energy is transferred to.2) may be regarded as a form of the first law of thermodynamics may be used as a means of defining the energy content E. If {he mass of the system is altered. a system returns to its exact original state. 7b. by the convention is done by the system. the energy content will be affected in the same proportion. or any other. The term "work" is used here in the general sense referred to in 3a. If. Similarly. If is the magnitude of the work done. The amount of heat transferred is represented by Q. but once the conventions have been decided upon they must be adhered to throughout and never changed. There is no particular reason why these. thus. conventions should be used. as a result of a series of processes. the system in the form of heat. and this is regarded as positive. manner is positive. Work. Since the system loses energy W. Q is positive when the system gains energy as heat. because of work done. as defined in 4d. of course. On the other hand. Q is negative. if heat is transferred from. thus. the reverse of that of A0. W W W W W A# = Q . so that there is a corresponding decrease of energy. it follows from equavalue in the final state minus that in the initial state of the process. Heat and Energy Changes. its energy content will be unchanged so that AS must be zero. In this event. so work. by convention. it (7.W.
All the energy lost by the system appears in the form of heat.3). ENERGY AND HEAT CHANGES 39 work done by the system is equal to the heat absorbed in Q . the values of the heat and work terms vary with the path followed in proceeding from the initial to the final state. the work done for a given volume change will thus depend on the external pressure. the increase AJS in the energy content depends only on the initial and final states. and the heat absorbed Q is equal to the work done by tke This equation first the W system. the magnitude of which may vary according to circumstances. does not vary with the path taken.2). It is seen. As seen abpve.7d tion (7. as in a combustion bomb ( 12g). the difference Q W. According to the first law of solely thermodynamics. i. no work being done.W. at constant volume. that even though Q and are both variable. and vary similarly. for their difference must have a definite value for a given change of thermodynamic state. however. Obviously.. so that the energy W W W W . the heat absorbed in the process.3) is an expression of the impossibility of "perpetual motion of 6c. That this is the case may be shown in a number of ways. in accordance with equation (7. The heat and work terms involved in any change of thermodynamic state differ from the total change of the energy content in one highly important respect. It was seen in 3g that when a system expands the work done is equal to the product of the external pressure and the increase of volume of the system. A process. 7d. that the the process. This is.e. and independent of the path taken in the process. Incidentally. i.. The variability of heat and work terms will be evident from other conFor example." as stated in any net change. it is impossible to produce work without drawing upon energy. Q. On the other hand. and the remainder into heat. but since AZ? is equal to Q by equation varies with the path. must (7. it will also depend on the manner in which the change is carried out. a certain mass of hydrocarbon may be completely siderations. (7. is referred to as a cyclic process or cycle. The value of will consequently not be determined W by the initial and final states of the system. These substances may be made to react with one another in a calorimeter. AE is zero. for it is determined only by the initial and final states of the system. namely heat. Another instance of a similar type is provided by a system consisting of zinc and dilute sulfuric acid. therefore. burnt in air. Dependence of Heat and Work on the Path. which is equal to AB. they are not independent. it should be borne in mind that although Q and depend on the path. In any cycle A? is zero. or series of processes. from an outside source.2). the quantity A2? for a given change has a definite value depending only on the initial and final states of the system. in an internal combustion engine a large proportion of the energy of the hydrocarbonair system is converted into mechanical work.e. Provided the system does not undergo kind. as a result of which the system returns exactly to its original thermodynamic state. not the case for Q and W'.
the respective amounts varying with the method whereby the change from the In other words. equation (7. for Q and the thermodynamic state of the system. a galvanic cell can be formed with the sulfuric acid as electrolyte. 1744 (1932). written in the form initial to the final state is carried out. constant pressure or constant volume. Phys. Electrical energy is then produced. Chem. ibid. For discussions of this and related topics. It should be understood that although the heat and work changes are variable quantities. the values It will be seen later of Q and for any specified path are quite definite. They merely represent different ways in which energy can enter or leave the system.4). The results obtained are then useful for thermodynamic purposes. 7e. ibid.1)]. 44. The differential. and this may be used to drive a machine. but the energy content cannot be regarded as consisting of definite "work" and "heat" portions. see Tuncll.. which may be treated in the manner described in integral of dE between the limits of the initial (A) and final (B) states of a EA or AJE [cf. thus doing meThe inert metal is unaffected in the process. Heat and Work Not Properties of a System. (7. . equation (7. these however. 44. energy. the performance of ways in which the energy of a system can be changed. MacDougall.g. equation (7. and so the chanical work. by combining the zinc with an inert metal. e. This is. for a given change in thermodynamic state. 713 (1940). be misleading. Instead.5) where dE is the increase in the energy content of the system accompanying an infinitesimal stage of an appreciable thermodynamic process.. work and the flow of heat represent dE = dQ . is that associated with the reaction between zinc and sulfuric acid to form zinc sulfate and hydrogen. 1 A process involving an appreciable change in the thermodynamic state of a system is often conveniently considered as made up of a series of inFor each of these stages. .. heat and work are not thermodynamic properties of a system. J. they will not be employed in this book. However.dW.40 THE FIRST LAW OP THERMODYNAMICS 7e decrease resulting from their conversion into zinc sulfate and hydrogen is accounted for almost entirely by the heat evolved. q is the quantity of heat absorbed and w is the work done by the system at the same 1 Br0nsted. appearing partly as work and partly as heat. In order to avoid the misunderstandings which may arise from the use of such symbols as dQ and dW.4) will be written as dW W dE = q  w. 36.. 699 (1940). that an adequate specification of the path can often be given in a simple manner. (7. not true for the quantities dQ and are not properties of quantities are not complete differentials. The conclusion to be W drawn from the preceding discussion is that unlike the energy content. process has the definite value EB in equation (7.2) is sometimes finitesimal stages. in the sense of 4d. such as copper or platinum. and dE is a complete 4e.4) but this equation is liable to The energy E is a thermo dynamic property of the system.
i. Processes of this kind are not thermodynamically reversible.8a time. when the given process has been performed and then reversed. In general. Further. as described above. but the process may be regarded as a series of thermodynamic equilibrium states. A process of this kind is said to be thermodynamically reversible. the system at every instant is in a state of virtual thermodynamic equilibrium. Although condensation of the vapor is taking place. it is necessary that the system should always be in a state of virtual equilibrium. 8. the latent heat. so that the system is always in virtual thermodynamic equi . REVERSIBLE THERMODYNAMIC PROCESSES In other words. Imagine a liquid in equilibrium with its vapor in a cylinder closed by a f rictionless piston. i. If the external pressure on the piston is increased by an infinitesimally small amount. A simple illustration of a reversible process is provided by isothermal evaporation carried out in the following manner. both the system and its surroundings must be restored exactly to their original state. external pressure is continuously adjusted so as to be always infinitesimally less than the pressure of the gas. Similarly. the liquid will vaporize extremely slowly.e. will be taken up by the thermostat. since the temperature is maintained constant. heat.. The system is changing. a large thermostat. and the pressure above the liquid will remain constant. Q and W. however. REVERSIBLE THERMODYNAMIC PROCESSES A particular type of path between 8a. Thennodynamic Reversibility. Hence. and placed in a constant temperature bath. the vapor will condense. two thermodynamic states is of special interest. q 41 may be taken as the energy entering the and w is the amount leaving it as work done during an infinitesimal stage of a process. This is the kind of path for which it is postulated that all changes occurring in any part of the process are exactly reversed when it is carried out in the opposite direction. since vaporization is taking place.e. but the condensation will occur so slowly that the heat evolved. The expansion will then take place extremely slowly. decreases. The isothermal expansion of a gas can be carried out reversibly by placing the cylinder of gas in a thermostat. if the external pressure is made just smaller than the vapor pressure. respectively. Rapid evaporation or conthe external pressure.. to system as which equation (7. by lead to temperature and pressure gradients within the system. if the it must be is to be supposed that the process thermodynamically reversible. and thermo dynamic equilibrium will be disturbed. in order to follow a reversible path. its own pressure finitesimally small amount.2) is applicable. will sudden or of the decrease increase densation. and again the temperature and pressure will remain constant. The temperature of the system will not rise. The algebraic sums of the q and w terms for all these infinitesimal stages will give the total heat and work changes. and this requires that the process be carried out infinitesimally slowly. and adjusting the external pressure so as to be less than the pressure of the gas by an inAs the gas expands.
If at any instant during the expansion the external pressure is adjusted so that it is maintained just infinitesimally greater than the gas pressure. but since the process is carried out extremely slowly the absorption of energy as heat keeps pace with the loss as work and the temperature of the system remains constant.g. It is necessary. The discussion given above has referred in particular to isothermal changes. temperature. the processes would not be reversible. its . by a sudden and large increase of the external pressure.42 THE FIRST LAW OF THERMODYNAMICS 8b The heat required by the gas. then from what has been stated in 8a it follows that the external pressure must be P dP. pressure and volume. Reversible Work of Expansion. that the process should take place in such a manner that the system is always in virtual thermodynamic equilibrium. 4b).. which is always in a virtual state of thermodynamic equilibrium.g. the process will be reversed. // the system is homogeneous and has A a constant composition. The work w done by the system when it increases its volume by an infinitesimal amount dV is equal to the product of the external pressure and the volume change ( 3f ) thus. The changes would not involve a continuous succession of equilibrium states of the system. w  (P  dP)dV. If P is the pressure within a system undergoing a reversible process. and expansion accompanying complete solution is possible in certain cases. apart from infinitesimal differences. but reversible processes are not necessarily restricted to those taking reversible path may involve a change of place at constant temperature.. however. where dP is a very small quantity.g. the form of work against the external pressure. A general expression for the work of 8b. The sum of the PdV terms may t W * Such a system will sometimes be referred to as a "simple system" (cf. . and hence they could not be reversible. follows that (8. it Neglecting the very small. e. There would be both temperature and pressure gradients which would be different in the expansion and compression. as the volume changes from its value in the initial state (Vi) to that in the final state (7 2 ). to balance the energy expended in librium.1) w = PdV. second order. product dPdV. as well as of pressure and volume. Since P and V are definite properties of the system. the conditions for a thermodynamically reversible process would thus not be applicable. e. is taken up from the thermostat.* two thermodynamic variables. will be. by suddenly releasing the pressure on the piston. or the compression were rapid. If the expansion were carried out rapidly. The total work done in the process will then be equal to the sum of a continuous series of PdV terms. and the gas will be comAt every stage in the compression the system and surroundings pressed. will completely describe its state at any point in a reversible process.. d V is a complete differential. in exactly the same thermodynamic state as they were at the corresponding point in the expansion. a reversible process may be readily derived. e.
V* (8. i. *2 (8. . the equations (8. the value of the integral This may be in equation (8. dV = P(F 2 . 5 or Fig. nRT. According to equation (8.. (8.3) F2 V\ is equal to AF. and P the vapor pressure.. reversible expansion of n moles of an ideal gas. 6. in Fig. then becomes pressure W=P where is V* f Jv. PV . dV = Fo nRT\n^Fi X^ y ^ (8.. hence equation (8. the pressure. such as Fig. nevertheless. remains constant throughout. In the isothermal vaporization of a liquid. which is equal to the vapor pressure at the specified constant temperature. while V* and Pj represent the final state. the work of expansion will clearly be a variable quantity. l An PiFi alternative form of this result is often convenient. By specifying the reversible path it is possible to determine the actual value of the work of expansion from equation (8. between the initial and final state are possible. so that P = nRT/V.8b REVERSIBLE THERMODYNAMIC PROCESSES 43 thus be replaced by the definite integral between the limits of Vi and so that F2 . Since the state of a simple system at any point of a reversible process can be described completely by the F . the equation of state is gas. W XVt . and so Pi/Pz'. expansion.4) . I'. Since various paths.2) since T and R are constant.2) the work done in such a path is equal to the area enclosed by the curve and the two ordinates at the initial and final volumes.2).2) for the work of expansion. The results just derived were based on the supposition that the change was one involving an increase of volume. is equal to P2F 2 . and volume. at constant temperature.2) As may be expected from the discussion in 8a. C PdV. All that is necessary is to take Fi and PI as representing the system in the If initial state of the process. I". this value of P may be substituted in equation (8. Another case of interest is that in which the system consists of an ideal For n moles.5) are applicable to both expansion and compression.70 = PAF. the increase in volume of the system. For an isothermal expansion involving n moles of an ideal gas.2) depends on the path between V\ and 2 seen more explicitly in another manner. Two simple cases may be considered. 6.4) and (8. such as I.4) can also be written as For an ideal gas F /Fi 2 is equal to TF = nffrin^. etc. The equation (8.5) for the isothermal.e. the path of the process can be represented by a curve on a PF diagram.
1 mole. P + is given by W Since = RT In ^ = 8. this is to be expected. Actually.2 X 2.5) are determined by those The energy units of of R. however. Substituting these data in equation (8. the pressure units are immaterial. On the other hand.5). the work done. and expected. given by equation (8.5). irrespective of the nature of the system. V* is is seen to be negative by equation (8. an exact relationship between and F.0 C.5). as given by equations (8. the work done by the system.00 and the final pressure 2 is 5.g. If this were done. this conclusion is applicable to any isothermal.4) or (8.. since the work depends on the ratio of the pressures.1 is negative. reversible change (cf. is evidently a definite quantity depending only on the initial and final states. the work done. 8c there is an expansion.314 X 10 T2 7 X 298.. it is apparent. the initial pressure Pi is 1.00 atm. from equation (7. revalue.2 K.2) that the work done in any isothermal. F 2 is greater than Vi.4). 25a). that both be determined by the initial and final states of the system only.00 atm. The only possible way of increasing the work would be to make the external pressure greater than in the reversible. Although the volume change in a process may result in expansion or compression. reversible expansion is that the work done is the maximum possible for the given increase of volume. W of Problem: Calculate the work of expansion in ergs when the pressure of 1 mole an ideal gas is changed reversibly from 1. W In the two special cases of isothermal. since the work of expansion is required in ergs. this is to be less than Fi. and negative when the volume decreases.3) and (8." It is seen to be positive when there is an increase of volume.99 X 1010 ergs mole. =  3.4) and (8. at a constant temperature of 25. the work done by the expanding gas would clearly be less than the value given by equation (8. in equations (8. fact concerning an isothermal. even if work other than that of expansion is involved. If the external pressure were made appreciably less.00 atm. it follows from equation (8. instead of infinitesimally less. if a compression occurs. and hence W.1 The absolute temperature T is 273. than the gas pressure.2 25 = 298. the work of expansion for 1 mole of gas W R X . versible process in which the work performed is exclusively work of expanand Q will sion. for the pressure of the gas increases in the process. Maximum Work in Isothermal Reversible Processes. the work is done on the gas. is positive.2). Since there is always e. the external pressure would be either equal to or greater than the gas pressure and hence expansion P W . pressure or volume.314 107 ergs deg.2). to 5.303 log J . therefore. reversible expansion considered above. isothermal expansion. for work is now done on the system. at a constant temperature. A notable 8c. the value of to be used is 8.4) or (8. and hence they will represent definite quantities. and hence the volume is decreased.44 THE FIRST LAW OF THERMODYNAMICS. reversible expansion must have a definite For an isothermal. is always referred to as "work of expansion.
hence. In general. . the state of equilibrium is important. consisting of 21% by volume of oxygen and 79% C? of nitrogen. Evaluate the energy.M.35 X 10 6 Should the accompanying loss of mass of the system be are liberated. the ideal to be aimed at is known. and must be regarded as ideal. each of mass 1. seen that the results derived from a study of reversible processes can be applied to reactions as a whole. the E. set free in the formation of 1 g. In the combustion of 1 mole of sucrose (CwEtaOn). cal. as will appear in later sections. approximately 1. and the quantity of electricity passing. . each of mass 1. In chemistry.8c EXERCISES 45 would be impossible. therefore. for it shows to what extent a particular reaction can proceed. from two protons. too.M. At increased 4. in the production of electrical work by means of a voltaic Cells of this type can be made to operate isothermally and reversibly cell. the reversible work of expansion is (numerically) equal to the minimum amount of work which must be done by the surroundings on the system in order to bring about the specified change in volume (or pressure). Determine the maximum work that can be done in the expansion of 5 moles of an ideal gas against an external pressure of 1 atm.0090.0076. of a given cell then has virtually its maximum value. detectable? 2.F. is less.F. As reversible processes must take place infinitesimally slowly. because the results indicate the maximum efficiency obtainable in any given change. even in engineering. In this way. EXERCISES 1. In the case of an isothermal compression. 3. it is clear that the same extent of chemical reaction in the cell will yield more work in the reversible than in the irreversible operation. by the methods of thermodynamics is of great value. of air. spite processes impracticability.F. This is true. even if they are actually carried out in an irreversible manner.0028. it follows that infinite time would be required for their completion. what is the minimum amount of work in ergs required to compress 1 kg. if large currents are taken from the cell. in calories. for example. therefore. that the reversible work of isothermal expansion is the maximum work of this type possible for the given change in thermodynamic state. It follows. atom of helium nuclei. by withdrawing current extremely slowly ( 331) the E. when its temperature is by t C. thermodynamics provides information of conIt will be siderable chemical significance. and two neutrons. Express the result in (i) ergs.M. (ii) defined cal. Assuming ideal behavior. Neverof in the of their reversible study theless. Such processes are. of mass 4. Since the electrical work done by the cell is equal to the product of the E. so that it functions in an irreversible manner. to 200 atm. The work of isothermal expansion done by a system in an irreversible process is thus always less than for the same increase of volume when the change is carried out reversibly. On the other hand. from 1 atm. the work that can be obtained in an isothermal change is a maximum when the process is performed in a reversible manner. not practicable.
. Explain how the compressibility diagram alone could be used to determine the isothermal. in Iiteratm. when the pressure of 100 g.) Compare the result with that to be expected for an ideal gas.. 9. Apply the method to . reversible work of ex at 26 amount pansion for 1 mole is given by where V\ is the initial and Fi . (ii) 0.001 atm.. Show that for a van der Waals gas. An ideal gas is compressed isothermally and reversibly from 10 liters to 1. assuming ideal behavior. required to expand 1 mole of carbon dioxide isothermally from an initial pressure of 200 atm. (Instead of solving the cubic equation to obtain the initial and final volumes. (ii) defined cal. of water vapor is decreased isothennally to 0. the isothermal. reversible work of expansion of any gas. pressure is to be evacuated C to a pressure of (i) 0. moles of gas are present in the system? 7. to a final pressure of 1 atm. The vapor pressure of water at 25 C is 23.the final volume. assuming ideal behavior.01 atm. 6. 10..5 The work done by the surroundings is 2. they may be obtained more simply by means of the generalized compressibility diagram. Compare the minimum of work required in each case. Exercise 9. Determine the reversible work.76 mm. 8. assuming van der Waals behavior.001 atm. at 50 C.250 caL How many liters at 25 C. Calculate the reversible work of expansion in (i) Iiteratm.46 5* THE FIRST LAW OF THERMODYNAMICS A vessel containing 1 liter of hydrogen at 1 atm..
For such processes the heat changes will have definite values. apart from isothermal. the same must be true for the heat change at constant volume. work of expansion. it follows that the E + PF. THE HEAT CONTENT 9a. an indefinite quantity. dependent only on the initial and final states of the system. so accompanying increase of volume AF may be represented by Ft that equation (9. the work of expansion may be replaced by is the increase of volume.CHAPTER IV HEAT CHANGES AND HEAT CAPACITIES 9. Writing the first law equation (7. using the and hence subscript V to indicate a constant volume process. there are certain simple processes.. Heat Changes at Constant Volume and Constant Pressure. is equal to the energy increase accompanying the process. where EI and #i. equation (9. where conditions by the subscript P. (9. it follows then from equation (9.4) P and quantity F are properties of the state of the system. Since the latter quantity depends only on the initial and final states of the system. (9. that the work is only mechanical work due to a change of volume. At constant pressure P.e.E ) + P(F. The work term will also be definite. that W W Qv  A#F . respectively.AE it will + W. For a process occurring at constant volume.1). there is no expansion or contraction.A#P The + PAF. previous history.2) so that the heat absorbed at constant volume.3) increase AJSp in the energy content is equal to Et Ei. thenno .Fi) + PF. as is the case in most thermodynamic processes which do not involve the performance of electrical work. Qv. i. like the energy E is dependent only on the thermoand not on its dynamic state. the Fi.1) takes the form AV AF W QP . similarly.2) in the form Q . for it is equal to zero. representing constant pressure PAF. (9. i.. in general. for which the paths are precisely defined.1) be supposed.e.) .(Bi + PFi).are the values for the initial and final states. will be zero. l y (9. Although the heat change is.3) becomes Qp = (E* = Since (E t . . 47 The extensive. reversible changes.
The value of Aflp is seen by equation (9. the heat capacity C may be defined as the ratio of the heat Q absorbed by a system to the resulting increase of temperature T 2 Ti. equation (3. and not on the path taken. Since the heat capacity usually varies with the actual temperature. For a process at constant pressure.7) is the quantity of heat absorbed for a small increase dT in the temdT. the heat absorbed has a definite value.* 9b and is dynamic property E + PV is called the heat by the symbol H. In view of the dependence of q on the path taken. it is evident that the heat capacity will also be uncertain. which is equal to is constant. since AE and Qp are here determined by the initial and final states. (9. since the former quantity depends only on the initial and final states of the system. The work done in the constant pressure process. equal to 2 Fi. equation (9. W P F W C = where q lim %  ^ al . At constant volume. . t (9.8) where qv and hence the heat capacity CV. it is obvious.48 HEAT CHANGES AND HEAT CAPACITIES content.. is independent of the path. respectively. and the volume change is also since the pressure definite.7) may be written as + CVg. i H and H 2 states. therefore.6) to be equal to Qp.5) Consequently.6) are the values of the heat content in the initial and final and A//P is the increase in the heat content of the system at constant pressure. Heat Capacities at Constant Volume and Constant Pressure.. equation (9. a definite quantity depending on the initial and final states of the system. //! (9. According to equation (9. (9. i. The use of the term "heat content/ 1 however. that is. 1 e. PAF.4) can be put in the form QP = where # 2 = A#P. // represented = # + PV. as AT is made very small. must not be interpreted as implying that the system possesses a definite amount of heat energy. the heat Qv absorbed in an appreciable process at constant * Engineers and physicists usually refer to it as the enthalpy. by definition. that must now also have a definite value. such as constant volume or constant pressure. unless conditions are specified. has a definite value. AT. which define the path. perature of the system from T to T in general. it is preferable to define it in terms of the limiting value as T 2 approaches 2\.e. Since the heat absorbed is rot.3)]. ment. seen in 3d. Aside from this arguAF. the same will be true for the heat term Qp.2). As 9b. thus [cf. for example. the heat absorbed under these conditions. the unusual notation q/dT is used to define the heat capacity at the temperature T.
as defined by equation (9. Qp. r <9 ' 9' The partial differential notation is used because E is a function of the volume as applied to the (or pressure) as well as the temperature. the subscript partial derivative in equation (9.11).6). Heat Capacity Relationships.  *T. The heat capacity of a system at constant volume is therefore equal to the rate of increase of the energy content with temperature at constant volume.9) indicates that in this case the volume is maintained constant. it is for such systems that the energy is dependent upon only two thermodynamic variables volume and temperature. it is possible to derive general equations connecting the heat capacity of a system at constant volume with that at constant pressure. e. As already seen. it can be shown in a manner exactly similar to that used in deriving (9. and it may consist of a single substance or of a solution whose composition does not vary.. g. defining heat capacities at constant volume and constant pressure. the heat absorbed in an appreciable process at constant pressure.9) mentioned that the important equations and (9. respectively.7) takes the form V Cp = and since qp is definite. pressure and temperature or 9c.9). Making use I)/ The heat capacity of a system It should be rate of the increase of heat content with temperature at constant pressure. Since the energy of a homogeneous system of definite composition is a singlevalued function of the volume and temperature.9C THE HEAT CONTENT 49 volume is equal to the increase &E V of the energy content in that process. that definite. At constant pressure^ equation (9. (9 . the increase of heat content in the process.g.10) the heat capacity CP at constant pressure is also of the fact that according to equation (9.n) at constant pressure is consequently equal to the (9. is equal to A// P. are applicable to any homogeneous system of constant composition. (9. becomes . of state. The (simple) system may be gaseous. From the results already given. dE is a complete differential which can be represented by E . For an infinitesimal stage in a constant volume process qv is equal to dE v and so the heat capacity at constant volume. liquid or solid.8).
as will be seen below. that there was no net heat change.6)1 *nd hence. A particularly simple system is that involving an ideal gas.9). were connected by a wide tube with a stopcock.50 [of.5)]. H = E + PV. 9d According to equation (9. by equation (4. relating pressure.](S?)/ By starting with the relationship which is permissible since the heat content of a simple homogeneous system. opened the temperature of the globe which originally contained the air fell. the value of Q was zero. GayLussac (1807) and J.g. and since CP is equal to (dH/dT) P it follows that Combination of this result with equation (9.10). the foregoing results will apply to any homogeneous system of constant composition. so that is equal to Cv. and this is especially true when an equation of state. Subsequent experiments. carried out along somewhat different lines by J.. when the volume of the gas was increased in the manner described. In the experiments made by J.14) yields immediately S). e. As already indicated. Two similar copper globes. Joule and . the pressure and the temperature. [equation (9. some simplification is possible. i. It appeared. therefore. P. and this type of system will now be considered. it is possible to derive the equation  by a procedure analogous to that used in obtaining equation (9. P. L. there was no gain or loss of heat. the heat capacity of the By definition . HEAT CHANGES AND HEAT CAPACITIES equation (4. volume and temperature. however. is dependent only on two thermodynamic variables. one containing air under pressure and the other evacuWhen the latter was ated..e. like the energy content. (dE/dT) v system at constant volume. In certain cases. is available. Joule (1844) it was found that when a gas was allowed to expand into a vacuum. but that of the other globe rose by an equal amount.16). 9<L Energy Content of Ideal Gas.
the by the system being equal to the work done by it. However. at constant temperature. The energy of a given quantity of the gas thus varies only with the temperature.g. from equation the work of expansion (7.20) expansion is carried out reversibly. result expressed by equation (9. that AE must be zero in the process.4) or (8. it must also be independent of the pressure. Effect of Pressure and Temperature on Heat Capacity of Ideal Gas. and so it is probable that for an ideal gas the value of Q in the free expansion described above would be actually zero. but AE is zero. hence. When an ideal gas expands against an appreciable external pressure. the heat absorbed (9.96 THE HEAT CONTENT 51 W. is independent of the volume.2). It follows. The same can be shown to be true for . of the gas. it appears that the more closely the gas approximates to ideal behavior the smaller is the heat effect. at constant temperature. against no external pressure. therefore. Thomson (Lord Kelvin).22) so that the heat capacity at constant volume of an ideal gas is independent of the volume. The energy of the gas depends on two variables. or pressure.5). that is.19) is a necessity for a gas obeying the the energy content being independent of the volume. thermodynamics. at PV = RT and pressures. between 1852 and 1862. Since the gas expands into a vacuum. is independent of its volume. viz. If the work done is given by equation (8. volume and temperature. showed that a temperature difference. reversible expansion of n moles of an ideal gas is determined by the same expression. in other words. a volume increase in which no external work is done.e. indicating a value other than zero for Q. it is consequently possible to write equation (9. relationship at all temperatures W Q = W.. There is an important consequence of the fact that the energy content of an ideal gas. i. that (9. the conclusion just reached may be represented mathematically in the form W if The x  any constant temperature. it follows.2) that for the isothermal expansion of an ideal gas. therefore. e. by utilizing the second law of ideal gas. (9. and hence the heat Q absorbed in the isothermal. has a finite value.19) is taken as one of the criteria of an It will be shown later ( 20d).21) 9e. from equation (7.9) in the form Cr = . is also zero. should have been observed. Q = nRT In = nRT ^ Kl In ^i /2 (9.. there is no change in the energy content of an ideal gas as a result of free expansion.. Since the energy content of an ideal gas.
5. etc. all gases do not behave in the same manner in respect ture. For reasons which will be made clear in Chapter VI. since that the heat content of an ideal gas is dependent only on the temperature.24) a. the result is + dVr For an \dVr I dV T ideal gas. e.g. Thus.23) cannot be employed.e. One of these. Experimental observations have shown that the heat capacities of some monatomic gases. however. E PV. respect are those containing only one atom in the molecule. which must be derived from the experimentally determined heat capacities over a range of temperatures. 7. The heat capacity at constant PV RT pressure can then be represented by equation (9. 21e).. i. if equation (9. is equal to zero. PV RT 9f.52 HEAT CHANGES AND HEAT CAPACITIES 9f H the heat capacity at constant pressure. thermodynamics alone cannot supply the answer. 21d.. should be independent of temperature Gases which might be expected to approximate to ideal behavior in this ( 15b).22) and (9. which may be regarded = either as based on experiment or on the postulated equation of state for an ideal gas. energy and heat contents are known to vary with the and hence Some equations (9. The form of the expression which represents this variation cannot be predicted by means of thermodynamics. It follows.. are constants. According to the kinetic theory of gases. It has been necessary to introduce the result that (dE/dV)r is zero. (dE/dV)r is zero.. as seen above. It must be realized that the conclusion that the heat capacities of an ideal gas are independent of pressure is not based on thermodynamics alone. are almost constant over a very considerable range of temperaIn general. which has been widely employed. at low pressures. wnose molecules possess translational energy only. pressure. the heat capacity of an ideal gas. the heat capacities of all gases containing two or more atoms in the molecule must vary with temperature.5). and so it is inadvisable to make a general postulate in this connection. 0.e. at constant temperature. and T is . and so purely empirical formulae are used. therefore.11) in the form (923) indicating that CP for an ideal gas does not vary with the volume or pressure. (9. to the effect of temperature on heat capacity as ideal behavior is approached. and [d(PV)/dV]T is also and hence is constant. Similar considerations are applicable to the problem of the variation of heat capacity of an ideal gas with temperature. the derived in later sections ( lie. and is independent of its volume or pressure. is a power series of the form CP where a + 0T + yT* + ST 78   . Heat CapacityTemperature Relationships. and it is necessary to introduce other information. helium and argon. expressions for the variation of CP and CV with pressure or volume will be For a real gas. is differentiated with respect to volume. i.
The constants in Table /II cannot be safely used for extrapolation outside this range.. it is found upon integration that CP = a r [a(r2  Tl) T.728 Table 3 at end of book. ei al.0807  0.* HEAT CAPACITIES OP GASES (Cp) AT IN CAL.84 23.3555 0.413 2.147 6.424 0. 25.267 3.468 1. (9.2801 0.787 gases. Eng.210 3. using the 250 (1942).9f THE HEAT CONTENT 53 the absolute temperature. 1859 (1945).342 6. Chem.057 0."1 MOLE.1581 0. PRESSURE Gas H. Ind. 2311 (1934).208 10. this value is then taken as constant for purposes of calculation.096 6. it is sometimes convenient to use the mean value of the heat capacity over a range of temperatures. CO HC1 HBr HO 8 CO* H.374 10. (54. J.955 2.687  4.3697 0.571 9.210 3.077 6.704 10.385 5.974 1.423 6.100 5.189  0.4325 0.947 6.830 6. see  0.253 1. usually within 1 per cent or less. D$ X 10* y X 10 a X 10 O 2 Nj Clj Br.974 6.103 9.017 0.732 6.200 0. DEO. For more accurate values and data for other Because of the variation of heat capacity with temperature..576 8.578 7. The mean heat capacity Cp in the temperature range from Ti to Tt is given by 2 ^r and if Xr _. Bryant. Tf. 820.317 2. * 6.25) It is then possible to calculate the mean heat capacity of any gas.537 7. CpdT 7p 1 > L 2 i the value of C P from equation (9.405  1. when inserted in equation (9. see also. i Spencer.396 6. Chem.965 0.515 13.24) they give the heat capacities of the respective gases. constants in Table II. .. 1022 (1933). Am. TABLE II.1 ft 1 ATM. The values of these constants for a number of common gases are recorded in Table II *.4808 0.449 7.S HCN NaO SO SO S NH.219 6.529 6. Soc. 67.24) is introduced. in the temperature range from 273 to about 1500K.) + tr(T! + ^jT 2 + H) + . 56.836 0.
be obtained upon multiplying the mean heat capacity Cp as given by equation (9. Am. 54. 8. Chipman and Fontana.24)..095 3 6 1 1 . Mines Bull. .. U. deg. The same result can.24) will be used whenever possible.017 X X (300) ] 10<t(400)  6. ft and y being quite different from those in Table II. Chtm. is obtained by the integration of equation (9.27) constant pressure being understood.. 2 #400  ffwo t/300 (6.300 K.253 X lO" ^ .54 HEAT CHANGES AND HEAT CAPACITIES 9g is It appears that in certain cases the variation of heat capacity with temperature better represented by a function containing a term in T~* in place of T* in equation (9. equation (9.yT~*> (9. see also. i.017 X lO" ^ cal. The difference in the * Maier and Kelley.253 X  10~3 [(400) a 1. Soc. the simple power series equation (9. using (9.. and hence the righthand side of equation (9.16) takes the simple form ' (3E/dV) T is zero for an (9 28)  The quantity (dV/dT)p represents the rate of increase of volume with temperature. it follows that CP = 6.24) to express CP as a function of T\ the result is )dT 9 T?) + . is C required to raise the temperature of 1 mole of at 1 atm.a + &T . The heat required to raise the temperature of a system from TI to T.. 8243 (1932). the increase of heat content. ideal gas. at constant pressure.26) the constants a.095 + 3.11). by the increase of temperature. however.017  8 X  (300)'] 710 cal mole"1 . pressure? + 3. thus.moleand since Ti is 273 + 27 . Problem: How much heat oxygen gas from 27 C to 127 From Table II. Chem.253 X 300) 10"8 !T i 1.e. 371 (1934).095(400  + i X 3. at constant pressure. it will be found necessary to employ a function of the type of equation (9. Am. Bur.28) may be taken as equal to the work of expansion when the temperature of the ideal gas is raised by 1 at constant pressure.' CP . of course.1. Since 9g.26) can be regarded as representing exactly the dependence of heat capacity on temperature. In some instances. because of its more straightforward nature.400 K.26). /. Difference of Molar Heat Capacities. 57. 48 (1935).24) nor (9. and T is 273 + 127 . (9. Since neither equation (9. Sac. /. Keiley.25).
as shown by equation (9. and hence. in addition to that due to the work of expansion. whereas if the . 10. w. dE may be replaced by C vdT. P represents. thus differ by a constant amount. 1. at constant volume there is. However. it is seen that (dV/dT) P is equal to R/P. between CP and CV must include an allowance for the change in energy content due to the increase of volume. dE is equal to pansion. although the discrepancy should not be large.1) It will be observed from this result that in a reversible.29) where CP and C v are now the molar heat capacities of the ideal gas. deg. at any For every infinitesimal stage of the process q is zero. (10.C v  . If the work is restricted to work of exequation (7. ADIABATIC PROCESSES Expansion and Compression.. the temperature must fall.22).5). except perhaps at high pressures and low temperatures when departure from ideal behavior is considerable. so that under these conditions P is the pressure of the system. and hence so that from equation (9.. In this equation. i. An adiabatic defined as one in which no heat enters or leaves the system. respectively.~* For real gases CP mole"" 1 Cv will not be quite equal to R. the external pressure.987 cal.27) CP . w is given by PdV. Reversible Adiabatic is process dE . by stage. equal to the molar gas constant. i. since the energy content is independent of the volume. if the adiabatic process is carried out reversibly.PdV.. strictly speaking. (9. . this calculation is based on the tacit C. Actually this is quite small for most gases Under ordinary conditions as is apparent from the value of the mechanical equivalent of heat derived in the problem in 6b. as a result of the increase of volume at constant pressure.1Q* ADIASATIC PROCESSES 55 heat capacities of an ideal gas at constant pressure and constant volume may thus be attributed to the work of expansion. thus. so that lOa.e. assumption that (dE/dV)r is zero for air at Since for 1 mole of an ideal gas PV = RT. the actual pressure of the system is virtually identical with the external pressure ( 8a). if the volume of the gas is increased.e. of course. no work of expansion. so that CvdT   PdV. adiabatic process the signs of dV and dT are opposite. The values for constant pressure and constant volume. Further theoretical consideration of this subject will be given in Chapter VIII. For an ideal gas. in such an^adiabatic expansion. for an ideal gas. B. It will be understood that this condition can hold only For real gases the difference if (dE/dV)r is zero.
and as no heat enters or leaves the system. the energy content of the gas must decrease. Assuming ideal behavior. volume so that substitution for P in equation (10. The equation (10. and Vi and V*.4) pacities at constant pressure or its equivalent.3) For 1 mole of an ideal gas.R In ^ . and taking Cv for air as 5 cai. If 1 mole of the gas is considered. lationship between the pressure (or volume) and the temperature of an ideal gas in a reversible. (10. R is equal to CP CV. Problem: A quantity of air at 25 C is compressed adiabaticaliy and reversibiy from a volume of 10 liters to 1 liter. be expected from general considerations: a gas does work when it expands. after making this substitution and converting the logarithms. Since the energy is independent of the volume at constant temperature. Temperature Changes in Reversible Adiabatic Processes.R In Kl K 2 (10. in a compression.29). it is possible to integrate equation (10. adiabatic process with an ideal gas.2). PV is equal to RT. so that. by (9. deg. the corresponding volumes.5) or TV~ = TVRICv = l constant. . the initial and final temperatures. the limits being T\ and T%. equation (10.1) gives CvdT =RT~> dV dT^^dV that is C vd In T = .3) becomes 'Cp = where the symbol 7 is (7 l)log^.56 HEAT CHANGES AND HEAT CAPACITIES 10b This is to is decreased. (10. adiabatic expansion or compression may be derived in the following manner.4). the temperature will rise.2) where CV is the molar heat capacity of the ideal gas at constant volume. used to represent Cp/Cv> the ratio of the heat caand constant volume. The relOb.~ x mole"1 . the result is CVln ~? Jtl . this decrease of energy is accompanied by a fall of temperature. can be utilized to determine the temperature change in a reversible. ' * ' \RICv (10.Rd In 7. If Cv is assumed to be independent of temperature. calculate the (approximate) final temperature of the air.
+ .5) 1 .7) pycpicv = constant. is 1 liter.0 cal. hence. it is found that fall of The marked P or 1 V\ = l\Vl or PiFF r/Cr = P*VS flCv . Since an ideal gas is under consideration.5) so as to eliminate Vi and it is found that iRICp or T The results of equations (10. For many purposes it is more useful to develop an expression relating the temperature to the pressure in a reversible.0 cal.IOC Utilizing equation (10. (10. 25 = 298 K. . lOc. Pi is 200 atm. calculate the temperature.. 1 F. ADIABATIC PROCESSES 57 is T l is 273 Cv is and sufficient accuracy (note that T* 298 R may be taken as 2. The final temperature is thus 154  273 ~ 119 C. be summarized in the . 5. mole*" 1 with same units). * 1 i Problem: quantity of air at 25 reversibly from 200 atm.0 cai. Since In this case 1\ is 273 Cv = #i as for Cv was given above as 5. convenient form P2 = 1 r2 = 1 Vi lo log logTT p g^r 1 1 K V2 Lp CK . By combining equations (10. deg. deg. deg. temperature accompanying adiabatic. T and = constant.0 cal. temperature is thus 749  273 = 476 C.6). deg. by equation (10. adiabatic change. jr 2 = "" / 20 \ 200 298 7 T 2  298 X (A) 2/7 = 154 K.~ l mole" 1 and assuming CP an ideal gas.6) so as to eliminate T\ and 7^.5) and (10. (10. _ 10\ T2 = The final V / 298 X 10 2/6 T = 749 K. Vi 10 liters. (approximate) final A C is Assuming allowed to expand adiabatically and ideal behavior. it follows that P\Vi = RT\ and P 2 V z = if these equations are combined with (10." Cv and R must be expressed in the / + 25 2/ft '  298 K.6) may .Volume Relationship in Reversible Adiabatic Process. and P 2 is 20 atm.5). or approximately adiabatic."" 1 mole" 1 Hence." 1 mole^ 1 . to 20 atm. . Cp is 7. Pressure. expansion is used to some extent for cooling purposes in connection with the liquefaction of gases.
That is to say. Work of Expansion in Reversible AdiaVolume batic Process. adiabatic process The pansion. to 5.2). is given by equation (10. Alternatively. that is.2). constant. The work of expansion w in an FIG.1) as CydT. will be steeper for an adiabatic than for an isothermal process.8)... is WIf /Kt I PdV = it /r 1 CvdT. Equation (10.0 atm.. the pressurevolume curve (Fig. the increase of volume for a given decrease of pressure will be less in an adiabatic than in an isothermal exversible.9) '(K) [/Pi\* * J> The anumption made ia capacity in the integration of equation (10. Since CP is always greater than CF.0 atm. of course. substituting the result in (10. which may be compared with the constancy of the simple product PV for an isothermal process. which will tend to In the isothermal prodiminish the volume. as explained above. adiabatic prostage isothermal processes cess.8) it is readily found that This problem /Cjp l (10. is greater than unity.58 HEAT CHANGES AND HEAT CAPACITIES relationship between the pressure 10d and volume at any instant in a rewith a given mass of an ideal gas * is thus represented by PVt constant.8) The negative sign means that work is done on the gas when T* an adiabatic compression. lOd. that the heat independent of the temperature.e. starting at the same point.8) > Ti. derived from equation (8. hence. The reason for the smaller volume increase in an adiabatic expansion is to be attributed to the accompanying fall of temperature. i. cess.6) with (10. respectively. the plot of the pressure against the volume. namely.c v (T  (10. i. (Compare the problem in 8b. TI being known. The molar heat capacities may be taken as equal to those of air. so as to eliminate Ti and T 2 and obtain expressions for the work of expansion in terms of the volumes or pressures. PdV. the temperature is.4) or (10. may be combined with equations (10.) and then may be solved by calculating T 2 as in the second problem in lOb. . Adiabatic and infinitesimal of a reversible.e.6). should be borne in mind. y. JY JT\ follows that l Cy may be taken as constant.. the ratio Cp/Cr. 7). i. by combining equation (10. for an appreciable process the total work of expanequal to sion W.c v (T* . Problem: Calculate the work of expansion in ergs when the pressure of 1 mole of an ideal gas at 25 C is changed adiabatically and reversibiy from 1.e. w in . which is for an isothermal expansion between the same pressure limits. 7. hence.ro .
the stopcock is allowed to remain open after the adiabatic expansion. Clement and C. and F 2 rises to PJ. During the expansion.  5 \ 2' 7 1 for the adiabatic process is seen to be somewhat less numerically than for the isothermal expansion. The results obtained in the preceding sections the ratio of the heat capacities have been applied in determining the value of In the method of F. and (10. Pi . Since the corresponding pressures PI and P% are known. the stopcock is then immediately closed. with TI = 273 25 298 K.0 X 4.12) are both based on the assumption that the gas behaves ideally. deg. hence. the result is W W . where (10.. therefore. R may be taken as 2. P\V1 = PjVJ. + . the ratio of the heat capacities can be calculated. .7) (10. and the temperatures before (T\) and immediately after (7^) expansion are measured by a sensitive thermometer. the result 7 log log P!P t log PI U U ' ' From the three pressure measurements. at the same temperature. The from which will be that of the factor CV. The initial pressure Pi is observed. deg. which is virtually adiabatic. the gas is cooled from the initial temperature T\ to the lower value T 2 and as it warms up to its original temperature.0 cal. the pressure If V\ is the volume of 1 mole of an ideal gas at pressure Pi. it follows that .106 ADIABATIC PROCESSES 59 can be derived directly by means of the available data.~ l mole' 1 . and since 1 mole still occupies the volume V 2 because the vessel was closed after the expansion. this is 5. because of the smaller volume change. B. Lummer and E. for actual gases. the lefthand side refers to the initial state final state. Ratio of 3. Desormes (1812).1.0 atm. log (Pi/p)  log It will be recalled that equations (10. however.18 X 10 7 ergs deg. Heat Capacities. .10).6) in the form log ft log P.5. . Pringsheim.0 and CP as 7. pressure greater than atmospheric is placed in a large vessel provided with a stopcock and a manometer for indicating the pressure. is and the righthand side to the Eliminating V\ and V* from equations log P. Substituting these values in equation (10. the adiabatic expansion. the gas at a of a gas.9).64 X 10 10 ergs mole" 1 [/ j^j 1 ( . the results must be corrected to ideal behavior by the use of a suitable equation of state.7).0 and Pa .. 1891). % . is the volume after the adiabatic expansion when the pressure is P 2 then by equaWhen the original temperature T\ is restored. y can be obtained from equation (10. Pin = p. the pressure of the gas is P(.n. In a modification of the foregoing procedure (0.1 mole'1 immaterial as long as they are consistent.~l mole" 1 or energy unit of In the exponent the units of R and C v are 5.0 cal.The work required lOe.10. after tion (10. and the stopcock is opened to allow the pressure to fall to that of the atmosphere P*.11) and (10.
g.50 of the heat capacities decreases with increasing temperature. This matter will be explained in Chapter VI.41 100 1.60 HEAT CHANGES AND HEAT CAPACITIES For an ideal gas. . e.c 21d). a useful approximate rule for ordinary temperatures and pressures. The tube was made of a material having a low heat conductance.. 2. for the volume is increased by F 2 at the pressure P 2 while decreasing by the volume V\ at the pressure PI. it follows that the loss of energy from the AZ? system in the form of work.67 for monatomic gases. such as water. i. it varies appreciably with pressure and temperature. so that Q is zero.65.2).403 1.60  79 C 1. Since the whole process is assumed to be adiabatic. By the use of the throttle the expansion took place slow1 and the pressure on each side of the Fro.53 1. As the pressure is increased y increases.e. and the conditions were made as nearly adiabatic as possible. It may be noted that the heat capacity ratio for hydrogen gas increases at low temperatures toward the value for a monatomic gas. 8. for air at 79 C the maximum was observed at 150 atm. but for real gases. by equation (7. W. pp.45 100 2. THE JOULETHOMSON EFFECT lla. the ratio TABLE III. the value of y should be constant. must be equal to the decrease in the energy content. In the experiments of Joule and referred to in 9d. W 1 Data mainly from International Critical Tables.401 1. 1... the corresponding temperatures are T\ and 7V The volume of 1 mole of the gas at PI and The work done Ti is Fi. and P 2 ^ the constant pressure after the passage. ammonia and methane. 8182.20 1. other than monatomic. boxwood. Thomson. When actual data are not available.77 1.83 1. 200 atm. whereas at P 2 and T2 the molar volume is F 2 by 1 mole of the gas as it streams through the plug is equal to P^Vi PiFi. Expansion Through a Throttle. 9 In general. Vol. carbon dioxide. Throttled expansion of a gas plug was maintained virtually constant. passing through a maximum and then decreas^8 (cf.30 for simple polyatomic gases. 8). V. as shown by the results for air. VARIATION OP RATIO Cp/Cv FOR AIR WITH TEMPERATURE AND PRESSURE Pressure 1 Temperature 50 1.40 for diatomic gases. a gas was allowed to stream from a higher to a lower pressure through a tube containing a "throttle/' consisting of a porous plug of silk or cotton (Fig. If EI and E* are the energy con T2 ^ . given in Table III. 11.33 1. Suppose PI is the constant pressure of the gas before passing through the throttle. is to take y as 1. but at O and 100 C it occurs at higher pressures than are given in the table. 1.
a system is For a process in which the heat content is constant.4) is equivalent to ' (1L5) . lib. equation (11. /d(PF) . i.lib THE JOULETHOMSON EFFECT and final states. By rearrangement of equation (11. PiVi E* 2 2. by definition.e. this expression takes the form and since E is a function of P. 61 before and after tents of 1 mole of the gas in the initial passage through the throttle. so that in +PF the heat content H is equal to E + PV.1) the lefthand side representing the decrease of the energy content. so that (11. of content of the system remains constant. so that dH is a complete differential. thus. it is equal to the rate of change of temperature with the pressure in a streaming process through a plug or throttle. it follows W\ _. and the righthand side the work done.2) that Hi = H*. so that. According to equation (9. Cp. .. The JouleThomson Coefficient.11 KN Utilizing the relationship H = E + PV..1). then  (E. The quantity (dT/dP) a is called the JouleThomson coefficient. or ()().P2 7 2  Ptfi. it is seen that Ei and since.11).e. from (11. (3H/dT) P is the heat capacity of the gas at constant pressure. +  (11. from equation (4.EJ . i. the heat content determined precisely by the thermodynamic state of the system.. and is represented by the symbol MJ./().T. taking pressure and temperature as the variables.9) that V and T 9 which are not independent. (11.3) may be to indicate constant heat equated to zero. inserting the subscript H content.2) it follows the throttled expansion process the heat As seen in 9a.
it is seen from equation The JouleThomson coeffi(11. but it becomes positive at high pressures.5). therefore. (dE/dV)r is zero. (dE/dV)r has the dimensions of energy/ volume. will have a positive value. at low pressures. a JouleThomson (throttled) expansion. it follows that the first term in the bracket on the righthand side of equation (11. as in Fig. except hydrogen and helium. term in the equation of state for the real gas. unlike that of an ideal gas. for an ideal gas.* for its of thermodynamics without assuming any specific properties of the system. gas or liquid.. 22a).T. and these all show that (dE/dV)r is usually positive Further. Turning to the term [dCPF)/dP]r. in fact. 2 it has. it may be regarded as a measure of the pressure in the interior of a fluid.e. since increasing pressure. .6) that for an ideal gas MJ. i.e. since (dH/dP) T is zero for an ideal gas (cf. . is equal to MJ. Hence. hence. There are several methods for obtaining an indication of the magnitude of the internal pressure. liquid or gas. but they are usually employed for gases. since it is approximately equal to a/F it increases with increasing pressure. it is seen that this is the slope of the for real gases. does not necessarily approach zero at very low pressures. on the other hand. especially in connection with liquids. it follows that the JouleThomson coefficient In other words. is invariably accompanied by a decrease of volume. frequently referred to as (11. 2. in spite of the fact that (OE/dV)r approaches zero and PV approaches RT (cf. or analogous.6) are negative. and since PV = RT. At low and moderate pressures. readily seen from an examination of the pressurevolume isotherm of a gas that the numerical value of the slope (dV/dP^T is large at low pressures. been identified approximately with the a/F term of the van It is the because der Waals equation (cf. this is negaplot of tive for all gases. since CP is finite.T. Physically. 20d).4) or (11. 2 against P. resulting from the attractions and repulsions of the molecules. must be zero. t The quantity lie. 9e). is not independent of the volume. so that there should be no change of temperature when such a gas expands through a throttle.6). However. i. most a decrease of temperature as the result of gases experience (dT/dP)n. that it is 2 necessary to introduce the a/F . At ordinary temperatures. and diminishes as the pressure is increased. PV both terms in the bracket of equation (11. it is. fThe same conclusion may be reached directly from equation (11. its numerical value being approximately independent of the pressure. at moderate and low pressures and * The foregoing equations are really applicable to any fluid.f cient of an ideal gas should thus be zero.6) is quite general derivation based entirely on the first la\y the internal pressure. which is equivalent to force/area and hence to pressure. is always negative.T. therefore. since MJ. t It may be noted that for real gases MJ.T. The factor (dV/dP)r in equation (11. it follows that td(PV)/dP^r is also zero.6) is usually negative. and since the heat capacity Cp is always positive. Sign and Magnitude of the JouleThomson Effect.62 HEAT CHANGES AND HEAT CAPACITIES Equation is lie and should apply to any gas. as seen earlier.. at constant temIt can be perature. energy content of a real gas..
there is evidently an inversion tern 100 and 150 C. 43. with increasing pressure. 287 (1930). Arts Sci... effect see JouleThomson . 785 (1934). derived from the purely thermodynamic equation (11. actually about 126 C. Thomson effect should be observed. 64. J.. 48. under these conditions a throttled expansion will be accompanied by an increase of temperature. From what has just been stated^the inversion temperature for any gas should increase with the pressure. 4 At 200 atm. 45. .. 46. that the value of the JouleThomson coefficient passes hightemperature through a maximum as the temperature is changed. Sage. is thus to be expected. the numerical value of the first term in the bracket remains approximately constant. pressure. at this temperature MJ. Am. as may be seen from the data for nitrogen recorded in Table IV. GOi.6) in conjunction with experimental data on the compressibility of gases. passing through a zero value. Eng. but it deperature between It will be observed.. just above 200 C at 200 atm. especially at the creases with decreasing pressure. the coefficient MJ. It follows.T. higher pressures. Phys. Chtm.. and higher pressures will be required before a reversal occurs. and finally changing At sufficiently high pressures. zero. inversion point. such inversion points have actually been observed. Ind. should increase as the temperature is diminished. Lacey. The temperature at which the JouleThomson effect changes sign.v. At lower temperatures not only larger at is the numerical value of [jd(PV)/dP~]T low pressures. that at low pressures the JouleThomson coefficient MJ. Chtm.llC THE JOULETHOMSON EFFECT 63 ordinary temperatures. 715 (1936). 400 (1942). 240 (1939).. for other determinations of the Roebuck. a reversal of the Joulesign. 4 Roebuck and Ostqrberg. 60 (1933). A Rev.T. Proc.T. 369 (1939). 28.g. 55. but higher pressures must be attained before it changes sign. are in complete agreement with direct observations of the JouleThomson effect.. This subject will be considered more fully from another standpoint in 22b. et aL. becoming negative. 60. at the same time the second term decreases numerically. Soc. 8. 31.. 450 (1935). Phys. PA. at a given pressure. Acad. The foregoing conclusions. is called the inversion temperature. therefore. and eventually becomes This means that the JouleThomson coefficient should decrease positive. 322 (1934). 627 (1940^ J A tn Chcm. therefore. et a/. 64. of course. Rev. e. As the gas pressure is increased. is. 537 (1925).
e. is about 0. This means that the (upper) inversion temperature for below the ordinary atmospheric temperature at all as compared with that of other gases at normal temperatures. is The difference in behavior exhibited by these gases. therefore. and consequently the JouleThomson coefficient is negative under these conditions. At sufficiently low temperatures. hydrogen and helium behave like other gases. and preferably at low pressures. Utilizing . Because of the variation of the JouleThomson coefficient with both temperature and pressure it is not easy to calculate the change of temperature resulting from a given throttled expansion. in the pressure range of 200 3. even when such data as in Table IV are available. It is now approximation. Effect of Pressure on Heat Capacity. to 1 atm. at suitable temperatures and As seen above.) means a fall of temperature of 28. can thus be accounted for. This is seen to be about atm. pressure. some indication of the fail of temperature can be obtained. it decreases and eventually changes sign as the pressure hydrogen and helium pressures.155 atm.T.64 HEAT CHANGES AND HEAT CAPACITIES For hydrogen and helium the value of lid PV increases with pressure at all [d(PF)/dP]r is pressures.\ _ ~ ffg . Cooling by the JouleThomson Effect. to 1 atm.~ l so that the decrease of pressure by 199 (approx. however. and hence the order o* differentiation on the righthand side of equation (11.14 atm. Since Cp is equal to (dH/dT) P . By estimating a rough average for the JouleThomson coefficient. 200 atm.. The fall of temperature that lid. \dP The heat content dynamic of a simple state.0 C. Problem: Estimate the final sion of nitrogen.valued function of the thermotemperature and pressure. and hence the cooling accompanying the expansion will be most marked.~ . so that the fall of temperature is 31. leading to a final temperature of . As a first 3. to 1 atm.0 C.7) is immaterial. of the )T BTdP ( ' system is a single. at ordinary temperatures. by a series of approximations. An examination of Table IV shows that at 25 C. positive at all pressures. at low temperatures. J it lie. is increased. the temperature of the gas to be liquefied is first reduced either by the performance of work in a gas engine.g. from 200 atm. and temperatures of 25 to 0.T. follows that the variation of the heat capacity with pressure. where it undergoes something approaching adiabatic expansion ( lOd). In order to obtain the maximum efficiency. given by (dC. . therefore.6 C. the JouleThomson coefficient has the largest positive values. the final temperature is seen to be possible to estimate a more accurate value of MJ. occurs when a gas undergoes throttled expansion. thus. This can be done. hajs been utilized in the industrial liquefaction of gases. pressures. at constant is temperature. having a positive value for the JouleThomson coefficient at moderate and low pressures. the mean value of /XJ. in the range from 200 atm. or by utilizing the cooling effect of another portion of the gas which has been passed through a throttle. initially at 25 temperature accompanying the throttled expanC.
2 1 deg. From Table IV.. 1.1. therefore.atm.mole .5 X 10~8 atm. at ordinary temperatures and pressures..81 X 10. and (dnj.mole.mole" for an increase of 1 atm./dT)p are both zero.45 1. The heat capacity cal. By combining equations ..5 x io X 10~ 2 1 1 1 deg. 2 1 deg.5) and (10. At about 300 K.1 and (dm. ..t. it is seen that ..lie equation (11. of nitrogen should thus increase by approximately 1. ^ = d* IP ) x 10~ 3 cal.8). when 1 mole of a diatomic gas at C expands from 10 ml. it EXERCISES follows that 65 (dCP \ \dP = \JL(*!i /T giving a relationship for the variation of heat capacity with pressure which is For an ideal gas /XJ. to 1 liter. = ~ T 1. Determine the work done in literatm. 2. that the heat capacity does not vary with pressure.5).18). in the pressure.." 1 mole" 1 1.8) derive an expression for the work of reversible.41 + X 1. From data on the variation of the JouleThomson coefficient and heat capacity with temperature it is thus possible to determine the variation of the heat capacity of a fluid with pressure. this conclusion is in agreement with that reached in 9e.mole . deg. at ordinary temperatures and pressures is seen to be about 0. From Table II. adiabatic expansion of an ideal gas in terms of the initial and final volumes. at ordinary temperatures and pressures.1 if these results are inserted into equation (11. x 10 ~8 + 6 87  x 1.mole. therefore.21 atm.81 X lO'T cal.T.36 .87 cal. (10. for nitrogen CP = 6.T. MJ. CP = ( \ 6. ~ P 10~ 3 X 0. Problem: From the data in Tables II and IV estimate the variation of the molar heat capacity of nitrogen with pressure./dT)p is approximately . The subject of the influence of pressure on heat capacity will be con21d.0  21 x L36 cal.0 X 10""2 1 1 deg.T. so applicable to all fluids. 1 1 deg.. This procedure has been utilized in certain instances.41 X  10~3 !F 2  0. sidered from another thermodynamic point of view in EXERCISES Give the complete derivation of equation (9.7 !T2 7 cal.
and the final temperature in the reversible. the specific volume of the vapor is then 1675 cc. 500 and 1000 C. adiabatic compression of 1 mole of oxygen from 10 liters to 1 liter. the gas being allowed to regain its original temperature between the two stages. The heat of vaporization of water is 539 cal. is given by 8. Suggest why the value of &E in this case is sometimes called the "internal heat of vaporization." 11.0 atm. Chapter 1 III. and AJ57 for the vaporization of 1 mole of water 10. pressure. 13.~l. 12. the density of water at 25 C is 0. A the initial AH .9971 g. to 25 atm. must be supplied to 100 g." 1 and that of the liquid is approximately unity. of carbon dioxide in order to raise the temperature from 27 C to 727 C at 1 atm. ja 1 deg. deg. pressure? 7.001 cal.00 atm. the heat capacity has been assumed to be independent of temperature.16) and the result derived in Exercise 11. Which process can be carried out with the smaller expenditure of energy? 9. Calculate the (approximate) increase of internal energy in calories when mole of carbon dioxide is expanded isothermally from 1 liter to 10 liters. its temperature is observed to increase from 25 to 200 C. reversible expansion from a pressure of 1. show that the increase of the energy content in the isothermal expansion of 1 mole of the gas.~ x at the normal boiling point. 6. to 5 atm.) . from 5. show Cv for a gas such as nitrogen should pass qualitatively that the value of CP through a maximum as the pressure is increased (cf.0 X 10~< deg. The mean heat capacity of water may be taken as 1. With the aid of equation (9. from 1 atm. Assuming (dE/dV)T for a van der Waals gas to be equal to a/7*. Compare the values of at 100 C and 1 atm.66 HEAT CHANGES AND HEAT CAPACITIES 3. Correlate this result with the analogous term in the expression for W in Exercise 8. in calories. Evaluate the amount of heat in ergs which must be supplied to an ideal gas in the isothermal. (Note from Fig. Compare the results with the mean heat capacity in the range to 1000 C. . g. Calculate the molar heat capacity at 1 atm. 4. assuming van der Waals behavior.6)? (The gas may be assumed to be ideal in other respects. under such conditions that no work is done. When a gas is compressed adiabatically to half its initial volume. What would be the result if Cp were taken as having the constant (mean) value of 7 cal. Determine the values of and &E in calories when 1 mole of liquid water heated from 25 to 100 C at 1 aim. How could allowance be made for the variation of CP with temperature in equation (10. In the treatment of adiabatic processes in the text.*.~* and the mean coefficient of cubical expansion as 4. Estimate the (approximate) mean molar heat capacity of the gas at constant pressure... 21a). at 25 C. 2 that (dV/dT)p is larger at low pressures and smaller at higher pressures than for an ideal gas. pressure. g.) Use this method to estimate the work done. pressure of nitrogen at 0. cc. to 25 atm. The compression may be carried out in one stage or it may be performed in two stages.. to 25. temperature being 25 C. and then from 5 atm. in calories.~* g.~* mole"" ? AT diatomic gas is to be compressed adiabatically from 1 atm. How much heat. the initial temperature being 25 C.
00107 cal.010 atm. 21e). as in Table III (cf.0072IT. 1 / ~ b JouleThomson coefficient of a van der Waals gas at moderate pressures Show that for a real gas. 1 with P in atm.5) to derive an expression for CP CV at the JouleThomson inversion point. Rev. Exercise 11). the variation of Cp for carbon dioxide with pressure is represented by CP  8. at not too lie that the first term in the high pressures. atm. 1 atm.90 + 0. hence. At 25 C. pressure. .""1 ). What is the value for a van der Waals gas? 16. is given + 19. . i 138 3 ' 319. show that (dH\ _ 2a \dPJT~ and hence derive the result RT' 2a = for the (cf. Phys.~l atm. 17. .50 + 0.. Show that for a van der Waals gas (dE/dV)r is proportional to P1 (cf.~l CHoxton. The variation of the JouleThomson coefficient of air with the absolute temperature T at 1 atm."1 mole"1 in the region of 27 C and 1 atm. 1 l deg.08 atm.  ninT* 0.1975 + y^~ deg.0123P*. sarily zero even at zero pressure.80 0. Chapter II. If a is independent of temperature.. and the variation with temperature.EXERCISES 67 14.0 . the JouleThomson coefficient of the gas is 1. is given approximately by The dependence 1 of CP on temperature at . (The experimental value is about of pressure. and the van der Waals equation in the lowpressure form obtained in Exercise 7. the JouleThomson coefficient is not neces22a). By utilizing a relationship of the form of equation (4. together with the result of Exercise 11.9).""1 . atm. show that __ dPT~ RT By introducing and dP r RT H = E + PV. CP 6. Use the results of Exercises 11 and 13. justify the statement in bracket on the righthand side of equation (11. deg.~ mole Determine the rate of change of CP for air with pressure in cal. and (dV/dP)r is approximately proportional to 1/P1. pressure.T. pressure. and that both CP and Cp/Cv should pass through a maximum with increasing pressure.0343P + 0. 15. show that Cy for a van der Waals gas should be independent of the pressure (or volume) at constant temperature.T.6) is approximately independent In the vicinity of 1 atm.18) and (11. Combine equations (0. with temperature at ordinary pres0. 13. at (approximately) by CP = 6. 438 (1919)]. sures. 18. pressure is given by MJ. Determine the rate of change of MJ.
25 C. Heat of reaction or = Heat content of products ff (products) Heat content of reactants. the data are quoted directly Alas. and pressure. e. is equal to Afl>. especially since. values all refer to a specified temperature. and vice versa. This practice is invariably adopted in making thermochemical measurements. allowing for the different numbers of molecules that 9 H 68 . Heat of Reaction.e. The summation signs imply that the total heat contents. the heat absorbed in any process at constant pressure. heat content. it deals essentially with the conversion of chemical energy into heat energy. thus. e. as will be seen shortly.g. This is the quantity usually referred to as the heat of reaction. where the i. in other words.. determined only by the initial and final states of the system.g. the heat change has a definite value.CHAPTER V THERMOCHEMISTRY 12. as seen in 9a. Thermochemistry is. The heat change associated with a chemical reaction... the subject is based largely on the first law. However. with the heat changes associated with chemical reactions. It is for this reason that heat changes of chemical reactions are measured under constant pressure or constant volume conditions. the situation is considerably simplified by determining heat changes for the condition in which all the substances concerned are at the same temperature. Further. HEAT CHANGES IN CHEMICAL REACTIONS The science of thermochemistry is concerned 12a. (12. whereas combustion reactions are carried out at constant volume. if the process is carried out at constant pressure or constant volume. to be regarded as a branch of thermodynamics.. the increase of heat content at constant pressure ( 9a). in an explosion bomb. therefore.1) QP = Affp =  e. the heat change accompanying a chemical reaction under these conditions is equal to the difference between the total heat content of the products and that of the reactants. those for constant pressure. generally 1 atm. like that for any other process. processes involving liquids and gases are usually studied at constant (atmospheric) pressure. the data obtained in thennochemical studies are utilized in the evaluation of properties of thermodynamic interest. Since Qp. though the reactants and products of a chemical reaction might well be at different temperatures. 1 atm. For the purpose of recording and tabulating the results. or are converted into. is an indefinite quantity depending on the path taken.g. at constant temperature and pressure. #(reactants).
the symbol aq is employed.e. I and s indicate gaseous. dilute that the addition of further solvent. because the statement of the result in calories would suggest a greater degree where the symbols = of accuracy than has actually been attained. the observed heat change is adjusted so as to give the result that would have been obtained for the complete reaction..7 kcaL.700 cal. 12b. proceeds to completion.16 K. viz. strictly speaking.7 kcal. results in no appreciable change in the heat of reaction.. in general. liquid and solid state. s) + #(3H 2. e. respecis the It common practice in thermochemical work to express heat tively. Unless otherwise stated. of all the products or of all the reactants. presThe heat content of 1 mole of liquid benzene is thus 11. 0)] = 1L7 kcal. 2 Atf 298 = 13. that is. as represented by the appropriate chemical equation. Symbols and Units. 8C() + 3H 2 (0r) = CJffe. i. It may be noted. AH  tf (C 6 H 6. the value of AH would be independent of the pressure ( 9e). where 1 kcal. the difference between the observed value of AH at 1 atm. i.e. the reaction is accompanied by an absorption of heat..e. It may be remarked that in evaluating the heat of reaction it is assumed that the reactants are completely converted into the products. On the other hand. although for certain purposes it is desirable to express the data for the condition in which the gas behaves ideally. at 25 C or 298. about 11. ably less than the experimental error. is represented in the form of a thermochemical equation. abbreviated to kcal. water. at very low pressures. The heat change accompanying a reaction. it is postulated that the reaction. respectively. and so may be ignored (cf. than that of the carbon (solid) and hydrogen (gas) of which it may be re garded as composed.e..  [#(6C.50 kcal. if the reverse is the case. g.. thus. it is necessary to specify the conIf the solutions are so centrations of the various reactants and products. . however.. that if the heat content of the products exceeds that of the reactants. to specify the pressure in connection with any reaction involving gases. AH is positive. lft  11. at 25 C. In the great majority of cases. i. and 1 atm. the heat of dilution is zero. but as this is not the case it is necessary. In other words. If all gases behaved ideally...12b HEAT CHANGES IN CHEMICAL REACTIONS 69 may be involved.NaCl(og) + H O.. for example. A# 298 . For a reaction taking place in solution.7 kcal. heat is evolved when the reaction takes place.. changes in kilocalories. If this condition is not realized experimentally. that between solid carbon (graphite) and hydrogen gas to form liquid benzene. The equation given above 1 of the formation of mole that benzene from 6 gramatoms of liquid implies solid carbon (graphite) and 3 moles of hydrogen gas results in the absorption of 11. the pressure is usually 1 atm. are to be included.g. 1000 cal. pressure and that corrected for departure of the gases from ideal behavior is consider20e)... so that AH is negative. i. greater sure. + NaOH(ag) .
3) is in the determination of the Aff values for combustion reactions. is invariably so small. which is the work of expansion when the process is carried out at constant pressure.3) this expression the value of the heat of reaction at constant pressure can be calculated if that at constant volume is known. or vice versa. therefore. Heat Changes at Constant Pressure and Constant Volume. gases. Bearing in mind these arguments. tions from the work of expansion. that it may be ignored.2) gives RTAn. without specifying constant volume conditions for the latter. therefore. Qp Qv + RTAn. The subjects of heat of solution and heat of dilution will be treated below (see also Chapter XVIII}. and not on the actual volume or pressure. If V is the volume of 1 mole of any (ideal) gas at the experimental temperature and pressure. for such a reaction. since Lhe actual thermochemical measurements are made in an "explosion bomb" at constant volume.2) may be neglected. so that PAF = PFAn = and substitution in equation (12. If n\ is the number of moles of gaseous reactants.3) can be written as QP AS + PAF ~ Q v + PAY. or approximately ideal. then the increase of volume AF in the reaction will be equal to FAn. (12. heat change Qv at constant volume is equal to &E V the increase of the energy content at constant volume ( 9a). it can be taken as being approximately true for all reacThe change in the energy content due exclusively to a volume change. particularly in apart comparison with the values of &E involved in chemical reactions. For a reaction in which gases take part. at constant temperature. equation (9. Although this is strictly true only if the gases involved are ideal. For ideal gases. For a reaction involving ideal. it is possible to identify Qv with AE at the given temperature. the volume change AF is usually so small that the PAF term in (12. the volume change AF may be appreciable. If the reaction involves solids and liquids only. The 12c. (12. An important use of equation (12.70 THERMOCHEMISTRY 12C for the reaction between hydrochloric acid and sodium hydroxide in dilute aqueous solution.2) which gives the relationship between the heat changes of a reaction at constant pressure and constant volume. depends only on the temperature. and n 2 is the number of moles of gaseous products of the reaction. that the value of AS. and no gases. It will be assumed. In cases of this kind the heats of reaction at constant pressure and constant From . The difference between these quantities is thus equal to PAF. and it* value can be determined with sufficient accuracy by assuming ideal behavior of the gases concerned. which is equal to Qv. PV is equal to RT. the process is accompanied by an increase of n% n\ = An moles of gas. AS would be independent of the volume.
law of thermodynamics. i. The reaction is CioH. but opposite in sign. thus. by equation (12.e.0 kcal. are based on the principle of conservation of energy.fo).2 kcal. has a definite value at a given temperature and pressure ( 9a). . compound is formed from in direct its elements. within the limits of experimental error. The law of Lavoisier and Laplace may be extended into the general form that the heat change accompanying a chemical reaction in one direction is exactly equal in magnitude. or 2 X QP = The  = 1. .0 +  (2 1. Lavoisier and P. equations the sign of A/7 is changed. perature is . provided foregoing conclusion. therefore. and hence QP and Qv are equal. and then decomposing it. equation (12. that the heat content of a substance. For any reaction in which the same total number the gaseous molecules only. Problem: When 1 mole of solid naphthalene was burnt in oxygen gas to yield carbon dioxide gas at constant volume. L. and R may be taken as 2 1 deg. . the heat absorbed (Qv) was found Calculate A// for this reaction. The total heat content of the reacting substances must.. The tem10~8 kcal. An = n 2 is 12.227. As a consequence of the thermochemical can be reversed.3). in which gases as well as solids or liquids take part. so that the number of molecules of gaseous reactants (HI) molecules of gaseous products (n 2 ) is 10.CH 4 (0) + 20.CO 2 (0) + 2H 2 O(Z). 25 C.227.80 kcal. ent of pressure. the quantity of heat which must be supplied to decompose a compound into its elements is equal to the heat evolved when the This experimental result is. or system. at 25 C. or vice versa. According to A. Thermochemical Laws. The factor An in equation (12. the value of AF for a reaction. hence. Two important laws of thermochemistry 12d. Ajff 298 Aff 298 . assuming it to be independto be 1. for otherwise it would be possible to create heat energy by making a compound from its elements.1)]. Since the volume changes due to solids and liquids are negligible."* mole" hence. and a numerically equal decrease of the chemical reaction []cf.0 1.12d HEAT CHANGES IN CHEMICAL REACTIONS 71 volume may be taken as identical.227.212. at 25 C. Laplace (1780). = 2. there is thus a definite increase Aff in one A/f in the opposite direction direction.2 X = 10~ 3 X 298 X  2) 1. 298 K. This conclusion follows directly from the fact. S. of gaseous molecules occurs on both sides cf the chemical equation An is zero.3) then refers to applies to the gases only.80 kcal.228.() + 120 2 (0) = 10C0 2 (0) + 4H 2 0(0. to that associated with the same reaction in the reverse direction.. differ from that of the products by a precise amount. value of A// for the reaction may thus be taken as 1.212. derived from the first law of thermodynamics. first agreement with the + 2O 2 (0) 2H 2 0(Z) .2 kcal.228. of course. and the number of HI cal.
the difference between these two states does not have any considerable effect on the value.8 determine the heat change of the reaction C 2 H4(0) f H 2 (00 = C 2 H 6 ((7) at 25 C. A useful practical applicarespectively. H (0) + 10fo) . the change of heat content AH AH AH is indicated by the symbol AHQ As an example of the standard heat of formation. however. on the initial and final states. One result of Hess's law is that thermochemical equations can be added and subtracted.72 THERMOCHEMISTRY I2e Another important law of thermochemistry was discovered empirically H.3 kcal. just like algebraic equations.05 kcal. as indicated earlier. When all the substances concerned in a reaction are in their respective standard states. and not on the intermediate states through which the system may have passed. Atf 298  32. C 2 H 4 (0) 2 2 2 2 2 2 6 2 2 2 AH = AH . it is known as the law of constant heat summation.. C H (0) + 3JO (0) . 12i). Where accurate thermochemical data are available. tion of this result is in the calculation of heat changes for reactions which cannot be studied directly. by This law states that the resultant heat change. G. The physical significance of these operations is that the heat contents of the various elements and compounds concerned are definite (extensive) quantities.2CO (0) + 3H 0(0. Hess (1840). when 1 mole of the substance is formed from its increase of heat content elements at a given temperature and pressure. so that K H. reference may be made to the reaction C() + Otto) = ' COsfr). The value of depends on the physical state and condition of the substances involved (cf. The required result can be obtained very simply by adding (i) and (ii) and subtracting (iii). the distinction between the two states is significant ( 20e). as already seen. the standard state is chosen as 1 atm. although in certain cases the ideal gas is postulated. The law of Hess thus also follows from the first law of thermodynamics for.3 372. A#g98 =  94. Heat of Formation. it leads to the conclusion that AH (or AE) depends only on the initial and final states of the system and is independent of the path connecting them. For gases. by a specific amount (or amounts).AH . and so it is generally postulated that the elements are in their socalled standard For liquids and solids. Problem: Given the following heats of reaction at 25 C: (i) (ii) (iii) + 30 (0) .H 0(Q. the standard states are usually taken as the states.fo) C 2H4 (0)  CJEUfo).8 kcal. . in a given chemical reaction is the same whether it takes place in one This means that the net heat of reaction depends only or in several stages. The heat of formation of a compound is the 12e. at constant pressure or constant volume.2C0 (0) + 2H 0(Z). and the addition or removal of a substance (or substances) from a system means that the heat content is increased or decreased. . stable forms at the atmospheric temperature and a pressure of 1 atm. 68. 337.
atom of graphite less carbon of of 1 mole and 1 mole of oxygen by 94. Heat Content and Heat of Formation. C 6 H Propane (g). 19231936. Prosen and Rossini. pressure.4 Methanol (g). etc. the gases. C 6H 6 COOH (s). PER MOLE Inorganic Compounds A/f Substance A// Substance Substance Aff HC1(0) HBr(0) . C0H] 2 (s). C H 4 Propylene (g). Pitzer and Rossini. CO(NH 2 ) 2 Benzoic acid (s). Kilpatrick.e. Chem. ibid. "The ThermochemisChemical Substances. For reviews of experimental methods. Z. 33.9 64. 1 .22. Taylor. 684 (1941). between the heat of a reaction. sec also.219 CO(0) PbSO 4 (s) Organic Compounds Substance A//  Substance A// C H8 Ethylene (g).6 64. are both at 1 atm. 18..3 SO 2 (0) SO(0) CO(g) 62 330 343 . Folkins and Miller. C H 6 Acetylene (00. 34.8 14.3 98. There is a useful connection 12f. Bichowsky and F. Kilpatrick. 38.42 94. Eng. 94 (1932).. 34.4 For further data.* STANDARD HEATS OP FORMATION AT 25 C IN KCAL. LandoltBornstein. sec Table 5 at end of book. at 25 C and 1 atm. 467 (1945). Pitzer and Rossini. i. 233 (1936). J.03 70.05 30. C 6 H 6QH Aniline (/).4 93. ibid.. Elek. CH 8OH Ethanol (g). 1 Data mainly adapted from try of the .05 kcal. Bur.4  C 6H NH 2 Urea (s). 45 335 (1939).32 NHtfo)  5. ibid. ibid.5 HgOM FeO() Fe 20.. The standard heats of formation of a number of compounds at 25 C are recorded in Table V.0 56.4 26.9 94.. in general. 36. . CioH 8  17. 34.6 5. D.195 380  21. at a temperature of 25 C and a pressure of 1 atm.3 79. Wagman.2 Sucrose Ci 2 H 22Oii  533. 263 (1945). Wagman. Rossini..06 .4 7. the standard state..3 104. PhysikalischChemische Tabeilen. 35. oxygen and carbon dioxide. Pitzer and Rossini. Prosen. 8 48.. C 2 H 6OH Ethanol (I) C 2 H 6 OH Phenol (s). 27. Res. 1 (1940).3 68." 1936.56 4.23 11. CH 8OH Methanol (/). R. for this is the stable form. 8 2 3 Methane (g). The standard heat of formation of carbon 94. Kilpatrick. TABLE V. .96 54.3 11. Thacker.3 66.82 12. CH 4 Ethane (g). C 2 H 6  Cyclohexane Naphthalene * (/). Nat. mole"" 1 The heat content dioxide at 25 C is then said to be dioxide is thus than that of 1 g.12f HEAT CHANGES IN CHEMICAL REACTIONS 73 Here the carbon is in the form of graphite.8. Pitzer and Rossini..05 kcal. 143 (1945)..7 14. Stand. and the heats of formation of the compounds involved. Chem. It will be evident that in thermochemical studies no F. Prosen. C 2H 2 Benzene (/). 403 (1945). Ind. 38. Roth. 559 (1946).1 57. see Rossini. Rev.(s) Al 2 8 (s) NaCl(s) KCl(s) AgCl(s) Hg 2 Cl 2 (s) .24 24.89 20.
For this reason it is permissible to choose any arbitrary scale of reference for heat content. i. provided they are expressed in the same units. which are based on variations of the heat content of a system with temperature.32 A//J 98  1. 2 X 68. the procedure may be reversed. the convention is to take the heat content of the system. irrespective of whether the actual temperatures are recorded on the absolute or centigrade similar situation scales. just as the zero of the centigrade temperature scale is arbitrarily chosen as the ice point. exists in connection with the heat content. 68. In this case. Consider.. provided the heats of formation of all the other substances involved are known. are expressed on an absolute irrespective of whether the heat contents The convention usually employed scale or an arbitrary. but only with regard to the differences of their heat contents. A H the formula.e.17.2 X 68. a zero of heat content may be chosen by convention.2 kcal.228. pressure at 25 C. it follows that on the basis of this convention the heat content of a compound is equal to its heat of formation. for example. CioH 8 () x * + 12O 2 fo) = 10CO 2 (0)  + 4H 4 2 0(0. Utilizing the heat contents derived in this manner.74 THERMOCHEMISTRY 12f information is obtained concerning the actual or absolute heat contents of substances. element or compound. by convention. the standard heat change of a reaction can be readily calculated from the known standard heat contents.05  (2 X 68. in thermochemistry is arbitrarily to take the heat contents of all elements as zero in their standard states at all temperatures* The heat of formation of a compound is the difference between the heat content of the compound and that of its elements.89 + 0) =  212. and the heat of formation of a compound derived from the heat of reaction.05 +  2H. it is CH 4 (<7) + 20*07) = 17. to be zero at C.80 kcal. of the substances concerned. The f (. and writing the standard heat + A#S 8 = [ 94. the reaction. the standard heats of formation.0(0. tion of 1 Problem: From the result of the problem in 12c..32 of formation at 25 C of each species below seen that the total heat content of the products is 94.32)] .89 standard increase Aff of heat content in the reaction is thus given by the difference of these two quantities. conventional scale.( 17.05 0. viz. Instead of using the heats of formation to calculate the heat of reaction. that is. at 25 C. Differences of temperature are the same.05 X For certain problems dealing with changes of a physical nature..fo) 94. determine the heat of formamole of solid naphthalene from graphite and hydrogen gas at 1 atra. 10 X 94.32) whereas that of the reactants is . and since the latter are taken as zero. .89  C0. the A// value will be the same.
AH . The standard heat of formation AH (The result is not particularly accurate in difference between two large numbers. The heats of combustion combustion of methane at 25 C is of solids and liquids are usually measured at constant volume in a "bomb calorimeter". Nat. Chem. also Rossini. the results can then be used to calculate Aff. Prosen.4 kcal. and the heat of combustion of propane is is (Unless otherwise stated.. x being that of the naphthalene. Examples of such calculations are provided by the problems in 12d. 12f.781.5 1. 29. at a given temperature and 1 atm. 4 Ethylene (ff). Eng. Ind.3Butadiene (g). Bur.6 326. C 2 H Propane (g). is called the heat of combustion. The results are of interest for certain theoretical purposes.4  732.3 607. or together with oxygen. C 4 H. ibid..8 530. From the data in the preceding section. 36. CO(NH 2 ) 2 Ethyl acetate (0. but they can also be utilized for the derivation of heats of formation and heats of combustion.228.088 CH OH 6 (s) f C H6COOH fl 771. pressure. Ethanoi (0. The heat change accompanying the complete combustion of 1 mole of a compound. Ci 2 H On 22 CioPIg Urea (). The change of heat content accompany12h.2 kcal.0 337. wPentane (0. PER MOLE A# Substance Methane (g).) Utilizing the 8 See ref. Heat of Combustion.2 .0 934. Res. The standard heats of combustion of a number of familiar organic 2 The data may be used to calculate compounds are given in Table VI. /.0 Naphthalene (s). Johnson and Rossini. 27.32)]  (x + 0).8 372. which is required. 33.5 CeH 6NH 2  538.6 kcal.80 kcal. HEATS OP COMBUSTION AT 25 C IN KCAL.. 1. because it represents the Organic compounds containing carbon and 12g.OH 4  212. 29. Sucrose (s).7 Benzene (0. constant pressure to be understood. 289 (1941). 269 (1946). C 8 Hi Benzole acid Phenol (). for example. this instance. 455. TABLE Substance VI.. at 25 C.4 kcal. as explained above.12h HEAT CHANGES IN CHEMICAL REACTIONS 75 the standard heat of formation of each species being written below its formula. C 7 H 8 Xylene (0.9 173. it is seen. 94. 35. 1.2 1. it follows that  1228. ing the hydrogenation of 1 mole of an unsaturated compound has been determined in a number of instances. CH 4 Ethane (g).0 811. C 6H 6 Toluene (0. C 2 H 5OH CH CH. Since A// is 1..(10 X x = 14. can be burnt in oxygen gas to yield carbon dioxide and (liquid) water as the sole products. Stand.6 kcal.) of naphthalene at 25 C is thus 14. Heat of Hydrogenation. . CH. C6Hi 2 nHexane (0.0 838. Proeen and Rossini. hydrogen alone.6 688.9 heats of reaction and of formation which cannot be determined directly. 463 (1946). 255 (1944).05)  (4 X 68. C 2 H 4 1. 1424 (1937).348. 36. that the heat of 212.[. 141 (1945). CH 8 nButane (g).228. is Problem: The standard heat of hydrogenation of gaseous propylene to propane 530.7 995. 8 Methanol (0. CH 3 COOC 2H 6 Aniline (0.9 151.
0313 atm. greater than that of the same weight of liquid water at 100 C and 1 atm.Atf 29.).O() = HiO(i) = H H 2 2 0(0.0 68. and transition from one crystalline modification to another. The results may be expressed in the form of equations similar to the thermochemical . such as vaporization of a liquid. (ii) and (iv) in any event. of the two phases under consideration at the temperature and pressure at which the phase change takes place. etc.3CO 2 (0) + 4H C() + 0to) .6 cal. A phase change.76 THERMOCHEMISTRY 12i heats of formation of carbon dioxide ( 94. pressure. changes. Thus.2 0(Z). 12L Phase Changes. thus. fusion. 2 A# . The data are as follows: ( known (i) (ii) (iii) C.. is invariably associated with a change of heat content. or 1 mole. fusion or sublimation of a solid. it is found that . 2 A# ==  491." contents of 1 gram. although the tendency at the present time is toward the omission These quantities represent the difference in the heat of the term "latent. the heat of vaporization of water is 583." 1 and this quantity of heat must be supplied to 1 g.0 kcai. The heat of combustion can either be obtained from this result by reversing it and adding three times equations (iii) and (iv).76 mm.6 kca? 530. determine the heat of combustion and the standard heat of formation of propylene.438 kcal.4 cal.). to know the heat of a particular reaction when one (or more) of the sub . O(0. g. thus at 25 C.6 94.C 8 H 8 (0). or 0. g. at the given temperature and pressure. add equations (i) and (ii). A7/ W 3 A//373 = 1. C 8 H 8 (0) + 5O 2 (0) .3 kcal. Molar heats of vaporization and fusion are frequently employed in thermodynamics. 3C(s) + 3H 2 (0) = C H 6 (0)." 1 the pressure being 23.717 kcal.. latent heats of various types vary with the temperature. (iii) and four times (iv). Such heat changes are often referred to as the "latent heat" of vaporization. A# = A// . or it may be derived by utilizing (i). 3 A// = 5.) and of liquid water 68. 1 atm. it is sometimes required tion with thermochemical problems. 9.C0 (<7). CaHeto) + 4K>2(fiO = 3CO 2 (0) + 3H O(0.3 To and then subtract the sum from three times equation the result is obtain the standard heat of formation of propylene.9 kcai. the heat content of 1 gram of steam (water vapor) is 539. The heat of vaporization of water at 100 C is thus 539. but for the present they will be employed in connecFor example.0 kcal.4 cal. Heats of vaporization and fusion are utilized in the treatment of phase changes (Chapter XI).H 6 (0) + H a (0) . (iv) Hfo) + JOtto) = H0(l). H. of liquid water at 100 C to convert it Like other heat into vapor at the same temperature and 1 atm. pressure. equations represented above. and these are the changes of heat content associated with the vaporization or fusion of 1 mole of the substance under consideration.
0313 atm.45 kcal. atom of carbon as diamond to the stable form. A# 298 = A#S 98 = 10. g. An expression for the variation of the heat of reaction with temperature can be derived in a simple manner. the difference in the heat content at 1 atm.514 kcal. spectively.e. the result would be the same as that given above. 20e) as only 0. i. A#298 = 10. H. the necessary adjustment can be readily made.e. at 25 C. 2 2 i.e. 0. viz. Htfo) + *0. 2 1 atm.0313 atm. at 25 C is associated with a decrease of 0.(flf) . in the heat content. per stances taking part mole... with each substance in standard gaseous state. diamond 94.) = H O(0.50 and and graphite. When C(diamond) C(graphite) + O (0) == CO (0). H O(Z) = H O(0r.  57. which is 583. pressure from that at 0. atom" 1 reat 25 i.. Although water vapor is not ideal. If HA is the total heat content of .). i. For the present purpose it is necessary to know the value of AH for this process with water vapor at 1 atm.05 By subtracting these two thermochemical equations. the heat of transition of one form to the other can be evaluated. graphite.).0313 atm. 94.005 kcal.). 68.H 0(Z).. since AT would be independent of the pressure ( 9e).(0).016 cal. the heats of combustion of the two allotropic forms of carbon. 0. Suppose the standard heat of formation of water vapor at 25 C is required. there is change in the crystalline form of any substance involved in a reaction there is a change in the heat content. mole""1 . pressure.52 kcal.. 12j. . If the data for a given reaction with two separate forms of a particular substance are available.32 kcal. H 2 O($r. 2 1 atm. + O.e.12 j HEAT CHANGES IN CHEMICAL REACTIONS 77 is in a different physical state than usual.fo) = CO.fo) + i0 2 (0) = its H 2 0(<7). Combination with the preceding equation gives H and hence 2 O(Z) = H O(<7. or 10.. are known to be 94.80 kcal. as the following instance will show. that it is immediately seen C (diamond) = C (graphite). Aff298 = 0.50 kcal.e.514 kcal. C. 2 2 Aff 298 A# 298 Aff 298 == 94. has been calculated (cf. i. use is made of the heat of vaporization of water.6 X 18.32 kcal. 2 A#2 08 .. If the vapor behaved as an ideal gas. transition of 1 g.45 kcal. The = 0. The standard heat of formation of liquid water at 25 C is 68. Effect of Temperature on Heat of Reaction: The Kirchhoff Equation.005 kcal.05 kcal. For example.
8) ACp . (6H/dT)p is equal to CP. R.8) of the species indicated. respectively. although a similar result was obtained earlier by The rate of variation of the heat of reaction with temperaC.LfaCp).E(nCp)/ .1)]. respectively. is given by pressure. and/ refer to the initial first state (reactants) and final state (products). C. The subscripts i is (12.HA .6) is the increase in the heat capacity of the system thus. and so the heat capacity of the system in its initial state is the sum of the heat capacities of the reactants.6) takes the accompanying the chemical reaction. Person (1851). of the reactants and the products. If this equation entiated with respect to temperature. and so form it may be represented by ACp.9) where n is the number of moles of each substance taking part in the reaction and CP is its molar heat capacity. then. at the given (constant) The righthand pressure. which is the expression of what is generally know as the Kirchhoff equation (G. so that the . (12.4) is differ the quantities referring to the same pressure. it is seen that According to equation (9.78 THERMOCHEMISTRY 12j the reactants and B is that of the products. 1858). Ttye expression in the first set of brackets in equation (12.11). side of equation (12. ture. and that in the final state is the sum of the heat capacities of the products For the general chemical reaction of the reaction.8) gives the total beat capacity of the products. (12. is thus equal to the increase in the heat capacity accompanying the reaction. (12. equation (12. as indicated in H AH AH all *= HB. the increase of heat capacity [Z(Cp) L + m(Cp) M +] thus given by [(Cp) A + 6(Cp) B +]. at constant pressure. at the same temperature and I2a [cf. The heat capacity is an extensive property. so that the difference is equal to the increase of heat where the Cp terms are here the molar heat capacities capacity for the reaction. An alternative form of (12. Kirchhoff. aA + 6B + ACp is  IL + mM + . and hence where (Cp) A and (C P ) B are the total heat capacities.. and that in the second brackets is for the reactants.
The application of the 12k.9) is the 79 term on the righthand side for the products. If.. these are consequently not the ordinary latent heats. 57.TI is 75.92.. AH AH Problem: The mean molar heat capacities. oxygen and water vapor in the temperature range from 25 C to 100 C are as follows: Ha(flr).7) . It is required to find AH* by using equation (12. whereas the second reactants.12k HEAT CHANGES IN CHEMICAL REACTIONS of equation (12. if ACp is taken as the mean value ACp in the temperature range from T\ to T2 it follows from equation (12. 8. as constant and independent of temperature over a small range or. i.AH* 2.10) that AC P (T 2 . For a phase change. vaporization or transition with temperature is required. since the reaction can be carried out at two or more temperatures and AH determined at the same pressure.52)  2. e. but one highly important limitation must be borne in mind. Application of the Kirchhoff Equation. 8.03 cal.Ti).10) when a change of (12. 2 1 (12. calculate the standard heat of formation of water vapor at 100 C. + 57.. For a chemical reaction there is no difficulty concerning (dAH/dT)p. Kirchhoff equation to determine the heat of reaction at one temperature if that at another is known involves the integration of equation (12." 1 mole' 1 Utilizing the heat of reaction at 25 C obtained in 1 2i. e. O 2 (0).g. H 2 0(0).80 . (12. temperature is accompanied by a change of pressure. and for this purpose the same heat units.04. 1 atm. such as fusion or vaporization. better. thus. reaction is AP  p(H 2 0. at constant pressure. TI is 25 C and T 2 is 100 C. The so that. deg." 1 In this case. If the variation of the equilibrium heat of fusion. 6.. so that JTi .92 + 3.41 cal.g. the ordinary latent heat of fusion or vaporization (AH) is the value under equilibrium conditions.80 kcal. between the temperature limits of TI and T* the result is /Tl Tf AH* . deg. at constant pressure. must be used for the AH's and ACp. the variation of AH with temperature. If to be applied to a phase change the AH's must refer to equation the same pressure at different temperatures. term is sum of all the nCP terms the corresponding sum for the The Kirchhoff equation as derived above should be applicable to both chemical and physical processes.Aff i = f ACpdT.7) is J Tl two temperatures. AHi is known from 12i to be 57. kcal. however.03  g)  [ (6. as will be seen in 271.e. .41 X 10~ X  75.7) must be modified. 7. mole*.11).98 kcal. of hydrogen. equation (12. ACp may be taken . . in each case. hence.11) where i AH and AH* are the heats of reaction at the in the simplest case..
208. and T 2 is 100 . since A#i .Cp(H 2 0.(298) ] cal.7). which yields AH  Atf o + TACWT..AHi = .182 kcal. values for all the substances concerned are available from Table II. g} so that = = = 7. as obtained in the preceding problem.182 cal. integration of (12..095 + 2. it follows that A# 2 3 T is 25 C.12) into (12.2670 X + 0.295 X 10~ 6 C. X . for the general reaction given in 12j. $ 0.200 3.776 + 0." 1 Hence.0170 10r*T* lO^T72 lO' 6 ?12 .5 = .12) where. (12.776(373 (298) ] + J X 0.298) + J X 0. cleg.10). Since A#i is . .947 X 10~ 3 r + . C P (H 2 0.947 6.57. Since the variation of the heat capacity of many substances can be expressed by means of equation (9.4808 X 1. it Inserting equation (12.776. mole~ l at 25 C.[Cp(H 2 g) + = .253 X X + 0. and by equation (12.14).0.947 X 10~ 3 .2. mole~l . 298 K. In some connections it is useful to derive a general expression which will give the heat content change at any temperature. y.13) integration..80 kcal.e.14) so that the change of heat content at one temperature can be calculated if that at another temperature is known.8 + 2. . .295 X 10. 3 3 2 is 57. . i.Aa + A0T + A7T + 2 . (12. this may be done by the general integration of equation (12.24). ft. g} . AY = 0.2..80 THERMOCHEMISTRY 12k In the general case.e. Problem: Calculate the standard heat of formation of water vapor at 100 C allowing for the variation with temperature of the heat capacities of the reactants and the product. 2 373 K.374 X  1Q~*T lO' 3 ? 10" 3 T 7 + 0.A#i is . (ZTL + WTM +) 6/3B (TA + &7B + + ) ).10) is possible if ACP is known as a function of temperature. AH From Table II.) + *A7(rS 71) + . and the a.947 X 10~ [(373) 2 6 i.98 kcal. .2 + 23. g) g) Cp(0*. A/3 = l 0. A? = and so oil. and A# .219 6. and taking as 57.15) .295 X 10~ G T 2 cal. is found that and carrying out the  T. (12.80 kcal. it follows that AC P . . (12. Cp(H 2 . Aa =  2.[(373) .
. irrespective of its form.8) or (12.457 X ACp 10~ 6 !T 3 cal. and if the expression for ACp were valid down to that temperature.13 kcal.[iCp(N. AH 0.787 X lO'T 6.7212 Cp(H 2) = 10.03 kcal.12) into (12. utilizing the data in Table II... e.12k HEAT CHANGES IN CHEMICAL REACTIONS 81 where the integration constant A# may be regarded as the difference in the heat contents of products and reactants if the substances could exist at the absolute zero. then equations such as (12. can be applied to any chemical reaction. g) 2. l atom1 .24).189 10.707 iCp(Ni) = 3. the result is A# = The Affo + AaT + ^A^T + \&yT* + 7 72 .673 f 2. mole.38 7.A#S = AH? 103 !T 3. Insertion of the results in (12. etc. . from i. is given by (graphite).9). mole1 . the appropriate equations can be (12. g) + $C P (H X X + X + X + X X + 298 K.6 !T 2 0.J X 1.16) can still be employed. mole" 1 at 25 C.1 1. W~*T* .409 7.47 X 10~ 9 !T3 kcal. ACp = Cp(NH 8 Cp(NHs) 0.38 7. A# The reaction is and hence. + + X .7).457!T Aff .15).14) and Otherwise.0.421 . and so a knowledge of the integration constant A# to be calculated. and hence it is found this equation that A# is 9. CP = 2. derived without difficulty.1 7.14). In the evaluation of ACp by equation (12. . A.16) then gives an equation for the heat of reaction as a power series function of temperature. (12. so that _ 9 13 _ 7 46 x 10 sy + 3>69 x iQer*  0. If the variation of the heat capacity with temperature of the solids or liquids concerned can be represented by an expression of the form of (9. Although the examples given above have referred to reactions involving only gases.46 7 ..e. the equations derived.0404 X W~*T* 0. the appropriate nCp term must be included for every reactant and product.15) and carrying out the integration. are presumed to be known from heat at any one temperature will permit capacity data. the value of A# is . The result will be applicable over the same temperature range only as are the empirical heat capacity constants a.. etc.300 X W~3 T = !T 10~ IQT* cal. Upon inserting the general equation (12.03 kcal. At 25 C. (12.~ g. 7.3 !T .C2 A 1Q~*T + 1.69 X lO^T2 0.11.0.. AY.728 X 7. (12.. deg.17 X 10 6 !T~ 2 cal.47 X 10!T3 kcai. Problem: The variation with temperature of the heat capacity of carbon between 273 and 1373 K.g. of ammonia gas is Problem: The standard heat of formation 11. (12.41 7. derive a general expression for the heat of formation applicable in the temperature range from 273 to 1500 K. .16) values of Aa.225 3 10. deg. etc.
. for it depends upon the amount of solvent. s) + 0. place in solution. Thus.82 THERMOCHEMISTRY 121 Utilizing data already available derive a general expression for the heat of the reaction C From Table II >. are given below.555 100 LI 50 I 17.278 Moles H 2 O/Moles HC1 400 200 0. that is.13 kcal. the matter of interest is the total heat change per mole of solute when solution is complete.36 10~ 3 T  [Cp(C. after converting ACp into kcal.. The heat of solution per mole at any instant thus varies during the course of the solution process.130 0.066 X 1Q. C are 57. This is because the formation of a solution is almost invariably accompanied by a change of heat content. the composition of the solution changes from pure solvent to the final solution.17 + X 102 r~ l kcal. gradually dissolves in a particular solvent.80 and 2 O(0) and CO(g) at 25 (standard) heats of formation of 26.g. H A# When a reaction takes 121. Inserting these values in the result just obtained.17 X 0)] 7lO 6 ! 2 . + H 0fo) 2 COfo) + H. The . at 25 C. i.54 17. deg.03 17. When a solute. At the present time.. or when one or more of the reactants or products are in solution instead of the pure state. of solvent.~ l A// = A//o A//o + + 3. Heat Changes of Reactions in Solution. 1. e.15). Molality (m) 0. heat is evolved or absorbed. this is the integral heat of solution. The integral heats of solution for various solutions of hydrochloric acid.000 grams.to) for the heat capacity of carbon. a solid. mole~ l respectively. the heat change is affected just as for a phase change. 0)]  3..68 X 10~r  0.397  + C P (H X Z.397 X 10T  1. however. 1. if AJET is the total change of heat content when m moles of solute are dissolved in a definite quantity. of different molalities.~ l Hence. as a function of the temperature. by equation (12.42 kcal. the heat of solution at a given temperature varies with the concentration of the solution. referred to as the heat of solution. A// is can now be calculated at any temperature found to be 30.. cal.g. so that A// for the given reaction is 31.022 X 10"+ T* 1. known as the "differential heat of solution" will be considered more fully later (Chapter XVIII). The heat change per mole of solute dissolved. and hence in the specified range.e. the integral heat of solution is equal to Aff/ra. 298 K. and the expression given above 0) = 3. In other words.70 17.40 kcal. deg. at 25 C. is not a constant quantity. this quantity. in the range specified above.6 T 2  Cp(H 2 O. e.38 kcai.
i. 17. HC1(50H 2 0) As indicated in + aq = HCl(o^) AH =  0.* variation of the heat of solution with the compoa solution from one concentration to another is also accompanied by a heat change. as for gases in general. HC1(60H 2O) + 350H O(Z) = 2 HC1(400H 2O). the total heat evolved is 17.30 kcal. at 25 C.. the heats of solution are unusually large.48 kcal. .121 If HEAT CHANGES IN CHEMICAL REACTIONS 83 the heat changes are extrapolated to infinite dilution the integral heat 17.30 kcaL The dilution of the HC1(50H 2 0).70 kcal.139 molal. per mole.40 kcal. solution is thus accompanied by the evolution of a total amount of 0.88 kcal. integral trapolated of any solution to infinite dilution can be calculated in an analogous manner.e. 12b. i. A number of values of heats of solution are given in Table 6 at the end of the book. For solids which do not interact with the solvent. however. the symbol aq implies a large amount of water. it is possible sition of the solution is that dilution of One consequence of the to write HC%) + 400H O(Z) = HC%) + 50H O(Z) 2 2 HC1(400H 2 O). the integral heat of solution is of dilution is usually positive. when 1 mole of found to be hydrogen chloride is dissolved in a large quantity of water. using the data for hydrochloric acid given above. 1. Because of the interaction between hydrogen chloride and water. The net change per mole of solute associated with the dilution of a solution from one concentration to another is the integral heat of dilution. For example.9 kcal. If the gaseous reactants are employed and the product is solid ammonium chloride. Further. the change may be represented by ) + HClfo) = NH C1() 4 A# =  41.88 so that. so that HCl(ag) refers to an infinitely dilute solution of hydrochloric acid. per mole of hydrogen chloride. 0. AH = AH = Aff 17. Thus.11 molal.88 kcal. at 25 C. so as to form an extremely dilute solution. thus. HC1(50H 2 O). known as the "differential heat of dilution/' will be left to a subsequent chapter. AH/m is negative in this case.40 so that by subtraction. The consequence of heats of solution in connection with the heat changes in chemical reactions may be illustrated by reference to the reaction between ammonia and hydrogen chloride. Consideration of the change of heat content per mole at any instant in the course of the dilution process. Results analogous to those quoted above have been obtained with other solutes of various kinds. By utilizing the exheat of dilution infinite the of at heat solution dilution.. not necessarily gaseous in nature. = 0.e. to the HC1(400H 2 0). 17. as is the case with most hydra ted salts in water. HC%) + 50H O(Z) = HC%) + aq = 2 HC1(50H 2 0) HCl(og) AH = AH =  17.
Maximum Reaction Temperatures: Flame Temperatures. called the "partial molar heat capacity.9 kcal. of the heat change of the reaction between aqueous solutions of ammonia and hydrochloric acid has confirmed the calculated result. Direct experimental measurement.. It is possible. Since the integral heat of solution varies to some extent with the concentration of the ammonium chloride solution. so that no heat enters or leaves the system.5 kcal." This quantity will be described in Chapter XVIII.5 which.. so that the products will be at a different temperature from that of the reactants.. From a knowledge of heats of reaction and of the variation with temperature of the heat capacities of the reactants and products. however.84 THERMOCHEMISTRY 13ft If the ammonium chloride eventually occurs in an aqueous solution containing 1 mole of the salt to 200 moles of water. but if A# is negative. If Aff at constant temperature is positive. the temperature of the adiabatic system will fall. In a reaction performed adiabatically the temperature of the system will change. NH C1() + 200H. viz.HC1(100H O) ) 2 8 2 2 2 Atf Aff  8. 13.0 kcal. as is usually postulated. this result is applicable in particular to the composition of solution specified. gives NH.0) + HC1(100H O) .0 kcal. the heat capacity to be employed is a special quantity. the thermochemical equations are as follows: + 100H O(Z) _ NH (100H 0) HC%) + 100H O(0 . and that the heat liberated removed (or supplied) by the surroundings. in order to determine the variation with temperature of the heat content change accompanying a reaction in solution.(100H. i. so that by addition 2 NHafo) + HClfo) + 200H 0(0 = NH C1(200H O) 4 2 Aff  38. FLAME AND EXPLOSION TEMPERATURES Ida. For a constant pressure process.NH C1(200H O) 2 4 2 A# . If the reaction takes place between aqueous solutions of ammonia and hydrochloric acid. When applying the Eirchhoff equation. this means that AH will be zero. to conceive the reaction taking place under adiabatic conditions. In the foregoing treatment of thermochemical changes it has been supposed that the reaction takes place at constant temperature. then use is made of the known integral heat of solution.e. the temperature will rise during the course of the reaction. combined with the result obtained above.O) 4 Aff  3. heat is absorbed. in connection with a general discussion of the properties of substances in solution. 17. it is possible to calculate the final temperature (or absorbed) is quantity of heat . It is this which is recorded as the heat of reaction. 12.O(i) 4  NH C1(200H.
15 X 10~ 3 T  3. E(nCp). g) + 8 X C P (N 2 ). A//" (heating).. to T* must be equal in magnitude to the heat of reaction. . be zero. so that If S(n(7p)/ is the total heat capacity of the products.396 14. thus. ture of the products. This temperature is of particular interest in connection with the combustion of gaseous hydrocarbons in oxygen or air. then the heat required to to T 2 i. In such cases it gives the maximum flame temperature. at 25 C. the actual temperature being somewhat lower because of various disturbing factors. X 10.  191. i. 20 2 (0) . 298 K.438 51.52 CH4 (0) + It + 2H 0(0). all based on the same fundamental principles. Afl (heating) = /rt A# 298 (reaction) = I ^(nC P ) fdT. pressure at is 10.405 X + 4.80 kcal. g) = 8 X Cp(N ) 2 2 Cp(CO 2 )  6..52 kcal. assuming combustion to be complete. consisting of 1 mole CO 2 2 moles 2 which were associated in the air with the 2 moles of O 2 used in the combustion of If T z is the maximum temperature attained in the combustion. then the heat required to raise the temperature of the products from 25 C.646 X 3 7 72.e. at the high temperaat ordinary temperatures is required with water vapor as A# CH4 (0) + so that 20 2 (0) .~ l .CO 2 (0) t 2H 2 0(0.3. and then to find to what temperature the products can be raised by means of the heat evolved in the reaction. as postulated above. the value of the product. deg. are available for calculating the maximum temperature attainable in a given reaction. X Cp(H O. (13.80 kcal.534 X 10~*T* + 11. + 2 X Cp(H 2 0.C0 2 (0) A# 2M = A#298 A#29* *2 212.76 kcal. Since the water will ultimately be in the form of vapor.e. ture. 25 Using the data in Table II calculate the maximum temperature of the flame when methane is burnt in the theoretical amount of air (1O* to C 4N 2) at 25 C and constant pressure. The simplest is to imagine the reaction taking place at ordinary temperature (25 C).13a FLAME AND EXPLOSION TEMPERATURES 85 of the system.43 + 26. but opposite in The sum of A// for the temperature increase and Aff for the reaction must sign. the difference in the heat contents of liquid water and vapor at 1 atm. is given by raise the temperature from 298 H A# K . 1 mole of CHU. 2H 20(/) = 2H 2 O(0). 2 . Problem: The heat of combustion of methane is 212. assuming this to be the initial temperature of the reactants. may now be supposed that this quantity of heat is utilized to raise the temperaand 8 moles of Nt.1} ^298 In the present case.100 X W~*T .Cp(CO) and from Table 2 so that II.300 X lQr*T .0.592 + 10.748 X lO" ? + 0.517 X lO^P cal. Several different procedures. for the whole (adiabatic) process is zero.
13b with A#(heating) equal to follows that Upon  Atf lf . it is found that T> is about The calculated maximum 13b. been estimated for several hydrocarbons. Further. it is unlikely that the reaction can be carried out under such conditions that the process is adiabatic.1).(298)'] 72. i.  (298)'].1. .(reaction). flame temperature for the combustion of methane in the theoretical amount of Similar results. the "products" will then include the oxygen remaining when the combustion is complete. From a knowledge of be less the equilibrium constants of the dissociation reactions and their variation with temperature it is possible.517 X . it is improbable that the theoretical quantity of air will be sufficient to cause complete combustion In practice. The value for methane.08 X lOTJ .nto carbon monoxide and oxygen is very appreciable. or hydrogen and hydroxyl. for example. for combustion in air. 53. when the temperatures are much higher. Actual flame temperatures have been determined in a number of cases. Chem. or 191.e.43T. the temperature attained will be lower than if combustion were complete in the theoretical amount of air. 2250 K or 1980 by the method C.. By the same procedure it is also possible to calculate the maximum flame temperature when a hydrocarbon is burnt in excess of air. have air is seen to be nearly 2000 C. and also for carbon monoxide and hydrogen..1. excess air must be used. .08 X 10^C!Z1 . of the carbon dioxide \. These reactions involve the absorption of considerable amounts of heat. Am.760 cal. Finally. allowance for which should be included in the calculation.. the discrepancy is greater. to obtain a more accurate estimate of the flame temperature.172 X . will be found to than 2250 K. In the first place. approximately 2000 C.43!T 10*[!F. + 13. especially. * Jones. 1 There are several reasons why the results obtained in the manner described are higher than the experimental flame temperatures.172 X [72. 869 (1931). ture of the additional oxygen. and since the temperaof the hydrocarbon. it may be mentioned that the combustion of a hydrocarbon is not the Various relatively simple process represented by the usual chemical equation. For combustion in oxygen.15 X 10r*T* . and no heat is lost to the surroundings.86 THERMOCHEMISTRY inserting this result into equation (13.43(7'.J X 3.298) + 13. Friauf and Perrott. so that the presence of nitrogen in the air lowers the theoretical maximum by nearly 2000. the values being about 100 below those calculated. must be raised by the heat of the reaction. by a series of approximations. Calculated and Actual Flame Temperatures.72. dissociation of the water vapor into hydrogen and oxygen. in addition to the nitrogen and the actual reaction products. as well as that of the large amount of accompanying nitrogen. of successive approximations. /. are of the order of 100 lower than those which neglect dissociation. Another reason why observed flame temperatures are lower than the calculated values is that at the high temperature attained in a burning hydrocarbon.760 214. it 191.470 Solving + * X 26. and.76 kcal. The maximum temperature is found to be over 4000 K. Soc. For most common hydrocarbons the results derived in this manner. 191. The effect of any "inert" gas not utilized in the reaction can be readily seen by performing the calculation in the problem given above on the basis of the assumption that the methane is completely burnt in the theoretical amount of pure oxygen. Lewis.
i. so that (13. it follows that Atfo(reaction) + f Jo J^(nCP )jdT .5) sum of the two AH values given by equations (13. the method described above may then be used. 13c. Jo l and combination with (13.A# (reaction) + f ^(nCP)fdT .6) gives * Affr (reaction) + f JT *L(*Cp)jdT . or an expression for. at ordinary temperatures. AH AH(reaction) = A# (reaction) + I ACpdT. (13. (13.5) must be % zero. however. from the temperature T\ to the final (maximum) temperature T 2 is * AH(heating) Since the = f JT\ (nCp^r. the temperature of a hydrocarbon flame may be increased by preheating the reacting gases.4) takes the form The value may AflV(reaction) . e.f ^(nCp)idT JT 0.2) The increase in the heat capacity ACp may be ACp E(nCr). and TI is the maximum temperature attainable in the reaction under adiabatic conditions at constant pressure.4) On the other hand. initial the expression for AH for the heating of the products. In the calculation of the maximum temperature it is necessary to for the reaction at the temperaobtain.. so that the heat of reaction AHr is given at the initial temperature of the . 25 C. T\ is the temperature to which the reactants are preheated.2) becomes Atf(reaction) = A# (reaction) + Jo (nCp^/dT Jo (nCp^dT.g. thus avoiding the necessity of first calculating A/7 (reaction) .3) as in equation (12.e. (13. Influence of Preheating Reacting Gases. (13.7) where. as before.f Jo LfaCp^dT.4) and (13. An alternative procedure is.15). by (13.13C FLAME AND EXPLOSION TEMPERATURES 87 compounds other than carbon dioxide and water are frequently formed. and so the heat of reaction is not equal to the value determined from measurements in an explosion bomb. the value of.6) of AH o(reaction) and the heat capacities of the reactants and products be presumed to be known. The heat of reaction at any temperature Ti is given by equation (12. ture to which the gases are heated.f *(n(7p)<dr Jo 0. in this case equation (13. in the presence of a large excess of oxygen. (13. Apart from the use of oxygen. and so it is possible to calculate the maximum temperature T 2 for any given initial temperature T\ of the reactants.9). first.  represented (nC/>)i. as follows.. An alternative treatment makes direct use of AHr (reaction) at any temperature T. It is of interest to note that if TI is made identical with jT.
. AE + XXntfvMT. which may be modified according to circumstances. This condition is unlikely to be satisfied by the system. The value of AH for the reaction H (0) + i0 2 2 (0) = H O(0). mean heat capacities are to be used.1) takes the form is AS+ 7298 Pl>cv). In order to simplify the calculation.6)..tO. since 2 moles of nitrogen.1). can be made with sufficient accuracy by means of equation (12. equation (13. instead of at constant pressure. are included in the "products.~ mole" ) and of water vapor (11. Estimate the maximum explosion temperature and pressure. at 25 C and a total pressure of 1 atm.  298) = 0. From the maximum temperature. may be used. for the reasons given in connection with flame temperatures. 57. The conversion of AHp to AEv t i.7) or (13.. CV. is exploded in a closed vessel. that (7i("V)/ is 0. instead of those for constant pressure. equation (13.8 kcal. deg. and are based on the supposition that the system is in a state of thennodynamic equilibrium when the rapid combustion is completed. maximum values.3) that Qv(or AE) is For the present purpose. equation (13..3 cal. utilizing the approximation that the gas laws are applicable.. for the temperature range from 25 to 3000 C. and since An is here it follows from known to be 300 cal. since RTAn is equal to equation (12. 57.3 +2 X + . associated with the J mole of oxygen employed in the combustion of the mole of hydrogen. The value at constant presonly changes necessary are (a) the replacement of the sure by AE at constant volume. equation (13. g) v(N 2). Hence.dr and since the = o. deg. and (b) the use of the heat capacities at constant volume. if T is Q and then equation (13. the results give a good indication of the maximum pressure AH AH AH accompanying an explosive reaction. i. deg. l l 1 l deg."1 mole"1 less than the value of Cp at the same temperature (cf . nevertheless. e.7) may be taken as the general expression. to (13. Problem: A mixture of hydrogen gas and the theoretical amount of air. it follows from the data.e. 2 . often referred to as the explosion temperature. applicable to all cases.500 cal. Further. In the present case 23(nvO/ is equal to Cv(H.e. at 25 C. and failing other information the heat capacity CV of a gas may be taken as 2 cal.3). of Qp to Qv.3 cal. attained in a combustion reaction at constant volume.. The explosion temperatures calculated in this manner represent maximum values. The pressures calculated in this manner are. Maximum Explosion Temperatures and Pressures. The additional information required is either the original pressure or the volume of the vessel and the quantities of the gases involved." Assuming Cv to be less 2 than CP by 2 cal. assuming adiabatic conditions. The methods de13d.7). however. may be used to calculate the maximum temperature.g. they may be regarded as independent of the (moderate) pressure.7) reduces T becomes equivalent to E. 21a) . the pressure attained in an explosion at constant volume can be estimated.~l mole" 1 .~~ mole~ ). scribed in the preceding section.88 taken as THERMOCHEMISTRY 13d reacting gases.7) becomes identical with (13. of course. the mean heat capacities Cp of nitrogen (8.
1424 (1937). 263 (1945). the mean heat capacity of the experimental gas. From this the corresponding temperature can be calculated by using the ideal gas law. 2920 K.600 + 21. is . at 1 pressure 2920 it is K atm. Heats of Combustion.298) = !T a  0. Bur. M. This procedure has been reversed in a method for determining heat capacities.. octane (CgHi*): calculated. are placed in a steel bomb. Ewell. can be calculated. Bunsen (1850) and improved by M. and that in any homologous series there is a change of 150 to 160 kcal.~ l . . Thornton. Not. first used by R. contributes a more or less There is a possibility. and 298 K. /. the latter is found to be about 2400 K. The maximum explosion temperature is thus about 2900 K. A . 34.g. easily shown that the maximum explosion pressure is In the foregoing treatment the calculation of the maximum pressure involves a knowledge of the heat capacities of the products. of developing approximate rules relating the composition of the given substance to its heat of combustion. consisted of 1EU. ibid. 33. Ind. Although the results obtained are not always accurate. and the maximum pressure attained is measured. 5n kcal. definite amount to the heat of combustion. CALCULATION OF HEAT OF REACTION number of methods have been proposed 14ft. 29.9(2** . they are useful when experimental data are not availAn examination of the heats of combustion of organic compounds able. Since the heat capacity of the water vapor is known. which must be inert in character. respectively. A known amount of a mixture of two volumes of hydrogen and one of oxygen and a definite quantity of the gas whose heat capacity is to be measured. consists of 1H 2 derived from the ideal gas equation. 32. for more exact rules applicable to paraffin hydrocarbons. Res..9 oal. Eng.. where n is the number of atoms of oxygen is about required to burn a molecule of the compound. which is considerably higher than the corresponding flame temperature. Phil Mag. for the calculation of heats of formation and combustion from a knowledge of the formula of the substance concerned. per mole for each CH 2 group. 1917) 4 is that the heat of combustion 52. deg.14a CALCULATION OF HEAT OF REACTION 21. e. per mole. Data extending to very high temperatures have been obtained in this manner. hydrocarbons.. 14.. 4 Thornton.  57. Stand. The gases are then exploded by a spark. One such rule (W. 89 X 6. 196 (1917). seo Roeaini. 778 (1940). Pier (1908). shows that isomeric substances have almost the same values. observed. Proeen and Roemni. therefore. with V and R constant. The maximum gas. Heats of combustion calculated in this manner are in satisfactory agreement with observation for 1312 kcal..3 Hence. CAem. These results suggest that each carbon and hydrogen atom that is burnt to carbon dioxide and water. The original 62 and 2N 2 whereas the final gas at and 2N 2 Since PV = nRT.
. from a methane molecule. benzene (C 6 calculated. atom as the heat of vaporization of carbon. but which are shared with oxygen. the heat of formation of the compound from its elements can be calculated ( 12g). one of which. the C bond energy is onefourth of the amount of energy required to break up a mole of methane molecules into separate. when combustion is complete. is equivalent to stating that the heat of combustion is However. Bond Energies and Heat of Reaction.. kcal. observed.g. and by the use of these correction factors results have been obtained which are within one per cent. Further.1350 kcal. i. 1940. but the socalled bond energy is the mean value. 782 1307 kcal. 131. A more fundamental approach to the problem of calculating heats of formation and reaction is by the use of bond energies. or less.. in carbon dioxide. suc356 kcal. required to break a particular bond in a molecule and separate the resulting atoms or radicals from one another.90 THERMOCHEMISTRY 14b (CuH 2 aOii): calculated. Thus. Nat.. In its simplest form. S.e. "The Nature of the Chemical Bond. as calculated by L. where of a liquid compound at constant pressure is equal to x is the number of valence electrons of carbon not shared with oxygen in the original substance. /. per g. it has been possible to derive the mean energies of a number of different bonds. e. per mole.. liquid or gaseous. 26. but are less satisfactory for compounds containing oxygen. observed. 14b. There are good reasons for believing that different energies are required to remove the successive hydrogen atoms.e. In general... 2. 787 kcal. By the bond energy is meant the average amount of energy. namely the estimated heat of combustion. are given in Table VII. . Stand. pp..g. of the experimental heats of combustion.05x kcal. gaseous. Res. 367 kcal. they usually involve the difference between two relatively large numbers. for the errors are probably greater than the latent heats. per mole. solid. Some of these 6 values. i.. e. carbon atoms and hydrogen atoms. so that this rule 52. Kharasch (1929) 5 The molar heat of combustion is virtually the same as that just described. i.1260 kcal. The results will not be very accurate for. x is equal to twice the number n of oxygen atoms utilized in the combustion of a molecule. as indicated earlier..e. From a knowledge of heats of dissociation of various molecules into atoms and of the standard heats of formation of others. they are based on 125 kcal. in formaldehyde. . 359 (1929). Bur.. Pauling (1940). It is perhaps unnecessary to mention that from a knowledge of the heat of combustion. Pauling. may be appreciably in error. thus for C=O.. L.. of the compound under consideration. sucrose cinic acid (CJIeO^: calculated. the method proposed by M. they are certainly not sufficiently accurate to permit of a distinction between AB and A/f. In kcal. it is 142 kcal. no allowance is made for the state. Although the results were meant to apply to heats of combustion at constant volume. Kharasch has realized the necessity for including allowances for various types of structure in the compound. 63. observed. one at a time. For the and CssN bonds the energies vary to some extent with the nature of the compounds. . AJS?. H):  H C=O ' 6 Kharasch.." 2nd ed.
14b
CALCULATION OP HEAT OP REACTION
91
149 kcal. in other aldehydes, and 152 kcal. in ketones, acids and esters. The bond is 150 kcal. in most cyanides, but 144 kcal. in energy of the hydrogen cyanide.
CsN
TABLE
VII.
BOND ENERGIES
IN KCAL.
PER MOLE
Energy
71.4 kcaL 48.6 70.0 66.5 54.0 45.5
Bond
Energy
103.4 kcal. 58.6 57.8 46.1 36.2 87.3 83.7 110.2 102.7 87.3
see text.
Bond
H H
C C
Cl
Ci
H
I
Br
I
Br
I
C H
C N C O C Cl C Br C I
N H O H H Cl H Br For C=O and C=N,
By the
c=c
118 170 100 123
use of the bond energies in Table VII it is possible to derive satisheats of formation and reaction in many cases, provided the subfactory stances involved do not contain certain doublebonded compounds. Whenever wavemechanical resonance is possible, the energy required to dissociate the molecule, as calculated from the results given above, is too small. It is 7 necessary in such instances to make allowance for the 'resonance energy." Although this varies from one compound to another, its value is approxi1 l mately 38 kcal. mole" for benzene and its simple derivatives, 75 kcal. mole~
i
for naphthalene compounds, 28 kcal. per kcal. mole"" 1 for esters.
mole for carboxylic
acids,
and 24
Suppose
'
it is
is,
ethane, that
required to determine the standard heat of formation of the heat of the reaction
2C(s)
CH
e (flO.
be regarded as equivalent to the vaporization of 2 g. atoms of X 125 kcal., the breaking of 3 moles of bonds, requiring 3 X 103.4 kcal., the resulting atoms are then combined to form one C C bond, yielding 58.6 kcal., and six C bonds, yielding 6 X 87.3 kcal. in ethane. The gain in energy, which may be taken as A#, accompanying the formation of ethane at ordinary temperatures is thus given by
This
may
solid carbon, requiring 2
H H
H
Aff

[(2
X
125)
+
(3
X
103.4)]

[58.6
+
(6
X
87.3)]
=
22.2 kcal.
The value determined experimentally from the heat of combustion is 20.24 25 C. From the heat of formation, it is possible to calculate the heat of combustion, using the known heats of formation of carbon dioxide
kcal. at
and water.
7
Theoretically,
it
should be possible to evaluate the heat of
"The Nature
of the
See, for example, L. Pauling,
Chemical Bond/' 2nd
III.
ed., 1940,
Chap. IV;
S. Glasstone, "Theoretical
Chemistry/' 1944, Chap.
92
THERMOCHEMISTRY
Hb
made
for the
combustion directly, but in doing so allowance should be resonance energy of carbon dioxide, 33 kcal. per mole.
Problem:
Utilize
bond and resonance
energies to evaluate the heat of
com
bustion of benzole acid.
The
reaction
is
CHfiCOOH
and the bond energies are as
Reactants
+ 7K>2
= 7CO 2
+ 3H O,
2
follows:
Products
Bonds:
14O=O
60
Resonance:
H
2128 kcal. 661
231
7CO 2
3020 kcal.
2254 kcal.
The increase of heat content for the combustion is thus 2254
(The experimental value
is
3020
=
766 kcal.
771 kcal. at 25 C.)
The bond energies recorded in Table VII are based on data for substances
they should be used for reactions involving gases only. However, molar heats of fusion and vaporization are usually of the order of 1 to 10 kcal.; hence, provided equal numbers of molecules of solids and liquids appear on both sides of the chemical equation, the conventional bond energies may be employed to yield results of a fair
in the gaseous state; strictly, therefore,
degree of accuracy.
EXERCISES
*
1. The heat of hydrogenation of ethylene (CaHO to ethane (CjH$) is 32.6 kcal at 25 O. Utilizing the heat of combustion data in Table VI, determine the change of heat content accompanying the cracking reaction nbutane (C 4 Hio) * 2C,H4 H, at 25 C. 2. The heats of combustion of nbutane and isobutane are 688.0 and 686.3 kcal., respectively, at 25 C. Calculate the heat of formation of each of these isomers from its elements, and also the heat of isomeriaation, i.e., nbutane > isobutane, at 25 C. 3. Calculate P and Ai?r at 25 C for the reactions
+
&H
+ 7JO,  3H,O(J) 4 6CO, + 7*0,  3H,0(g) + 6CO,,
* Unless otherwise specified, heat capacity and heat content data will be found Tables II and V, respectively, or at the end of the book.
in
EXERCISES
and that
93
using heat of formation data. The heat of vaporization of benzene is 103 cal. g.~ l of water is 583.6 cal. g.~l at 25 C. 4. Calculate the change in heat content for the reaction occurring in the lead storage battery, via.,
Pb
+ PbOj + 2HtS0
4
(in20%aq.soln.)
2PbS0 4
+ 2H O (in 20% H*SO
2
4
soln.),
assuming the volume of solution to be so large that its concentration does not change appreciably. The integral heat of solution (A//) of sulfuric acid in water to form a 20% solution is 17.3 kcal. mole"* 1 at 25 C. The heat of formation of water in the acid solution may be taken as the same as for pure water. 5. The change of heat content for the reaction
Cl 2 to)
is
+ 2H 0(J)
2

HS0
4 (aq)
+ 2HCl(a$)
74.1 kcal. at 25
C.
The
of sulfur dioxide, sulfuric acid
kcal., respectively.
its
and hydrochloric acid are 8.5, Determine the heat of formation of pure
integral heats of solution (Aff) at infinite dilution 23.5 and 17.9 sulfuric acid from
elements.
6. Taking the mean molar heat capacities of gaseous hydrogen, iodine and l hydrogen iodide as 6.95, 8.02 and 7.14 cal. deg.~ respectively, calculate the heat of formation of hydrogen iodide from the gaseous elements at 225 C. The heat
,
of sublimation of solid iodine is 58.5 cal. g.~ l at 25 C. 7. The heat of solution of zinc in very dilute hydrochloric acid solution is 36.17 kcal. per g. atom, but in a solution consisting of HCl.lOOHsO, the heat of solution is 36.19 kcal. The integral heat of solution of 1 mole zinc chloride in 200 moles water is 15.30 kcal., and in an infinite amount of water it is
What is the integral heat of infinite dilution of the HCl.lOOHsO 16.00 kcal. solution per mole of HC1? 8. Derive a general expression for the variation with temperature of the change of heat content for the reaction
H,Sto)

+
U0,to)
= H0to) +
S0to).
Calculate the value of A// at 800 K.
9. Derive a general expression for the variation with temperature of the standard heat change of the reaction
Calculate the value of 10. Determine the maximum flame temperature when methane is burnt with the theoretical amount of air (10 2 to 4N 2 ) at 25 C and constant pressure, assuming combustion to be 80% complete. Dissociation of the products at high temperatures may be neglected. 11. Carbon monoxide is mixed with 25% more than the amount of air (1O 2 to 4N 2 ) required theoretically for complete combustion, and the mixture is preheated to 500 C. Determine the maximum flame temperature, assuming the carbon monoxide to be completely converted into the dioxide. 12. small quantity of liquid ethanol is placed in an explosion bomb together with twice the theoretical amount of oxygen at 25 C and 1 atm. pressure. Taking the heat of vaporization of the alcohol as 9.5 kcal. mole" 1 at 25 C, calculate the maximum explosion temperature and the maximum explosion pressure, assuming
ZnOW + C() A# at 600 K.
Zn()
+ CO to).
A
94
THERMOCHEMISTRY
adiabatic conditions and ideal behavior. The combustion of the ethanol is to be taken as complete, with water vapor and carbon dioxide as the sole products. 13. Compare the maximum flame temperatures for the complete combustion
of (i) acetylene, (ii) hydrogen gas containing by weight of atomic hydrogen, in the theoretical amount of oxygen, originally at 25 C, at 1 atm. pressure. For is  103.4 kcal. at 25 C; the heat capacity the reaction 2H = 2 , the value of of atomic hydrogen may be taken as independent of temperature, with Cp equal
2%
H
A#
to 5.0 cal. deg."1 mole" 1 . mixture of equimolecular 14.
A
amounts
of
hydrogen and carbon monoxide,
together with the theoretical quantity of air (10 2 to 4N 2 ) for the combustion, at a total pressure of 5 atm. at 25 C, is exploded in a closed vessel. Estimate the maximum temperature and pressure that could be attained, assuming combustion to be complete. The heat capacity data in Table II may be regarded as being applicable in the required pressure range, and the gases may be treated as behaving
550 C is mixed with the theoretical amount of air, assumed to consist of 21 moles 02 to 79 moles N 2 at 25 C, and the mixture is passed into a converter in which the gases react at 450 C. Assuming virtually complete conversion, how mucn overall heat is liberated for each mole of sulfur trioxide formed? 16. Steam at a temperature of 150 C is passed over coke at 1000 C, so that H 2 (0) takes place with an efficiency of the reaction C(s) + H 2 0(0) = C0(0) 80%, i.e., 20% of the steam remains unreacted; the gases emerge at 700 C. Calculate the amount of heat which must be supplied per kg. of steam passing over
,
ideally. 15. Sulfur dioxide at
+
the coke; the heat capacity of the latter may be taken as equal to that of graphite. 17. The reaction C() 2 0(0) J0 2 (0) = C0(g) is exothermic, whereas C() = C0(0) is 2 (0) endothermic; theoretically, therefore, it should be possible to pass a mixture of steam and air (10 2 to 4N 2 ) over heated coke so that its temperature remains constant. Assuming virtually complete reaction in each case, estimate the proportion of steam to air, both preheated to 100 C, which should maintain the temperature of the coke at 1000 K. 18. According to Prosen and Rossini (see ref. 4), the heat of formation of a gaseous normal paraffin containing more than five carbon atoms at 25 C is given 4.926n kcal. mole" 1 where n is the number of carbon atoms in 10.408 by the molecule. Calculate the heat of formation of gaseous nhexane (C6HiO and compare the result with those given by the rules of Thornton and of Kharasch, and with the experimental value derived from the heat of combustion. 19. Estimate from the bond energies the approximate heat changes for the
+H
+
+H
,
following gaseous reactions:
(iii)
(i)
CH I + H
3
S
= CH 3 OH
H +
2
$O 2 =
H
2
0,
(ii)
C H4
2
+
Br 2 =
+
HI,
(iv)
3CH 3 COCH 3
(acetone)
(mesitylerie) 20. Determine
3
+ 3H 0.
2
C 2 H 4 Br 2 = C 6 H 3 (CH3 ) 3
,
A// for the reaction
3 (Z)
CH COCH
+ 20
2 (0)
=
CH COOH(0 + C0
3
2 fo)
+ H 0(0),
2
427 and taking the heats of combustion of liquid acetone and acetic acid as 209 kcal., respectively. Compare the result with that derived from bond energies allowing for the resonance energy in carbon dioxide and acetic acid.
CHAPTER
VI
CALCULATION OF ENERGY AND HEAT CAPACITY
15.
CLASSICAL THEORY
The treatment of heat capacities 15a. The Kinetic Theory of Gases. given in the preceding chapters has been based partly on the use of thermodynamic relationships, and partly on experimental data relating to the actual heat capacities and their variation with temperature. The results and conclusions are, therefore, independent of any theories concerning the existence and behavior of molecules. However, by means of such theories valuable information has been obtained of a practical character, having a definite bearing on thermodynamic problems. For this reason, consideration will be given to certain theories of heat capacity, especially as some of the principles involved will be required in another connection at a later stage. If it is postulated that an ideal gas consists of rapidly moving, perfectly elastic particles, i.e., the molecules, which do not attract each other, and which have dimensions negligible in comparison with the total volume of the gas, it is possible by the application of the laws of classical mechanics to derive an expression for the gas pressure. This approach to the study of gases, known as the kinetic theory of gases, leads to the result
PV =
\Nmc\
(15.1)
where P is the pressure of the gas, V is the volume containing JV molecules of mass m, and <? is the mean square of the velocities of the molecules at the experimental temperature. If this result is combined with the equation of state for 1 mole of an ideal gas, viz., PV = RT, is found that
%Nmc? = RT, %Nmc* = %RT,
where
is
(15.2)
N is now the Avogadro number,
if
i.e.,
the
number
of individual mole
cules in one mole.
mole
Jme?, it of gas;
Since the mean kinetic energy of translation per molecule follows that %Nmc? is equal to the total translational energy of the
this is xepresented
by Etr equation
.,
(15.2) gives
tr.
=
fflr.
(15.3)
15b. Kinetic Theory and Heat Capacity of Monatomic Gases. If the energy of a molecule is supposed to be entirely translational,* then ir as
E
.
of energy, e.g., electronic and It will be seen nuclear, but these may be regarded as being independent of temperature. from equations (9.0) and (9.11) that only energy which varies with temperature can affect
*
Monatomic molecules undoubtedly possess other forms
95
96
CALCULATION OP ENERGY AND HEAT CAPACITY
identified with the energy content
(9.9)
15c
given by equation (15.3) may be mole of gas, so that by equation volume is *
E of
1
the molar heat capacity at constant
Cr(l
The molar heat capacity of an ideal gas, whose energy is that of translational motion only, should thus have a constant value, independent of temperature Since R is 1.987 cal. deg. 1 mole1 as well as of pressure ( 9e), namely f/J.
,
it
follows that
Cv =
2.980
cal.
1 1 deg. mole
.
It was seen in 9g that for an ideal gas Cp under consideration, CP = C v + R = fR
Cv = R,
so that for the gas
=
4.967
cal.
1 1 deg. mole
.
(15.5)
The
respectively,
ratio of the heat capacities of the gas at constant pressure is given by equations (15.4) and (15.5) as
and volume,
= I ^ Ly
1.667."
(15.6)
For certain monatomic gases, such as helium, neon, argon, and mercury and sodium vapors, the ratio of the heat capacities at moderate temperatures has been found to be very close to 1.67, as required by equation (15.6). The values of the individual heat capacities at constant pressure and constant volume are 5.0 and 3.0 cal. deg.~ mole"" 1 respectively, in agreement with equations (15.5) and (15.4). It appears, therefore, that for a number of monatomic gases the energy of the molecules, at least that part which varies with temperature and so affects the heat capacity, is entirely, or almost
l
,
16f). entirely, translational in character (see, however, 15c. Polyatomic Molecules: Rotational and Vibrational
Energy.
For
gases consisting of molecules containing two or more atoms, the ratio of the heat capacities is less than 1.67, under ordinary conditions, and the values of CP and Cv are larger than those given above. The only exceptions are the diatomic molecules hydrogen and deuterium, for which equations (15.4) and (15.5) have been found to apply at very low temperatures, about 50 K. However, the values are not constant, as they often are for monatomic molecules, and at ordinary temperatures Cp and Cv have increased to ap
proximately 6.9 and 4.9
1 l deg.~ mole" respectively; the ratio is then about 1.4, as it is for most other diatomic gases, e.g., nitrogen, oxygen, carbon monoxide, hydrogen chloride, etc., ( lOe). In each case, further
cal.
,
the heat capacity, and so these other forms of energy can be neglected for the present. Polyatomic molecules also possess rotational and vibrational energy; these vary with temperature and so contribute to the heat capacity ( 15c). * Since E^. is independent of the volume, the partial differential notation in equation (15.4) is unnecessary, but it is retained here and subsequently for the sake of consistency.
I5d
CLASSICAL THEORY
97
rise of temperature causes the heat capacities to increase, although the difference between CP and C v always remains equal to about 2 cal. deg.1 mole" 1 provided the pressure is not greatly in excess of atmospheric. The reason why the heat capacities of polyatomic molecules are larger than the values given by equations (15.4) and (15.5) is that molecules of this type possess rotational energy and vibrational energy, in addition to the energy of translation. The rotational energy of a polyatomic molecule is due to the rotation of the molecule as a whole about three (or two) axes at right angles to one another, and vibrational energy is associated with the The inclusion of these eneroscillations of the atoms within the molecule. gies in the energy content of the molecule, and their increase with rising temperature, accounts for the discrepancy between the actual behavior of polyatomic molecules and the theoretical behavior described in 15b. At sufficiently low temperatures the effect of the rotational energy and, especially, of the vibrational energy becomes inappreciable; this explains why hydrogen and deuterium behave like monatomic gases in the vicinity of 220 C. Other polyatomic gases would, no doubt, exhibit a 50 K, i.e., similar behavior, but they liquefy before the rotational energy contribution to the heat capacity has become negligible. The decrease of CP and Cv to 5 and 3 cal. deg."1 mole"" 1 respectively, although theoretically possible, can thus not be observed. 15d. Principle of Equipartition of Energy. The contributions of the vibrational and rotational motions to the energy and heat capacity of a molecule can be calculated by classical methods, and although the results are not correct, except at sufficiently high temperatures, for reasons to be explained later, the procedure is, nevertheless, instructive. According to the principle of the equipartition of energy, 1 each kind of energy of a molecule that can be expressed in the general form ax*> referred to as a "square term" or "quadratic term," where x is a coordinate or a momentum, contributes an amount \RT to the average energy of 1 mole. The translational (kinetic) 2 2 22 ), where x, y and z represent y energy of a molecule is equal to Jm(x the components of its velocity in three directions at right angles. The momentum px for example, is equal to mx, and so the energy is given by By the prinP*)/2ra, thus consisting of three quadratic terms. Pv (pl ciple of the equipartition of energy, therefore, the translational energy should be 3 X !#T, i.e., f RT, in agreement with equation (15.3). The rotational energy of a molecule, assumed to be of constant dimensions, is proportional to the square of the angular momentum, so that each type of rotation is represented by one square term, and thus should conA diatomic molecule, or any tribute \RT per mole to the energy content. linear molecule, exhibits rotation about two axes perpendicular to the line The rotational energy of a diatomic, or any linear, joining the nuclei.
, ,
+
+
,
+
+
1 R. C. Tolman, "The Principles of Statistical Mechanics/' 1938, pp. 93 et seq.; R. H. Fowler and E. A. Guggenheim, "Statistical Thermodynamics/' 1939, pp. 121 ei seq.; J. E. "Statistical Mechanics," 1940, pp. 144 et *g.; 8. Glasstone, Mayer and M..G. Mayer, 9 "Theoretical Chemistry/ 1944, pp. 300 et teq.
98
CALCULATION OF ENERGY AND HEAT CAPACITY
15e
molecule should thus be 2 X \RT, i.e., RT, per mole. A nonlinear molecule, on the other hand, can rotate about three axes, so that the rotation should contribute 3 X $RT, i.e., fflT, per mole to the energy of the system. The energy of a harmonic oscillator is given by the sum of two quadratic terms, one representing the kinetic energy and the other the potential energy of the vibration. By the equipartition principle, the energy is thus expected to be 2 X i/23P, i.e., RT per mole for each possible mode of vibration. In 6 modes of general, a nonlinear molecule containing n atoms possesses 3n vibrational contribution that the should be so 6)RT (3n energy vibration, 5 vibrational per mole. Diatomic and linear molecules, however, have 3n 5>)RT per mole. modes, and the vibrational energy is expected to be (3n 15e. Classical Calculation of Heat Capacities. For a diatomic molecule two types of rotation are possible, as seen above, contributing RT per mole to the energy. Since there are two atoms in the molecule, i.e., n is 2, there is only one mode of vibration, and the vibrational energy should be RT per mole. If the diatomic molecules rotate, but the atoms do not vibrate, the total energy content E will be the sum of the translational and rotational = fRT, per mole; hence, energies, i.e., f RT + RT
9
CV(tr.
+
rot.)
=
(?}
&
*fl,
so that the heat capacity at constant volume should be about 5 cal. deg. 1 mole1 The same result would be obtained if there is vibration of the atoms in the diatomic molecule, but no rotational motion. If, however, the molecule rotates and the atoms also vibrate, the energy content should be
.
f#T
+ RT + RT
i.e.,
%RT, per mole; then
CV(tr.
+
rot.
+ vib.) =
.
about 7 cal. deg.1 mole" 1 The heat capacities of the diatomic gases, hydrogen, oxygen, carbon monoxide and hydrogen chloride, are all very close to 5 cal. deg. 1 mole" 1
that
is,
It appears, therefore, that in these diatomic at ordinary temperatures. molecules there is either vibration or rotation, but not both, the rotational motion being the more probable. According to the classical equipartition 1 1 principle, the value of Cv should remain at 5 cal. deg. mole with increasof or vibration, until the other rotation ing temperature, type energy, i.e.,
respectively, becomes excited; the heat capacity at constant volume should then increase sharply to 7 cal. deg.1 mole"1 This is, however, quite contrary to experience: the heat capacity increases gradually, and not suddenly, as the temperature is raised. Even at 2000 C, the heat capacities Cv of hydrogen, nitrogen, oxygen and carbon monoxide are only 6.3, although that 1 1 For chlorine gas the value of .of hydrogen chloride is 6.9 cal. deg. mole. .
already 6.0 at ordinary temperatures, and becomes equal to 7.0 cal. 1 mole1 at about 500 C; it then increases, very slowly, to 7.2 cal. deg.1 deg mole1 at 2000 C.
is
Cv
16a
16.
QUANTUM STATISTICAL THEORY OP HEAT CAPACITY
99
QUANTUM
STATISTICAL
THEORY OF HEAT CAPACITY
It is clear that as far as diatomic 16a. Quantum Theory of Energy. molecules are concerned the experimental heat capacities and their variation with temperature are not entirely consistent with the equipartition principle; the same is found to be true for other polyatomic molecules. In every case, however, the theoretical heat capacity is approached, or slightly exceeded, as the temperature is raised. Nevertheless, the approach is gradual, whereas the classical treatment would imply a sudden change from one value to another. An attempt to overcome this discrepancy was made by suggesting that the development of a new type of motion, with increasing temperature, did not occur with all the molecules at the same time. Thus, at any tem
perature a gas might consist of a mixture of molecules, some of which were rotating and not vibrating, but others were rotating as well as vibrating. However, no adequate theoretical treatment could be developed to account
quantitatively for the experimental facts.
more satisfactory and complete interpretation of the observaprovided by the quantum theory, according to which a molecule As far as transacquires its energy in the form of definite amounts or quanta. lational energy is concerned, the quanta are so small that the energy is taken up in a virtually continuous manner. As a result, the behavior corresponds to that required by the classical theory. Rotational quanta are also small, although considerably larger than those of translational energy; hence, at ordinary temperatures nearly all the molecules possess appreciable amounts
tions
is
A much
(quanta) of rotational energy. The energy contribution is again in good agreement with that required by the equipartition principle, i.e., %RT per mole, for each type of rotation. The vibrational quanta, on the other hand, are much larger, and at ordinary temperatures the vibrational energy of most molecules is that of the lowest quantum level. In this event, the vibrational energy does not affect the heat capacity, as is the case for the majority of diatomic molecules. As the temperature is raised the molecules acquire increasing numbers of quanta of vibrational energy, with the result that the contribution to the heat capacity increases toward the classical value of R, i.e., about 2 cal. 1 1 deg." mole"" for each mode of vibration. This accounts for the steady increase of the heat capacities at constant volume of several diatomic molecules from 5 at ordinary temperatures to 7 cal. deg.~J mole"" 1 as the temperature is raised. With chlorine, the vibrational energy quanta are not too large, because the binding energy of two chlorine atoms is smaller than that for most other diatomic molecules (cf. Table VTI). Consequently, the number of molecules possessing one or more quanta of vibrational energy increases with temperature, even at normal temperatures; hence, the molar heat capacity CV of chlorine already exceeds fR at C, and reaches }/2 at about 500 C. The quantum theory thus permits of a qualitative explanation of the heat capacity observations for diatomic molecules, and also of
,
100
CALCULATION OF ENERGY AND HEAT CAPACITY
16b
is
It will now be shown that a quantitative interpretation also possible. 16b. The Partition Function. The molecules of a gas do not all have the same energy ; in fact any value of the energy, consistent with the requirement
other molecules.
be made up of whole numbers of the various quanta, e.g., of and vibrational energy, is possible. However, it can be shown by the methods of statistical mechanics that at each temperature there is a particular distribution of the total energy of a gas among its constituent molecules which is much more probable than any other
that
it shall
translational, rotational
distribution. 9
Consider a system, such as an ideal gas, consisting of a total number of According to the quantum theory, the energy of each molecule at any instant must have a definite value involving a specific number of quanta. Let * represent the energy, in excess of the lowest possible value, of one of these permitted states of the It has been shown by the methods of wave mechanics that even molecules. at the absolute zero a molecule would still possess a definite amount of energy, particularly vibrational energy; this quantity, referred to as the zeropoint energy of the molecule, is the lowest value which acts as the reference level postulated above. Suppose 7V is the number of molecules in this lowest energy state, and AT is the number in the level in which the energy is The most probable energy distribution among the molecules, contained in a vessel of constant volume, at the absolute temperature T, is then given by statistical mechanics as
N molecules which do not attract or repd each other.
.
(16.1)
equal to the molar gas constant result is an expression of the MaxwellBoltzmann law of the distribution of energy. Although the law was derived from classical mechanics, it has been found that, at all temperatures above the lowest, quantum considerations lead to a result which One modification is, is almost identical with that given by equation (16.1). however, necessary: this is the introduction of a statistical weight factor 0* representing the number of possible quantum states having the same, or almost the same, energy e*. The appropriate form of the energy distribution
is
R divided by the Avogadro number.*
where fc, known as the Boltzmann constant,
The foregoing
law
is
then
1
(16.2)
where
If
i,
j,
0o is the statistical weight of the lowest energy level. the various energy values, represented by the general term are etc., and the numbers of molecules possessing these energies are
,
<o,
flee
1 For a fuller treatment of this subject and of other matters considered in this chapter, the works mentioned in ref. 1. * The Boltcmann constant k is usually expressed in ergs deg.~l ; thus R is 8.814 10T 1 l 1 mole" and so the number is 6.023 k that is 8.314 mole" 10V ergs deg.~ Avogadro , 6.028 10*  1.380! KT" erg deg.~*.
X HP
X X
X
X
Ni molecules each possess energy e t the total energy content. Q  Z g*e' o ilkT . and is represented by the symbol Q *. by equation Eo (16. are the statistical weights of the respective levels.4) It follows.3) and (16. in general. ^gie*i (16.e< /fcr +) (16.e.4).2) written in the form (16.6) and hence.3) go to taken over all integral values of i. Energy. of the whole system of . that is. corresponding summation term in equation (16.~ Eo = #o + JViei + r N** + + N#t + . from zero to to all possible energy states of the molecules. then the total number of molecules of these individual numbers. If E is the actual energy content molecules and E Q is the total energy when they are all in the lowest possible level. then is of the N EE. This may be put in the form N where the summation is =  g#* tkr .4) that No/g Q = N/Q'.. of the molecules in the ith level is molecules total energy. The infinity.3) is known as the partition function of the molecule. and multiplying the result by kT*.5) 16c.7) differentiating equation (16. (16. the volume being constant.5) (<7o*oe"* + <7iie"'* r + + <7. N is equal N where ?o> result .. N .. from equations it is substituting this result in (16. . Since. thus. as postulated tion. etc. above. QUANTUM STATISTICAL THEORY OF HEAT CAPACITY 101 to the sum or Ni. in general. Heat Capacity and the Partition Function. in excess of the zero level. then given by the sum of all such terms. which defines the partition funcwith respect to temperature. seen that the distribution law may be Ni = kT . (16. in the excess of the zerolevel value. (16. therefore.16C etc.No + Ni + 9* JNT 2 +  + Ni +   g\ 9 0*. it is found that Upon ( * H) = is This should not be confused with the heat quantity for which the same symbol used.
<=. such as atomic oxygen and the halogens. . provided the gas is almost ideal.(!)'] where Q'   gjr** T and Q" = ^ (  Y gjr". for example. The energy values c 1. . of the equations derived late the heat capacity of . Corrections for deviations from ideal behavior can be made if necessary ( 21d).dQ/d(l/T) and Q"  dQ/d(l/!T). . gives The for the molar heat capacity of an ideal gas system at constant volume. . that is to say. remembering that EQ is constant.. 16d. .7) 16d It is evident. In order to simplify the computation of heat capacities from partition functions it is often convenient to utilize the fact that equation (16. t which have multiplet electronic levels at ordinary temperatures.8) Finally.8) with respect to temperature. at constant volume. allowance must also frequently be made for the electronic energy because the molecules are not necessarily all in a single electronic energy level. This is the case. rotational and vibrational contributions. * It should be noted that Q' . provided the forces between the molecules are small. differentiation of equation (16.9) can be converted into the form [.9) is applicable to any gas. in accordance with equation (9. value of C P can then be obtained by the addition of R. the molar gas constant. therefore.4)] refer to the total energy of a single molecule. The problem is thus reduced to a study of the evaluation of this property of a molecular species. used in the definition of the partition function [equation (16. . that may be written as is the Avogadro the system under consideration consists of 1 mole of gas. By means .29). and excited electronic states for which allowance must be made at higher temperatures. is equal to R. . the expression for the energy content per mole is then If N number and Nk (16. Separation of Energy Contributions. The result expressed by equation (16. above it should be possible to calcua gas at any temperature provided information concerning the partition function is available.102 CALCULATION OF ENERGY AND HEAT CAPACITY equation (16. including the translational. for a number of monatomic substances.
dT * dT d\nQ dT This result follows from the mathematical fact that the product of sums of the products. greatly simplifies its evaluation. er and represent the separate electronic.12). is equal to the sum . translational. At high temperatures. but in which g and The subdivision refer to the particular type of energy under consideration. the statistical weight factor g is equal also to the product of the separate factors for the various forms of energy. and ej c<. the electronic contribution to the partition function is virtually a factor of unity at ordinary temperatures.9) that the energy and heat capacity of a gas depend on the logarithm of the complete partition Since the latter is equal to the product of the factors for the function. consideration. Thus. each characteristic of one type of energy. rotational and vibrational partition functions. (16. the total energy content and heat capacity of the molecules will be equal to the sum of the contributions obtained by inserting the appropriate partition functions in the aforementioned equations. it is possible to write = or e</kT c + Ct + *T r + v = e*. It is evident from equation (16.8) and (16. several forms of energy. the complete partition function Q may be divided into a number of factors. may be taken as the product of a number of terms of the same type. this it There is also becomes important and must be taken into a nuclear effect on the partition function.. so that it can be ignored. As a result. which is probably justifiable.ii x e *rikT x e* lkT. InQ = InQe so that e + lnQt + t . one for each kind of energy. 24j).* viz. which defines the partition function. Further. translational.. translational and combined rotational and vibrational energies are concerned.4). term in (16. respectively. Qr and Q v are called the electronic. but be neglected for the present (cf. It will be observed from equations (16. (16. however.16d QUANTUM STATISTICAL THEORY OP HEAT CAPACITY of 103 For most common polyatomic molecules. with the exception oxygen and nitric oxide. Each of these is defined by an expression identical in form with equation (16. rotational and vibrational contributions.11) that each exponential respectively.4). Qe X Qt XQ XQ r v. of the total partition function into a number of products. where Q = where .11) is the total energy per molecule. at least as may If far as electronic. from equation (16. the various forms of energy of a molecule may be regarded as completely separable from one another.12) Qe Qt.fkT x cr.
ra is the mass of the molecule which is confined in a box of length I in the direction parallel to the given energy com27 ponent. Translational Partition Function. and h is the Planck (quantum theory) constant.14) the summation being carried over all values of the quantum numbers from zero to infinity. i. together * spaced. with the constant volume restriction. The summation in equation (16. the corresponding contribution to the partition function will be considered first.13). and so weight unity. as for the derived Qci) = L <r'* r = nO E e. showing that the translational quantum levels must be closely (16. Since all molecules. result may thus be compared with $kT. so that  jn r f (16. need not be used. etc. monatomic or polyatomic.e..15) This can bo shown by inserting the value for m. hence. after inserting the energy expression from (16. for any molecular species.* the variation of energy may be regarded as being virtually continuous. that the only partition function factor which is dependent on the volume is the translations! contribution. The latter will be found to be of the order of 10 17 times the former. This is determined by utilizing the expression (1(U3) component in one direction of the translational energy of a molecule.4).624 X 10~ translational is of each The statistical level sec. erg the partition function for translational motion in one direction is given by equation (16. 6. the energy The separation of successive quantum levels can then be found by setting n 1. and similarly for the heat capacity. This result is the basis of the procedure which will now be adopted for the derivation of expressions for the energy and heat capacity of various types of molecules.8). 2. It may be mentioned. possess translations! energy.104 CALCULATION OF ENERGY AND HEAT CAPACITY 166 Consequently. . instead of stepwise. as it actually is.11 ** (16. Since translational levels are very closely spaced. in anticipation.13). at ordinary temperatures.. in equation with the Planck constant. by means of wave mechanics. the average translational energy of a single molecule in one direction. by equation (16.14) may thus be replaced by integration. 16e. taking I as 1 cm. for example. in all other cases the partial differential notation. n is a quantum number which may have any integral (or zero) value.1 * 1 ' 8 .
states. Since the pressure is given. 1 The mass m of the oxygen molecule is equal to the mocc.2. Electronic States: Monatomic Gases. h and V are all constant.06 X 298.2) 3/ ' 82. since the quantum theory leads to the s'ame results as does the classical treatment. so that  Qi It  (2irmkT)*'* 3? RT T" see that can be readily shown that Qt is dimensionless. its value must be determined for the calculation of energies and heat capacities.atm. so that R should be in case. that the translational contribution E t to the energy.16) where at J 1 has been replaced by V. assuming the gas to behave ideally.. k. In this k and h are known in c.16) by RT/P.16)] is of the greatest importance in connection with other thermodynamic properties. temperature T is 298. 1 Problem: Calculate the translational partition function for 1 mole of oxygen atm. < '* V..313 X 1Q*3 X 1. in their normal dioxide.000 If 4. Nevertheless. it is readily found.28 X 10 30 . i. whose energy is appreciably greater than that of the Such excited states become increasingly occupied as the temperature is raised.16f QUANTUM The STATISTICAL THEORY OF HEAT CAPACITY 105 contribution of each of the components of the translations! energy. hence.e. as will be seen in Chapter IX. deg. 5.gjs. translational energy may be treated as essentially classical in behavior.g. unity. m. is represented by equation (16. pressure at 25 C. is equal to f RT per mole. 16f. the partition function derived above [equation (16. nitric oxide and nitrogen That is to say. in excess of the zeropoint value. In cases of this kind the electronic partition function is greater than unity and varies with temperature. oxygen. the expression for the translational partition function is inserted into equation (16. (16. units. Qt _ ~ (2 X 3. in three directions at right angles.00 divided by the Avogadro number. .313 X 10~ g. .8).380 7 3 X IP" 16 X 298. As stated earlier.2 (6.624 X 10* ) 1. which is precisely the classical value. have multiplet electronic ground states. so that all that is necessary is to numerator and denominator are expressed in the same units. since TT. greater normal (ground) states. Many monatomic substances. therefore. m. e. thus. it is convenient to replace V in equation (16.1416 X 5. and the complete translational partition function is obtained by multiplication of the three identical expressions.. as well as a few polyatomic molecules. states there are two or more different electronic levels with energies so close tofactor gether that they may be considered as a single level with a statistical weight electronic excited be there this to In addition than may possibility." 1 mole"" 28 The lecular weight 32. The corresponding molar heat capacity at constant volume is thus f R. P is 1 atm.15). the volume of the gas.
1 is unity. and since no higher (excited) level need be considered. the velocity of light.fkT . In the ground state. 1 were not unity.9977 10" X cm. equal to the translational value. The frequency in "wave numbers. the contribution to + + + + E be zero.""1 . in wave numbers. . Upon inserting the Appendix). but these may be neglected here." or cm.17) I)****.e. the ground state. at all reasonable temperatures.. a small increase would be observed.8) and (16. sec. divided by the velocity of light.19) where h * is the Planck constant and c values of h. i. from the spectra of these atoms.9)].18) 4 + 2e. the energy e. energy corresponding frequency \ where ground is state. The expression for the electronic factor in the partition function is then given by Q. . (16. the energy 1 is found from the spectrum of atomic chlorine. and mercury. because of the occupation of higher electronic levels. neon. + E7 + where c. the effect on the energy and heat capacity would still be 2j zero. Q.""1 units. therefore. normal or excited. the electronic energy of the upper level.106 CALCULATION OF ENERGY AND HEAT CAPACITY 16f The statistical weight factor of each electronic level. the value of j is f not very far above The electronic partition function for atomic this is another state in which j is chlorine at ordinary temperatures is therefore given by equation (16.^1 is represented by = is vhc. i. and so can be disregarded. in excess of the value in the At higher temperatures other terms would have to be included for The value of electronic states of higher energy. it is derived from the l separation of two lines whose frequencies. in the lowest state of the chlorine atom. where j refers to the ground state.e.438s cm. and hence it is an integer which and Cy will consequently is independent of temperature. function is thus 2j the lowest energy state is found to be zero.e. equations (16."1 units.. sec. where j is the socalled "resultant" quantum number of the atom equal to 2j in the given state. it is found that hc/k is 1. when e is zero. For example. i. c and k (see Table 1. etc. hence.. Provided the ground state of the atom is the only state which need be considered. however. (16. so that the exponential factor e~** lkT is unity. i. to the c the to a of According quantum theory. for these quantities are dependent on derivatives of the logarithm of the partition function with respect to temperature Ccf. The contribution of this state to the electronic partition For helium.* differ by 881 cm. 2.~ . is 1. and hence the appropriate terms must be included in the partition function. the value of j in 1. except at very high temperatures. is equal to the frequency expressed in vibrations per second. the elec2j Even if tronic partition function factor is also unity.. \R. =  (2 X f + l)<r'* r + (2 X * + l)e< (16. is zero. Qi is 2/ 1. It appears from spectroscopic studies that helium. If accurate observations could be made at high temperatures. argon and mercury atoms are almost exclusively in a single (ground) state and that higher (excited) electronic energy states are not occupied to any appreciable extent..17) as . is the energy of the electronic state in excess of the lowest state. behave in the manner required by the The heat capacities of these monatomic substances are thus classical treatment. For some atoms one or more electronic states above the ground state are appreciably occupied even at moderate temperatures. v cm. neon.e. These gases.
= 4 + 2e.~ g. 4 + 2e. The results in the problem given above show that at 300 the electronic contribution to the molar heat capacity of atomic chlorine is 0. atom" 1 .10). appreciable even at 300 K.128. contains one term only. 2.546 X 10 s / 200.546 X Q".029. Q . Q. chlorine at Problem: Calculate the electronic contribution to the heat capacity of atomic (i) 300 K. since t/k is 1268 for the higher level.18) and (16. as seen in equation (16.1268 X 2<r = (1268) 2 X 2e. since e/k is zero for the lowest level.8) and (16.8WAc/ * r = 4 + 2e1268/r . Q.8 #1 = . The calculation is most conveniently made by means of equation (16.20) Hence the electronic contribution to the energy content and the heat capacity at any (moderate) temperature can be determined by means of equations (16. As seen above. f > 10 5 ' " = ] 4. on the energy and heat capacity also becomes much more K apparent.236JK = 0. ] 4. hence.10). it may be stated that if for any level e/k is greater than about 5T. (16. deg. Q' tJ as defined in connection with equation (16.I6f QUANTUM STATISTICAL THEORY OP HEAT CAPACITY 107 for so that from equations (16.254 cal.02.9). and so this will affect the energy and heat capacity at temperatures exceeding 1268/5.128/2. The normal heat capacity f R. atom" 1 2 R r 2. deg. can contribute to the partition function if the exponential term e~* lkT has an appreciable magnitude. i. of atomic chlorine. i. which is lkT increases quite appreciable. [" R 4." 1 g.029 / J l 0.695 X 104 / 37. Hence.20).. of one term.1268/60 = 4.1268 / 300 = 37.469 cal. the effect.4 + 2e.695 X 104 . /fc is 1268 deg. . (ii) 500 K. = 1268 X 2e. for the first excited level of atomic chlorine. deg.1268 500 = 2.98 cal. As a very rough rule.158 (500) [ \ 4. respectively. then the contribution of that particular level may be neglected at the temperature T.e.8 \ 2 .158 l268/500 = 200. atom. Q" e also consists = (1268) 2 Q" 9 X 2<r 1268 ' 300 = 4. by equation (16. thus. Since e~* rapidly with increasing temperature.02 \ 2 2 = (ii) At 500 K. an energy level.~ g.K = 0.. (i) At 300 K. is and so the electronic contribution would be In general.10).029 (300) [ \ 4. about 250 K. electronic or otherwise.1 .19) the electronic partition function atomic chlorine is found to be Q. due to translational energy only.e.1268 ' 300 = 4.158 / J l 0.
it is not necessary to consider any state other than the ground state of a diatomic molecule.e. because variation with detectable temperature any the energies of the excited electronic levels are so much higher than that of the electhe normal state. each level has a multiplicity of two (A. If. Kundt and E. the actual value of the electronic partition function is important in another thermodynamic connection to be discussed in a subsequent chapter. In molecular oxygen. and the electronic partition function is 3. i. however. 1876). independent of the temperature. a triplet state. more particularly. Hence. at temperatures below at least 2000 tronic contribution to the energy content or heat capacity is negligible for all diatomic molecules. 16g. therefore. The energy separation between the lowest and the next (excited) electronic level of the oxygen molecule is probably one any diatomic substance. a doublet state. For other molecules.. and so the electronic partition function at all reasonable temperatures is unity. Warburg. would fail if applied to atomic chlorine at temperatures exceeding about 260 K.108 CALCULATION OF ENERGY AND HEAT CAPACITY 16g The foregoing calculations show how the classical treatment. however. and of oxygen exceptions in a singlet state. discrepancies would have been observed which would have proved inexplicable until the modern development of the quantum theory.0. since the energy of the next state is usually so high as to be of little practical interest. Spectroscopic measurements indicate that for the atoms of all these elements the energy difference between the lowest and next electronic level is so great that temperatures of several thousand degrees would be required for the second level to make an appreciable contribution to the energy and heat capacity. nitric oxide has two such levels.0. occur in a single electronic level. As mentioned earlier. with the notable nitric oxide. The higher the temperature the greater the discrepancy. it is evident that. . for all ordinary purpartition function. based on the kinetic theory. so that the electronic partition function is actually 4. for diatomic molecules the effect of electronic levels above the ground state can be neglected. the aforementioned substances had possessed lowlying electronic levels. that the molar heat capacity of a monatomic gas should be }/2 at constant volume.e. of the smallest for make a K * In nitric oxide. Similarly. in the vicinity of 300 K.0. still higher temperatures are necessary before electronic states above the ground level have any noticeable effect on the Consequently. atomic oxygen.. which does not take into account the possibility of electronic states. there are three very closely spaced levels. i. and * In neither case. Nearly all such stable molecules. In general. yet this excited level begins to detectable contribution only at temperatures exceeding 2000 K.type doubling).e. Diatomic Molecules: Electronic Partition Function. i. was confirmed first by measurements with mercury vapor (A.. is there so the electronic factor is virtually 2. poses. like atomic chlorine and. It was perhaps fortunate that the original prediction. which is an exception among stable diatomic molecules. and later with sodium vapor and the inert gases of the atmosphere.
.21).16h QUANTUM STATISTICAL THEORY OF HEAT CAPACITY 109 16h. such is the case. and for unsymmetrical molecules . (16. In order to obtain the complete rotational partition function. the statistical weights. so that the rotational energy of the Jth level may be represented by /. 5. with the most abundant isotopic form of molecular oxygen. 1. 3. e. (2i of the For all diatomic molecules. 24j). O2 and C1 2 this is not strictly true. at first sight. that it would be necessary to include a very large number of terms in the summation of equation (16. and hence have no actual existence. and in the other state it can be odd only.. i. 2. NO.e. the nuclear spin factor quantum numbers two l)(2i' nuclei. In principle. and even HD.. Diatomic Molecules: Rotational Partition Function. and the value of each (2J takes on a series of integral values. HC1. 2. viz. tion is therefore not so large as would at first appear. where the nuclei are of different isotopes. 0. The consequence of the nuclei being identical is then allowed for by introducing a symmetry number <r. with the exception of hydrogen below 300 K and of deuterium below 200 K. depending on the spin quantum IC1.g. depending on various circumstances. and hence the exponential factor e~* of which The number terms contribute appreciably to the summarapidly. where i and i' are the spin may be ignored for the present (see. H 2 Dj. a considerable simplification is possible for temperatures above the very lowest. the rotational quantum number J in equation (16.. but for molecules possessing two identical atomic nuclei. etc. included for molecules with dissimilar nuclei. have a statistical all rotational levels. it is necessary. the para states weight of zero. i. respectively.21). however. However. . apart weight is 2J from nuclear spin effects. 9 is 2 for symmetrical diatomic molecules.e. giving the number of equivalent spatial orientaThe value of tions thai a molecule can occupy as a result of simple rotation. for as J increases e/ also JtkT decreases even more increases. to use the correct nuclear spin statistical weight and the proper rotational quantum numbers for each state when making the summation indicated in equation It may be pointed out that a nuclear spin factor should also be (16. (i + l)(2i + 1) and i(2i + 1). the rotational quantum number J can have even values only.21) can have the successive values of 0. 1.21) The rotational energies j can be derived from a study of the spectrum of the JlkT term can be calculated as / V)e~' molecule. It may seem. e. 4. and the rotational factor in the partition function. therefore. all molecules of the latter type can exist in "ortho" and "para" states. etc. If this quantum number is zero.. . + + 1). for example. is given by + Qr  E (a/ + + I)*"**. but this has the same value for number i of the nucleus. The corresponding statistical 1. For a diatomic molecule having two different nuclei.. OH. since it is inde pendent of temperature and makes no contribution to the heat capacity. In one of the states.g. In the first place. either ortho or para.. this is not the case. etc. 3. in which both nuclei have a mass number of 16. The value of the energy of a molecule in any rotational level can be expressed in terms of an integral (or zero) quantum number J.
48 2.e. At temperatures at which the modification described above is permissible. for diatomic molecules. J(/ + l) JL .6 H HD D* 0.. in excess of the lowest. 24k).. consisting of two atoms whose by \jn/jn^/(m\ + WB)]T*. it does not actually affect the heat capacity. the summation may be replaced by integration and.2. i.4 19.9 14. /0. This is the quantity.31 4.22).23) represents the rotational energy. and / is the moment of inertia * of the molecule.66 3.459 0.e. Since the symmetry number is constant for any given molecule. virtually all temperatures at which they are gaseous.3 114. i. (16. so that c/ is zero. a diatomic molecule AB.34 1.* Molecule / g. i. 245 345 743 The moment of inertia of actual masses are m\ and ms. it is seen that Qr (2J + i)e J "+w*** lkT . zeropoint.3. Qr  i ff (2J JO.612 0. other than hydrogen and deuterium. therefore. a further simplification is possible. + l)e"' (16. 16h The rotational partition function is then given by T . but it is inserted here for the sake of completeness (see. one of fixed length. in the Jth level. in any level of quantum number J y is given by the expression e. 2 13. where r is the distance . The rotational energy of a rigid diatomic molecule.22) where J can have all integral values from zero to infinity. after neglecting certain small quantities. cm.e..23) where h is Planck's constant. / cm.1.31 X 10* N O 2 X H)* CO HF OH HC1 NO 2 C1 2 ICl HBr HI * Br a I. hence cj as given by equation (16. Inserting the expression for tj given by equation 0" (16. it is found that (16.920 1. is given between the centers of the atoms.5 16.24) TABLE Molecule VIII.110 it is CALCULATION OF ENERGY AND HEAT CAPACITY unity. however.23) in (16.1.2." Provided the moment of inertia is moderately large and the temperature not too low. In the lowest energy level J is zero. MOMENTS OP INEBTIA OF DIATOMIC MOLECULES g. which is to be used in the determination of the partition function. value.
and since the symmetry 1. / is X X 10~"40 g. one. "Molecular Spectra and Molecular Structure: Diatomic Molecules/' 1039. X .9). so that. 2 .24). part of the latter. the i. so that the rotational parThe values of the moments of inertia tition function can be determined. 2 and its symmetry number a is 2. .e. it is not necessary to know the actual partition For a rigid molecule / function. at all temperatures above the very 16L Rotational Heat Capacity of Molecular Hydrogen.e.624 X 10~27 ) 2 (ii) For iodine is chloride. + + s Data mainlyadapted from G.38 number unity. hence utilizing the known values of k and A.24) that at 300 K. A consideration of the units will show that Q r is dimensionless. The spin quantum and at ordinary (and higher) temperaof the hydrogen (H) nucleus is tures molecular hydrogen. in which the ortho and para forms have attained equil)(2i h 1). at 300 K. (i) From Table VIII. ^r ^ 8 X (3.71.459 lO^40 g.14) 2 X 0.. hydrogen and deuterium. it is readily seen from equation (16. dT and with those obtained from the equipartition prin15d). it is seen from equation (16. as a good approximation. X 245 (6. number .. For the present purpose. that n. is constant. Herzberg.624 X 10~ 27 ) 2 1820. except lowest. (i) hydrogen gas. The socalled relative amounts of ortho and para molecules remain unchanged. librium. but only its variation with temperature. using equations (16.14) 2 X 245 IP"40 X X 1Q" X 300 = (6. k and h are also constant. and since TT. cm.38 X IP" 16 X 300 2 1. the moment of inertia of molecular hydrogen is 0. three. cm. of a number of diatomic molecules in their ground states are given in Table VIII.8) and (16. i. Qr " = 8 X (3. consists of (t If the gas is cooled in the absence of a catalyst. classical methods can be used for the evaluation of the rotational energy and heat capacity of diatomic These ciple results are identical ( gases.161 QUANTUM STATISTICAL THEORY OP HEAT CAPACITY' 111 The moment of inertia can be derived from spectroscopic data or it can be calculated from the dimensions of the molecule.459 X IP"40 X 1. parts of the former to i(2i 1). 8 (ii) Problem: Calculate the rotational partition function of iodine chloride gas.
the rotational energy 2.23). The respective partition functions are now H D K K Q r (ortho)  f l)(2i + i)** 1 4 *' 7 ' ** and Qr (para) = i(2i + 1).23) that the energy separation between successive rotational levels is related in an inverse manner to the moment of inertia of the molecule. As the temperature is raised additional terms temperatures of 50 contribute to the rotational partition function. odd values of the rotational ortho states. separations are small enough for a large proportion of the molecules to occupy the higher levels even at low temperatures.3. the rotational partition functions of the ortho and para forms have been determined at a number of temperatures by summing the appropriate ge~' lkT terms in each case.9) that Cr (ortho) and Cr (para) will both be zero.112 11 CALCULATION OP ENERGY AND HEAT CAPACITY 16i "normal hydrogen. except 2 and HD. after making allowance for departure from ideal behavior.6. and then to calculate the corresponding heat capacities.2. and the values have been found to be in good agreement with measurements made from 80 to 300 K. that a temperature of about 300 has to be reached before the gas can be treated in a classical manner. the rotational heat capacity of "normal" hydrogen is then (7r(ortho) iCV(para). .'" E + l)e~^ kT f even values only of the rotational quantum number being permitted. and hence the rotational heat capacity of "normal" hydrogen will also be zero at and below. For all gases. the moment of inertia is so small (Table VIII). may thus be regarded as consisting of a mixture of three parts of orthohydrogen and one part of parahydrogen. The system is then At 20 it consists of almost 100 per cent para K hydrogen. By utilizing the j values derived from the spectrum of molecular hydrogen. The rotational partition function of orthohydrogen is + <?r (ortho)  (t + l)(2i + is 1) E (2J + l)e" kT . K * If orthopara equilibrium is attained at is form will increase as the temperature known as "equilibrium" hydrogen. With hydrogen. The behavior in respect to rotational energy is therefore virtually classical under all reasonable conditions.4. however. the nuclear spin factor has been included in each case. and that of the para form since only quantum number are associated with the Q ( P ara) r i(2i + 1) (2J /0. In fact. the proportion of the para lowered from about 900 K. In the vicinity of 50 virtually all the molecules of hydrogen are in their lowest possible rotational states. and the separation between successive rotational energy levels so large. every temperature. From these results the heat capacities of "normal" hydrogen have been calculated. It can be seen from equation (16. the quantum number J is then unity for the ortho and zero for the para molecules.* In order to determine the heat capacity of this gas at any temperature it is necessary to evaluate the separate partition functions of the ortho and para forms. for the given temperature. which is the gas commonly used in experimental work. /1. and the heat capacity increases. the heat capacities obtained from the partition functions. It is evident from the appropriate form of equation (16. using the values of ej given by equation (16. are probably more accurate than those derived from experiments at low temperatures.
 (1  e*/*r)i  (1  e1 4 *""). The statistical weight of each vibrational level is unity. Am. and so the partition function is v/kT terms.30) Dennison. Soc.25) wjiere v is the vibrational quantum number which can be zero or integral. The values of the energy in the various quantum levels of a harmonic oscillator are given by the Expression cw K = (v + $)hcu. and a) cm. (16. J.. (16. Davis and Johnston. as for other diatomic gases.1  . 1045 (1934).29) and consequently. tional factor in the partition function may be evaluated by using vibrational energy values cv derived from spectroscopic measurements. is thus oscillator.f ' kT = i?=0 e* h *i kT . for most purposes a simpler procedure is possible. A115. about 200 K.25) as ^fecoj. 4 . Except at high temperatures merely equal to the sum of the e' the number of such terms having appreciable magnitudes is not large.27) The exponential factor is of the form <?"*. as usual. and the corresponding heat capacity will thus be R. Roy. (16. However. (16. so that = where (1  6*) 1 .26) The vibrational partition function is then determined by Q = v e. in wave numbers. 56... Proc. of the given In the lowest energy level v is zero. a somewhat lower temperature. etc. 483 (1927). Chem. if required. a sufficient number of rotational energy levels contribute to the partition functions for the hydrogen gas to be treated in a classical manner. namely."" is the vibration frequency." 1935. Farkas.. is then given by equation (16. A.439 . vhcw. tirid. "Orthohydrogen.e. 4 The vibra16j. the Planck constant and the velocity of light.. Giauque. The rotational partition function will then be given by equation (16. the zeropoint energy. which is the value required for the partition function.24). Parahydrogen. 52. respec1 tively. i. h and c are. The vibrational energy of any level referred to the lowest energy state. (16. and the vibrational energy. 1. Diatomic Molecules: Vibrational Partition Function. is sufficient for virtually classical behavior to be attained. Soc. Since deuterium has a higher moment of inertia than ordinary hydrogen. and the summation can be made without difficulty. (16. 4816 (1030).16 j QUANTUM STATISTICAL THEORY OP HEAT CAPACITY 113 At temperatures of about 300 and above.28) *Q. where x is hcu/kT.
at 300 K. .31) where. x is equal to haa/kT.43X4405/300)l (i . cj is 4405 cm. follows that Qv (ii) = (1 __ e 1. omitting the partial differential notation which is here unnecessary ( 16d). to the energy content.000 (to several significant figures). . 565 cm. for the vibrational contribution to the heat capacity should not be Cv which is the total heat capacity at constant volume. is TABLE Molecule IX.439co/jP. Differentiation :>f equation (16. drogen.3. * (16 ' 32) confused with The symbol C. thus.30) is the vibration frequency.114 CALCULATION OF ENERGY AND HEAT CAPACITY 16 j This expression may be used for the vibrational partition function of a diatomic molecule at all temperatures. Nt CO NO Oj Cl IC1 HF OH HC1 HBr HI Br 2 I. in excess of the Q v as represented by equation (16. is vibrational contribution Ev by inserting dT RT hcu (16. assuming them to be harmonic oscillators.072. The values of this frequency for a number 5 of diatomic molecules are given in Table IX.8). H.~ l 4405 3817 3119 4141 3728 2989 2650 2309 Molecule cm. is obtained (1 (1  C l.439X565/300)l e.* hc I r Seeref.30) into (16.29). (i) For hydrogen.31) with respect to temperature then gives the vibrational heat capacity. but its effect not large. it Problem: Calculate the vibrational partition function of (i) molecular hy(ii) molecular chlorine.2  710 ) 1 = 1. the result." . 1 and since hcu/kT is equal to 1.^1 2360 2168 1907 1580 565 384 323 214 HD D. The anharmonicity correction must be made for precision calculations. the only approximation involved is that the oscillations are supposed to be harmonic in nature. which can be obtained from a study of its spectrum. For chlorine.)! = w is 1. as defined by (16.~ l and hence Qv = = The zerolevel value. The only property of the molecule required for the evaluation of Q9 by equation (16. VIBRATION FREQUENCIES OP DIATOMIC MOLECULES cm.
31) it is seen that hcw/kT. in fact.e. /. S. capacity of the gas increase at the same time. 639 (1943) H. i. nitrogen and carbon monoxide up to about 370 K. Aston).e.. more than 1 cal. must be gradual. 1942.32) to (16.e. There is. there is a rough temperature at which the vibrational contributions to the energy and heat capacity become equal to the classical values to a certain degree of accuracy. viz.32). w is large. on the other hand. 17 (1940) . bon monoxide are somewhat less than for hydrogen.. This means that virtually all the molecules are in their lowest. for the vibration frequency 1 is only 565 cm. the vibrational partition function is then close to unity. 35.. and hence e* may be neglected when x is small.* Upon making directly and C v Ev = and hence RT.. However. At sufficiently high tempera1 to be virtually equal to tures hew/kT becomes small enough for e hculkT in this substitution equation (16. As the temperature is raised hcu/kT decreases..^ 1 . Rev. v 17b). With molecular chlorine. + + + + . 4405 cm.. and the vibrational contribution to the energy and heat capacity will be zero. R. (16.e. and Ev and Cv are very small. vibrational level. as a first at high temperatures should consequently be approximation." 3rd ed. is simplified by tables which give E from x. as indicated earlier ( 15e). The temperature at which hcco/kT becomes small enough for the behavior to be classical depends on the vibration frequency co. of course. 641 (1942). 27. the transition from equation (16. 46. three significant figures. no exact temperature at which this condition arises. vibraThe vibrational contributions to the energy and heat tional energy levels. from hcw/kT. i. for the approach to classical behavior." and the vibrational contribution to the heat capacity becomes per mole at about 1000 K. Taylor and S. referred to as Einstein functions (cf. Appendix I. see also. Chapter IV (J. v = 1... and the partition function increases accordingly. oxygen and carof about 3500 K. Chem. i. which varies from one molecular species to another (Table IX). 2. quite considerable. 'Treatise on Physical Chemistry. Chem. Glasstone. with the values given by the classical equipartition principle.. deg. so that c* . etc.31) and (16. For molecular hydrogen. .g. Ind. Stull and Mayfield. but their behavior is nevertheless not completely classical below 3000 K.. 1 1 x. Wilson. R Sherman and Ewell. even at 300 K. v = 0. Such is found to be the case for hydrogen. i.""1 mole"" 1 . oxygen. Phys. G. e. * all terms beyond the second 1 # In the exponential expansion e* W2I .* At moderate temperatures hcco/kT is relatively large for many diatomic molecules. Chem. Eng. and the vibrational heat capacity does not attain the classical value of R per mole until a temperature The vibration frequencies of nitrogen.33) Cv = The energy and heat capacity identical. it is.33).16j QUANTUM STATISTICAL THEORY OP HEAT CAPACITY 115 The evaluation of the quantities in equations (16. x. This means that increasing numbers of molecules now occupy the higher.. thus accounting for the heat capacity of chlorine being greater than for other diatomic molecules ( 15e). the situation is changed.
translational and rotational contributions to the heat capacity will be classical.56# 1. For the accurate evaluation of partition functions."1 . or by the use of the tables of Einstein functions. degr 1 If the vibrational contribution 1. Diatomic Molecules: Combined Partition Functions. deg. some difference is to be expected. The general principles involved in the evaluation of the partition function.1 mole" 1 . and that excited states make no contribution to the total The electronic contribution to the energy in excess of partition function. making a total of $R or 4. The necessary corrections can be . Nevertheless. and to the heat capacity may thus be taken as zero.e. The treatof the preceding sections has been based on the assumption that vibrational and rotational energies are independent. the vibration has been treated fact that the atoms vibrate.12 cal. which has an odd number of electrons. the total is 6. the lowest level.) 16k. Unless there is definite evidence to the contrary.32). especially at moderate and high temperatures. and hence the energy and heat capacity. as there is for nitrogen dioxide.439 cm. is close to this result. of a molecule containing more than two atoms are quite similar to those described for diatomic molecules. in other words. it is found that Cv = At 300 K. 161. hca) W= 0. and to allow for the anharmonicity of the atomic oscilla ment It is sufficient to state here that the information required for this purpose can be obtained from spectroscopic measurements.116 CALCULATION OP ENERGY AND HEAT CAPACITY 16k Problem: Calculate the vibrational contribution to the molar heat capacity of chlorine gas at 300 K.12 is added. deg. as with monatomic and diatomic molecules. in spite of the In addition. the calculations have been carried out in a number of cases and the results are recorded in the tions. Estimate the total C v for chlorine gas at 300 K.* 1 mole"1 mole"1 (The experimental value which is not very accurate.09 cal. respectively. 21 d.97 cal. in any case. * 1. Polyatomic Molecules. it is necessary to take into account the interaction of the vibrational and rotational motions of the molecule. . it is supposed that the ground state of the molecule consists of a single electronic level. so that the translational motion contributes %RT per mole to the energy content and %R per mole to the heat capacity. the translational energy may be treated as classical at all feasible temperatures. since hc/k is 1. although the treatment of the data is not simple.. because the calculations given above are based on ideal behavior of the gas. the approximation has been made of taking the molecules to be rigid. deg. as perfectly harmonic in nature.. In this case. Further. f R and R. made by means of a suitable equation of state. taking the vibration frequency as 565 cm.. the . literature. i.439X565 300 2JL _ _ Either by insertion of this value in equation (16.
the sum of two of the moments = C.2. 85. For some molecules.78. and the rotational partition function is given by the same equation (16.* C. where A.68. NNO). The moments of inertia of a molecule can be derived from spectroscopic data.08. CH.34). If the nonlinear CCU.27 Molecule Moments 1. ed. so that the product is A*. Henbenc. of Inertia HCN* NjO* CO. molecule is planar. CHC1 3 and 3 C1.g. e. X 10" 40 * Linear molecules.* X 10* g.S SOi NH. 4. 8 . COS. so that the product of inertia becomes 2 C.3. Assuming that the molecule can be represented as a rigid rotator. B NH CH ABC A B +B C 6H6 (12). cm.3. (16. excluding the nuclear spin factor.9 71. The values for a number of simple molecules are given in Table X. i. For spherically symmetrical molecules.36.02. or they may be calculated from the interatomic distances obtained by electron diffraction methods. .61.C1 CH. 5.9 66. 7 HCN.94 2.e. etc.24) as for a diatomic molecule.8 5. A some polyatomic molecules are as follows: CO 2 . it is that Er is f RT and Cr is f R. 3rd Supplement. e. For A linear molecule containing more than two atoms is analogous to a diatomic molecule.5 2. two of the three moments of inertia. 4.85.H. It has two identical moments of inertia. 2.e.92. f Spherically (symmetrical molecules. given by and C are the moments of inertia of the molecule with respect to three perpendicular axes. A . as given by equation 5th 'Data main]y adapted from LandoltBSrnstein. PhysikalischChemische Tabellen. A and B..9 23. TABLE Molecule X.161 QUANTUM At all STATISTICAL THEORY OF HEAT CAPACITY 117 reasonable temperatures the rotational levels of a molecule conlike those of diatomic molecules.4 5. the rotational partition function..3 1. SC>2(2) 3 (3) ..78. NO 2 H . for a nonlinear molecule is taining more than two atoms. G. "InfraRed and Raman Spectra of Polyatomic Molecules/' 1045. HO H. 85. e.. The symmetry numbers of of inertia is equal to the third. such as CHi and and C are equal.g. MOMENTS OP INERTIA OF POLYATOMIC MOLECULES of Inertia Moment 18. 73. 2O. remembering that all the quantities except T are constant. benzene and water.. 3. are occupied sufficiently for the behavior to be virtually classical in character.46. These are the results to be exfound readily the from equipartition principle for energy expressible in three square pected be the case for a nonlinear molecule containing more than would as terms.76 12.. <r is unity.33 5. 61. and <r is the symmetry number ( 16h)..Br CH 4f ccut 520 2. PCU. are equal. NH CH (i. By differentiation with respect to temperature of Qr .g.4.
be taken as the classical values at all temperatures. two or more vibrations may have the same 8 frequency. HO 2 HaS SO 2 NH. 11. Thus. 5. so that the total is 3/J per mole. assuming ideal behavior.32). 1290. 612(2).' mole*. TABLE Molecule XI.9)] involve the logarithm of the partition function. each of the form (1 .5) factors. 957(2).30) to the overall vibrational partition function. 667(2). and (c) 0. respectively. 7. deg. 2900. . 1358(3)..0 and 11.96 cal. . the values of hcw/kT corresponding to the frequencies of (a) 1654. (c) 3935 cm. 950. for the energy and heat content [equations (16. the results for C. a molecule containing n atoms has 3n 5 modes if linear. 1300. The vibration frequencies of some familiar moleOn accules containing more than two atoms are recorded in Table XI. 1450(2). 2900. 3030. 2001. See ref. 729(2). deg.C1 3825. (ii) The translational and rotational contributions may be taken as classical. excepting hydrogen and the rotational contributions to the energy and heat capacity may deuterium. the latter is thus the product ~ The values of 3n 6 (or 3n .003 cal. this is indicated by the numbers in parentheses in Table XI. which is equal to the sum of the logarithms of the component factors. 461. Cy of water vapor at (i) 500 K. 596(2).77.35.8) and (16. 1151. 1340.32).~* mole" . Problem: Calculate the heat capacity 1000 K. 1460(2). l ) HCN NO 2 CO C H* 2 2 3451 2276 2349 1974. 1390(2). and then to add the results to obtain the total value for the molecule. 1020(2).118 CALCULATION OF ENERGY AND HEAT CAPACITY 161 Just as with diatomic molecules. and 3ra vibration contributes a factor of exactly the same form as equation (16. CH. each 1 being f JR. 1305. 776(3) ) Molecule Frequencies (cm. CH 3414(2) 732. 3157(3) 218(2). count of molecular symmetry. Each of these modes of vibration if nonlinear.004. 2611. (i) At 600 K. 3061(2) 4 CCU CHsBr For the determination of the vibrational contribution to the energy content or heat capacity it is not necessary actually to evaluate the product 6 (or 3n of the 3n The expressions 5) factors in the partition function. it is usually simpler to determine the contributions of each of the 3n 6 (or 3n 5) modes of vibration separately by means of equations (16. 3935 2684 1361 3334. 3374 3287. 1627(2). i. 6 modes of As seen in 15d. are (a) 0.~ 729(2). at each temperature. 3047(2. 314(3).e h * lkT)1 from obtained a study vibration are of the 3n 6 (or 3n 5) frequencies of the various spectra of the molecule or by a comparison with the results for related compounds. 610.392. two atoms.~ 1654.31) and (16. (b) 3825. (6) 0.e.* are 4. Setting these values of x into equation (16. 519. 1355. VIBRATION FREQUENCIES OF POLYATOMIC MOLECULES l Frequencies (cm.
viz. A comparison of thermodynamic properties obtained experimentally with those derived from the partition functions has revealed the fact that in many molecules.225 cal.38.67 respectively. the total number of internal rota6 for a nonlinear molecule. (ii) At 1000 K. 5. The total heat capacity at constant volume is thus 5.70 cal.16m QUANTUM STATISTICAL THEORY OF HEAT CAPACITY 119 the total vibrational contribution being the sum of these quantities. The allowance for interaction. l l deg. such as those mentioned above.40 = 6. is based on the approximation that rotational and vibrational energies are separable. the internal rotation would be virtually free and unrestricted. The contributions to the energy content. no satisfactory independent method is yet properties derived from it. increase of the heat capacity of water vapor with temperature is in 1. and related properties. If the internal rotations and vibrations is thus 3n tion is completely unrestricted and classical in behavior. the rotation is actually restricted.399 0.40 cal. respectively.. to each other. etc. not greatly different from those obtained by the approximate method that has been given here. For every type of internal rotation of a group within the molecule. 0. were known it would be possible to calculate. however. as for diatomic molecules. has been made in a number of cases by utilizing actual energy levels derived from spectroscopic measurements. If this amount were very small.265.96 f 0. and this If the magnitude of the required energy results in a restriction of the rotation.. Internal Rotation. freely past another.96 + total heat capacity of 1. but such appears not to be the case. the molecule as a whole possesses one less vibrational mode.74 cal.~ mole~ . deg.~ l mole"1 . There are certain molecules for which the foregoing procedure for calculating partition functions. the evaluation of the energy content and the heat capacity would not be a difficult matter. these are molecules containing groups which are apparently capable of free rotation about a single bond.~ mole. and that the oscillations are simple harmonic in character. l 1 deg.60 and 5. The procedure described above.36 cal.. Various lines of evidence show that the necessary energy is appreciable. are then appreciably different from those calculated on the assumpThe results indicate that before one group can rotate tion of free internal rotation.. etc. in which the two Most aliphatic hydrocarbons and alkyl derivatives of benzene.247. the molecules must acquire a certain amount of the appropriate energy. . water. the sum being The volume at 1000 water vapor at constant 7. The K should thus be 5. Provided the vibration frequencies of the molecule are available from spectroscopic measurements.74 = agreement with experiment. with a fair degree of accuracy. in which free internal rotation might have been expected. ammonia and formaldehyde fall into the same category. as in ethane. hydrogen sulfide. so that the corresponding contributions to the energy content and heat capacity are %RT and $R per mole. the energy can be represented by one quadratic term. One of the simplest examples is CHa groups might be expected to rotate with respect ethane. the values of hcw/kT are 2. is not completely satisfactory. The results are. 16m. (6) 0. and (c) 0. so that the contributions to Cv are (a) 1. the contribution of tjie restricted internal rotation to the partition function and the However.
""1 g. . 639.7 5. cal. Edmister.6 5. deg. deg. the contribution to the energy content will be RT per g. atom. HEAT CAPACITY OF SOLIDS Atomic Heat Capacity: Classical Theory.6 seen that at ordinary temperatures (about 20 C) the values of Cv are approximately constant. 17a. i. Lewis and Gibson.. Stull and Mayfield. 2413 (1941). and by correcting the observed.~* g. 1516 (1907). DBG. i.9 5. atom for each vibrational mode. 1 For empirical and semiempirical rules for calculating the heat capacities of hydrocarbons and other organic compounds. Chcm. Chm. 5. Once this restricting is other known..1 6. according to the principle of the equipartition of energy. 1859 (1945). TABLE Element XII. properties can be calculated by making appropriate allowenergy ances. N.9 5. and as they lie outside the 9 scope of this book it is not necessary to consider them further. 126 (1938).. HEAT CAPACITIES OF ELEMENTS AT CONSTANT VOLUME IN CAL.1 Aluminum Antimony Cadmium Copper Gold Lead Nickel Palladium 5. atom"" . Dobrate. The theoretical atomic heat capacity of 3R should apply to constant volume conditions. boron. 35. 2554 (1917). ibid. The details of the treatment are not simple. 1 deg. Fugassi and Rudy. Spencer. with the exception of carbon. Lewis (1907) obtained the results given in Table XII. ATOM" 1 CV 5. 582 (1942) . atomr1 This theoretical conclusion is in general agreement with the familiar empirical rule of Dulong and Petit. ibid. Z. solid may hence. Since the atoms would be free to oscillate in all directions in space.. beryllium and silicon.9 Thallium Tin Zinc 5. 29. each atom may be supposed to have three independent modes of vibration. Eng.9 5.96 cal. ibid. 39. Lewis..2.0 5.9. J. 1029 (1938).. ibid. phys.e.9 Element Iodine Iron CV 6.9 Element Platinum Silver Cv 5... Soc. 30. ibid. . with a variation of =t 0. and hence the heat capacity at constant volume should be 3fl. 1303 (1943). the mean being 5. If the vibrations are simple harmonic in character. Soc. Am.. measured at atmospheric pressure is about 6. 1165.""1 at ordinary temperatures. the energy can be expressed as the sum of two quadratic terms. Chem. 33..9).e.. Ind. 34. but not interacting with each other in any way.9 5. The energy content E of the ideal solid element should thus be 3RT per g. 759 (1941) ." 1 Q. B39. Glockler and Edgell. 63. /. Chm. see Bennewitz and Rossner. Am.9 5. G. constant pressure.4 cal. 352 (1038). Pitzer..120 available! CALCULATION OF ENERGY AND HEAT CAPACITY 17a and the procedure adopted is to estimate the value of the energy by experimental thermodynamic quantity. 67. ibid. 30. utilizing an accurate 17.8 6. which states that the atomic heat capacities of most solid elements. An ideal elementary be regarded as consisting of a space lattice of independent atoms vibrating about their respective equilibrium positions. measurements by means of equation 10 It is (21.
equation represents qualitatively. diamond. Further. at least. there are nevertheless significant discrepancies. The physical significance of the variation of the heat capacity of a solid with temperature is then similar to that given in connection with the vibrational contribution to the heat capacity of a gas ( 16j). number of atoms possess fairly large numbers of quanta of vibraand the behavior can then be expressed with reasonable accuracy by the classical treatment. the expression reduces to 3R. deg. the atomic heat capacity of a solid element should approach zero at very low temperatures. At sufficiently high temperatures a con where w is crystal lattice. is only 1. in wave numbers. as is to be expected. as given by equation (16. and it increases with increasing temperature. although the atomic heat capacities of most solid elements are about 6 cal.g.14 cal. boron. who applied the quantum theory in place of the classical The provement equipartition principle to calculate the energy of the atomic oscillators. of the atoms in the Comparison of this result with the contribution made by a single oscillator to the heat capacity. 17b.""1 g. and so other interpretations have been proposed. attaining a value of 5.17b HEAT CAPACITY OP SOLIDS 121 In spite of the apparent agreement between the experimental data and the theoretical prediction based on the equipartition principle. With increasing temperature the energy of the crystal increases and the higher levels are increasingly occupied. and do not increase markedly as the temperature is raised. This is in general accord with the experimental behavior. Einstein (1907). when hco)/kT is small in comparison with unity.32). but at high temperatures. In the first place. In fact. and they then contribute nothing to the heat capacity." 1 1 Somewhat similar results have been obtained with g. shows that the former differs from the latter by a factor of three. In spite of the fact that the Einstein siderable tional energy. The expression obtained for the atomic heat capacity of a solid at constant volume may be written in the form the oscillation frequency. atonor at 1080 K. The first step in the imof the theory of the heat capacity of solid elements was made by A. it does not completely solve the problem of the heat 11 See the wofks mentioned in ref. in agreement with the result of the classical treatment. 1..1 g.45 cal. Such a variation of the heat capacity of a solid with temperature is not compatible with the simple equipartition principle. At very low temperatures. deg. the variation of heat capacities with temperature. e. the heat capacity of carbon. hence the heat capacity becomes appreciable. According to equation (17. a striking decrease is always observed at sufficiently low temperatures. it appears that the heat capacities of all solids approach zero at K. beryllium and silicon. 11 Einstein Heat Capacity Equation. atom""1 at ordinary temperatures.1). . atom""1 at 293K. deg. all the atoms in the solid are in the lowest vibrational level.
and there will be a total of 3JV independent frequencies. The lowest frequency will be zero. As a result of interactions. of the oscillations is of the same order as the interatomic disIn order to determine the distribution of frequencies.3) At sufficiently high temperatures 6/T becomes small enough for all the terms in the brackets of equation (17. fall off of the atoms in a crystal.1) which may be written as ' has the  1)* \ T mean frequency. and hence the plot of C v against T/0 (or log T/0) should yield a curve that is the same for all solid elements. . The Debye Heat Capacity Equation.2). equal to hcu/k. it is very improbable that they will act as independent units oscillating with a uniform frequency. In this way an expression for CV contain wave length ing a complicated integral was obtained. 3JV coupled oscillators. (17. and even of a few * Since simple compounds. It will be seen from the Debye equation (17. for at low temperatures the calculated values more rapidly than do the experimental heat capacities. the integral can. but there is a definite limit to the highest frequency. elastic medium. but it requires some modification in detail. (1912) disregarded the atomic structure of the solid. f The same is true for the Einstein equation (17. the atoms will execu e complex motions. its essentials the Einstein theory of the heat capacity of solid elements is Owing to the proximity correct. There is little doubt that iu 17c. P. The vibrations of the atoms could then be considered as equivalent to elastic waves. e. . and treated it as a homogeneous. equation becomes where 8. propagated through this continuous medium. and it is an experimental fact that the heat capacities of many elements. where o> is the is smaller than the Debye which involves the maximum frequency. The Einstein characteristic temperature 0E.2) that CV is a function of B/T only. known as the characteristic temperature of the element. (a) moderate and high temperatures. ionic crystals such hcum has the dimensions of energy and k is energy per degree. to be neglected. but these may be regarded as being made up of a series of ample harmonic vibrations with various A solid containing atoms will thus behave as a system of frequencies. the atomic heat capacity (fe) very low temperatures. f The nature of the curve is shown in Fig.122 CALCULATION OP ENERGY AND HEAT CAPACITY 17c capacities of solid elements. dimensions of a temperature. designated by co m arises when the N . similar to sound waves. other than the first. and In the former case. is defined by * deg. this maximum..g. however. 9. Cv then becomes equal to the classical value SR. be evaluated in two special cases. Debye tances.
and hence with the large values the characteristic temperature of these elements. 3R. If the characteristic temperature of an element is rela^ tively small.6 0.3) the characteristic temperature 6 will be large is large.e. e.~~l g. the limiting value being reached only at high temperatures.17c HEAT CAPACITY OF SOLIDS 123 as sodium and potassium chlorides. ^ the value of T/8 will be equal to unity at temperatures below 300 K. 9. have been found to fall on or very close to this universal curve.4 0. T/0 is unity. the heat capacity is just less than the classical value 3 R. when If the characteristic temperature of any solid element is known.2 1. a temperature of 300 The atomic heat capacity will thus be well below of the Debye curve.856/2 5. less than about 300.0 1. the complete variation of the heat capacity at all moderate and reasonably high temperatures can be obtained from the Debye equation (17. For 0. this frequency is a rough measure of the binding if the frequency *> energy between the atoms in the crystal. and hence by equation (17. and it will increase rapidly with temperature. as it is for carbon and some other light will coincide with the rising portion elements. By giving a value of 1860. which crystallize in the cubic system.g.. 9 that the heat capacity of an element attains its classical value of 3R when T/B is ^ 7 Jj J approximately unity (see problem 7^ given below).2 0. = 2. This is the case for the majority of the solid elements. ~ K Problem: Calculate the value of Cv for any element when equal to the its temperature is Debye characteristic temperature is 0. According to equation (17. if is large. It is evident from Fig.8 1. when the temperature is equal to the characteristic temperature.. For such a temperature B/T unity. i. Hence.68 cal. deg. The slight discrepancies that have been observed are probably to be attributed to the approximation of treating a crystalline solid as a continuous medium in the determination of the distribution of the vibration frequencies. Dcbyc atomic heat capacity curve temperatures. The internal structures and high melting points of carbon.2) = ~ + ^ atom"1 . On the other hand.2) or the equiva . boron and silicon are compatible with exceptionof ally high values of the binding energy.4 such elements the law of Dulong and T/0 Petit will evidently hold at ordinary FIG. the variation of the heat capacity of diamond with temperature can be expressed with considerable accuracy by the Debye heat capacity equation.
) = 3R X = 5. F. From Table XIII. when Cv is about 3 cal. . 1 g. e. from elasticity measurements. 1 /i860Y_ atom. 17d. the solution of the complete The Debye Equation at Low Temperatures. acteristic temperatures of a number of elements are quoted in Table XIII. this means that for most sources. R. "Introduction to Chemical Physics. 12 TABLE Element XIII. 9) ." 1939. preferably made somewhere just above the middle of the rising part of the curve. the characteristic temperature 6 is 1860. Thermodynamics. 1 560^i080/ deg. A. given earlier. particularly from the compressiWhere such data are available it is bility and Poisson's (elasticity) ratio." 1939. at moderate and high temperatures. 1 1 The measurement should not be made in the region where deg. (17. The value of 6 can be derived from a single experimental determination of the heat capacity. Seitz. atom"" . C. deg. nor at too low temSome values of the charperatures.4) to hold." 1940.4 (Y      cal. by equation (17. '"J atom" 1 .2).14 cal. In order for equation (17. Fowler and E. g. (The experimental value.. Cv DEB YE CHARACTERISTIC TEMPERATURES OP ELEMENTS Element 390 140 104 225 1860 385 Element 315 170 450 90 290 350 Nickel $ Aluminum Antimony Bismuth Calcium Carbon (Diamond) Cobalt Copper Gold Iron 375 100 225 150 212 210 Potassium Platinum Lead Magnesium Manganese Sodium Silver Zinc Problem: Calculate the heat capacity of diamond at 1080 K. thus possible to obtain reasonably accurate heat capacities. dcg. is 5.1 1 . * l /1860V  ^1 ~20^ 1080> 0.8673 + .4) conclusions. for then equation (17. because of the flatness of the curve. therefore. that is.4 . Guggenheim. approaches 3/2."" g. At low temperatures Debye equation leads to the result 464. Sister.2) does not hold. hence.g.17 cal. H. to be drawn from the Debye theory are that at low temperatures the atomic heat capacity of an element should be proportional to I78 . "The Modern Theory of Solids. It may be mentioned that the Debye characteristic temperature can be derived from other properties of the element. and that it should become zero at the absolute zero of temperature..124 CALCULATION OF ENERGY AND HEAT CAPACITY 17d lent curve (Fig.1 g. it is necessary that the temperature should be less than about 0/10. 12 The important Data adapted from various "Statistical J. atom 1 .
is 0.2) 1 found that at 223 K. as is to be expected. 7 .17e HEAT CAPACITY OF SOLIDS 125 substances the temperature must be below 30 K. calculate the value at 223 Problem: The atomic heat capacity of copper K. for example. atom' 1 about 5. Such extrapolations are necessary in connection with the determination of an im portant thermodynamic property (Chapter IX). the relationship K Ce = aT i. This increase is attributed 300 mainly to the relatively free electrons of the metal behaving as an "electron gas. has been derived for the contribution of the For most metals a lies between 10~ 4 and electron gas to the heat capacity. less than 0/10.5 X 300 K 10~ 4 in calorie units.32 cal. 5.39 cal.1155 cal. The proportionality of heat capacity to the third power of the absolute temperature has been found to be of great value for the purpose of extrapolating heat capacities to the absolute zero. as described in 17c. deg.4). 2. deg. FermiDirac statistics. = 3R X (The experimental I7e. .~l g. and even for some simple compounds.) ment i.85 cal. atom~ l at 1300 K.13 to 0.20 K. viz.2). however.4 321. where the characteristic temperature 6 has been determined by two methods.~ at 20." By the use of the special form of quantum statistics. Since Cv is equal to 464. atom" 1 experimental determinations have shown that with The increase is.5. that the Debye theory is not perfect. (it is Upon inserting this value into equation (17. deg. Alternatively. With this known. showing. from heat capacity measurements at moderate temperatures.075 at and 0. atom1 at 1300 K. the agreement is not exact. one heat capacity value under these conditions can be used to derive the characteristic temperature.03 to 0. Heat capacity measurements made at sufficiently low temperatures have served to confirm the reliability of the T* relationship for a number of elements."1 g. that is. i.1155 6 = = 464. the values at low temperatures. atom" at and about 6.e. l 1 gradual. /321V = ! / 3 2i\4 " ' ' * j 20\223 ) +560V223/ J .96 cal.~ l g. if 6 is found. The influence of the free . From equation (17. from low temperature and high temperature measurements.~ l g. Heat Capacities at High Temperatures. l deg. where a is a constant for each element. Although the theoretical treatof heat capacities requires the limiting high temperature value to be 3R..~ g..904 5. the variation of Cv with temperature at higher temperatures can be obtained from equation (17..4) 0. deg.e. applicable to electrons. tne heat capacity of silver is 5. However. result is 0. can be estimated from equation (17. and so the electron heat capacity is 0.4 (T/0) 3 at very low temperatures. deg. increasing temperature Cv increases still further.5 cal.
unity. and also for some elements which do not form cubic crystals. 13 If the Debye function in some form were applicable to all compounds it would mean that at sufficiently high temperatures the molar heat capacity at constant volume would be equal to 3/2 X n. and no internal rotation. the contribution of the electron gas will apply even if all tinatoms are in their lowest electronic. although raised. Kopp (1865). silicon (3. Once these are available. states. as follows: carbon (1. 2554 (1917). especially metallic halides. t M M * The effect described hero is quite distinct from that duo to the occupation of tho higher electronic levels ( 16f). deg. deg.* 17f. graphite and iodine.2) gives the heat capacity per gram atom.2). where is the molecular (or atomic) given by Q = 1. Show that the translational partition function for 1 mole of an ideal gas is :i/2 20 T 3 'n'. phosphorus (5. .879 X 10 and is the V molar weight (or atomic) volume in cc. of a number of simple compounds. 3. (5. where n is the number of atoms in the molecule. thus CV should be approximately 6n cal. Chem. other compounds. and it must be determined empirically. n atoms? that the partition function for 1 mole must be a dimensionless quanVerify by reference to the expressions for the translational and rotational (diatomic) partition functions. who suggested that the molar heat capacity of a compound is approximately equal to the sum of the atomic heat capacities of its constituent elements. the variation of heat capacity over a range of temperatures can be represented. but with (T/ey in place of T/6. but for the lighter elements Kopp suggested somewhat smaller values. 39. Lewis and Gibson.g. the Debyo the with of the heat capacities. but they may The results given by Kopp's rule be useful when experimental data are not available. substances crystallizing in the capacity. calcium For certain potassium bromide.0). fluoride and magnesium oxide. the heat capacity per g. so thut it must be multiplied by the number of atoms in the molecule to obtain the molar heat The compounds are. containing 1. and sulfur (5. heroines nppiecisiblc as the temperature of Compounds.7). 2. in general. to which the Debye treatment is particularly applicable. equation (17. EXERCISES Assuming classical behavior. boron (2. particularly those of higher atomic weight.4). For most elements. as in equation The value of n is usually less than (17.8). Show tity. mention . AvS indicated above. atom is given by a Debye function. fluorine Among these.126 CALCULATION OF ENLKGY AND HKAT CAPACITY it 17f is electrons is thus not largo." 1 mole" 1 This conclusion is analogous to the rule proposed by H.0).8). Soc. e.3). Am. variation represents temperature equation In these cases at constant volume. what would be the maximum value of Cp for (i) a linear molecule. are very approximate. rhombic sulfur. Heat Capacities may be made of sodium and potassium chloride. (ii) a nonlinear molecule.4).. oxygen (4. cubic system.~*. thus the heat capacities must be known at two temperatures in order that and n may be obtained. the heat capacity at ordinary temperatures may be taken as about 6 cal. J. hydrogen (2..
18 cal.0 K and 300 K.330 deg. B and C are the three moments of inertia of the molecule in c. is negligible."" at what temperature might the excited level be expected to affect the heat capacity? 7. Calculate the molar heat capacity at constant pressure of methane at (i) 300 K.4 0.0 ~ 4. / is the moment of inertia in c. 13.s. (ii) 500 K.~ l and that between the j 1 Calculate the electronic partition (third) levels is 226 cm. assuming ideal behavior. For the heat capacities of gaseous paraffins and olefins. Calculate the molar heat capacity at constant pressure of carbon dioxide at (i) 300 K. atom" 1 .4 3. with more than three carbon atoms.51n + 10. . the contribution of that level to the partition function.0 2. Calculate the value of e~~ tlkT when e/k is equal to 5jP. . Evaluate the universal constant b in the expression Q r = b(r~ l (ABC) T312 for the rotational partition of a nonlinear polyatomic molecule.066 23. The Debye characteristic temperature of silver is 212.4.EXERCISES 127 4.3 7Xl.4n  0.7) cal.6 0.g. 0. The frequency separation of the first excited electronic level of atomic 1 oxygen from the lowest level is 15807 cm.g. using values of 0. Using the Debye curve obtained in the preceding exercise. T Cv 84. 8. 5. . K . Derive the value of the universal constant a in the expression Q r a<r~ l IT for the rotational partition function of any diatomic (or any linear) molecule. 15.1 K cal.4 cm. assuming ideal behavior.95m l 5. units and T is the absolute temperature.2). deg. obtained at low tempera3 tures. 11. 0.2 0. 1 and 0. 1 g.1 0. pressure and 25 C. 0. Determine the vibrational partition function of carbon dioxide at 25 C. compare the result with that obtained in Exercise 14.45 112. atomic heat capacity CV of this metal at 20. according to equation (17. (iii) 1000 K.3n2 + 4.56 + 0. The normal state of atomic oxygen is an "inverted triplet" consisting of The frequency separation between the three levels with j values of 2. > 5T.~ mole~ l . K atom" 1 . against !F and hence determine the (mean) Debye temperature.50 141.65mn + 4. deg l g. Determine the rotational partition function of the water molecule at 25 C. 2 (lowest) and the j 1 (second) levels is 157. Plot the Debye curve. Calculate the transiational partition function for 1 mole of oxygen at 1 atm.301 35.s. Plot the following values of Cv for aluminum. 17. Calculate the 16. 9) suggested the empirical formula CP = 2. 10." j = 2 and the j = and the corresponding contribution to the function of atomic oxygen at 300 atomic heat capacity. Calculate the rotational partition function of carbon dioxide (a linear symmetrical molecule) at 25 C. for Cv against T/6 1. determine the (mean) Debye characteristic temperature for this element.2 for the latter. (iii) 1000 K. m t .2. and the values of Cv for aluminum given below. assuming ideal behavior. 9.6. Justify the statement in the text that if for any energy level c/A. and consequently to the heat capacity. A. (ii) 500 K. Edmister (see ref. units.162 32. T Cv 19. Calculate the value of Cv at 25 C. 12. 6.110 27. 14.
mole. Am. For paraffins. CP 5.128 CALCULATION OP ENERGY AND HEAT CAPACITY in where n is the number of carbon atoms and m the number of hydrogen atoms the hydrocarbon molecule.1 . Compare the molar heat capacities of nbutane gas (C4Hio) at 500 K.58) cai.998 X lO" 6 ^ 10'!T3 cal. deg.706 X Calculate the value at 500 K. as given by the two expressions. the heat capacity of this gas is given by CP **  0. Chem. mole"1 . 67. 1859 (1945)].012 + 92. t is the centigrade temperature. deg. Soc. T is the absolute temperature.65n  0.~ l + 9. . where n is the number of carbon atoms.506 X lO'8 ? 7  47.lln + 1 1.62 + 10^(l. According to Spencer [J.. Pitzer (see ref 9) proposed the formula .
however. All that the law can state is that if this process occurred. this fact is embodied in the second law of thermodynamics. and its consequences are of great significance. deals with the conversion into work of energy absorbed as heat. the heat energy gained by one end would be exactly equal to that lost by the other. In order to understand 18b. The first law of thermodynamics merely indicates that in any there is an exact equivalence between the various forms of energy process involved. unless heat is supplied from outside. which is really fundamental to the problem enunciated above. CONVERSION OF HEAT INTO WORK Scope of First and Second Laws. or rather the 18a. oneugas will diffuse spontaneously into another until the mixing is complete and the system has the same composition in all parts. interest of the probability. The first law states that when heat is converted into work. it is of interest to examine certain processes which are known to be spontaneous. It is the second law of the thermodynamics which provides the criterion as to the possibility. the resulting decrease of energy content being equivalent to the work done against gravity. Another important aspect of the second law. of various processes. but it provides no information concerning the feasibility of the In general. there will be a fall of temperature. processes which take place without exThe expansion of a gas into an evacuated ternal intervention of any kind. Spontaneous and Irreversible Processes. all it states is that if water does run uphill. Diffusion 129 . question of whether a specified thennodynamic process is or is not possible. For example. takes place spontaneously. Similarly. until the pressure distribution is uniform throughout. To the chemist the essential second law of thermodynamics lies in the fact that it provides a means of predicting whether a particular reaction can occur under specified conditions. or from any region of higher into one of lower pressure. space. that is. the second law supplies an answer to the process. the first law does not indicate whether water can spontaneously run uphill or not. there is nothing in the first law of thermodynamics to indicate whether a bar of metal of uniform temperature can spontaneously become warmer at one end and cooler at the other. something of the conditions which determine whether a particular process will occur or not. Similarly. perature cannot be completely transformed into work without leaving some change in the system or its surroundings. the work obtained is equivalent to the heat absorbed. but it gives no information concerning the conditions under which the conversion It will be seen shortly that the heat absorbed at any one temis possible.CHAPTER VII THE SECOND LAW OF THERMODYNAMICS 18.
processes as the spontaneous concentration of a gas at one end of a vessel. By the use of an external agency. spontaneous 8a). at least in principle. as described in 8a However. will similarly take place without external intervention. Work would have to be done on the gas. expansion of a gas. or into a dilute solution. have never been observed.130 THE SECOND LAW OF THERMODYNAMICS 18C of a solute from a concentrated solution into pure solvent. and until the two bodies attain the same temperature. fundamental characteristic of the processes described. the initial state many * In order to avoid the possibility of misunderstanding. a tendency for the system to approach a state of therm odynamic represents of metal which is transfer of heat equilibrium ( 4c). This result is in accord with the statement made above that spontaneous processes are not reversible in the thermodynamic sense. has attained a uniform temperature. leaving a lower pressure at the other end. evaporation of a liquid and even chemical reactions. the gas which has ex A panded into a vacuum could be restored to its original volume by compression. that the complete conversion of heat into work is impossible. incidentally. founded processes are not thermodynamically reversible (cf. by introducing a piston into the vessel. .* This fact. It may be remarked. hotter at one end. without external intervention. of a in one vessel. It is a fundamental fact of experience. but the probability of this occurring. and in fact of all spontaneous processes. in the latter It will be observed that in every case the spontaneous process instance. in the former case. or a bar of metal becoming spontaneously hot at one end and cold at the other end. and the temperature of the gas would rise. which was originally processes will be considered. For example. that it is not altogether justifiable to say that these It is possible for a gas to concentrate spontaneprocesses are impossible. e g. In other words. Before stating the second law. then the original state of the gas would have been restored. Reversal of Spontaneous Processes. These processes will continue until the temperature of the bar is uniform. and to the spontaneous by radiation from a hotter to a colder body. the spontaneous unmixing of a uniform gas mixture. Such upon experience. A system which is in equilibrium under a given set of conditions will undergo no detectable change if the conditions are not altered. is that they have never been observed to reverse themselves without the intervention of an external agency. to judge part ously from actual experience. can be carried out reversibly. when they do occur spontaneously. however. is extremely small. reference may be made to the spontaneous conduction of heat along a bar hot at one end and cold at the other. without leaving some effect elsewhere. it may be pointed out here that changes which occur spontaneously in nature. Finally. other attempts to reverse spontaneous When a bar of metal.. and there would be no change in external bodies. If this heat could be completely reconverted into work by means of a hypothetical machine. it is possible to bring about the reversal of a spontaneous process. and at the same time an equivalent amount of heat would be produced. of the second law the basis is of thermodynamics. they are thermodynamically irreversible. 18c.
will dissolve spontaneously in of copper sulfate. A friction. in this process the heat is completely converted into work. work will have to be done on the system. a more useful form is that based on the inability to convert heat completely into work. reIt will be recalled from the statements in versible expansion of an ideal gas the work done is exactly equal to the heat absorbed by the system. so that the system has undergone a change. is not possible. is not thermodynamically reversible. Hence. and an equivalent amount of heat will be liberated. quent purposes. However. it would be necessary for the heat evolved in the original reaction to be completely converted into electrical work. for example. it will now be shown that similar considerations apply to chemical reactions. In other words. completely converted into work. but there is no net absorption of heat and no work is done. Once again. however. the complete conversion of heat into work without such changes is impossible.g. It is evident that certain spontaneous physical processes could be reversed if the complete conversion of heat into work could be achieved. it is impossible to construct a machine. e. that it is not possible to convert . The foregoing is an illustration of the universal experience. The work and ' heat quantities involved in the process are exactly the same as those concerned in the original expansion. Heat is withdrawn from one end of the bar. like the physical changes considered above. has been already given. it is important to observe that this conversion is accompanied by an increase in the volume of the gas. one of which. piece of zinc. The Second Law of Thermodynamics. thus regenerating metallic In order that the reversal might not leave changes zinc and copper sulfate. and then the work could be utilized to heat the other end of the bar. operating in cycles. which will produce no effect other than the absorption of heat from a reservoir and its conversion into an equivalent amount of work. elsewhere. without producing other changes. with the evolution of a definite amount of heat. thus. it is impossible to carry out this series of processes without leaving some changes for. The second law of thermodynamics has been stated in various forms.. 18d. according to the equation an aqueous solution Zn + CuS0 4 = ZnS0 4 + Cu. that the spontaneous chemical process.18d CONVERSION OP HEAT INTO WORK 131 might conceivably be restored in the following manner. If the gas is to be restored to its original volume by reversible compression. It is seen. This reaction could be reversed by passing an electric current between the metallic copper and the solution of zinc sulfate in an appropriate manner. concerning the For subseirreversibility of spontaneous processes. 9d that in an isothermal. as already stated. electrically or by Actually. the net result of the isothermal expansion and compression is that the system is restored to its original state. so that it can function continuously. 7c). therefore. experience shows that a complete conversion of this kind. The term "operating in cycles' is introduced to indicate that the machine must return to its initial state at regular stages (cf.
The ocean.. Similarly. Hence. may be regarded as a heat reservoir of constant temperature. i.. 18e constant temperature. when the energy of a moving body is converted into heat by friction.* and the law states that it is not possible to convert the heat continuously into work without producing changes elsewhere. The reversal of the process. that is. As indicated earlier.. the utilization of the vast stores There is nothing contrary to the of energy in the ocean and in the earth. there is merely a very great probability against If it it. i.e. for example. then to be regarded as applicable to macroscopic systems. e. . will thus have instant. first law of thermodynamics in this concept.e. a pressure difference would arise spontaneously within the vessel. the heat of the ocean into work is possible. resulting from the absorption of heat by a body. represents an increase in the kinetic energy of the random motion of the molecules. provided it is permissible to speak of pressures when a few molecules are concerned. If the vessel contained a large number of mole would is * cules. been converted into directed motion. if a vessel contained only five or six molecules uniformly distributed.. The probability of this occurring in a system consisting of a large number of molecules is very small. fundamental basis of the second law of thermodynamics may be obtained by According to this utilizing the concepts of the kinetic theory of matter. would require that all the molecules should spontaneously acquire a component of motion in one preferred direction. instant all five molecules will have a preferred component of motion in one direction. Imagine a system consisting of It is not improbable that at some five molecules possessing random motion. A consequence of the impossibility of converting heat isothermally into work in a continuous manner is the impracticability of what is called "perpetual motion of the second kind.e." that is. the directed motion of the body as a whole is transformed into the chaotic motion of individual molecules. The system as a whole will then have directed motion at that The chaotic movement of the molecules. there would be a considerable probability that at some instant there will be a larger number of molecules at one end of the vessel than at the other. This may be regarded as another aspect of the second law of thermodynamics. and since Where it is (partial) conversion of the there are temperature differences in the ocean. spontaneous processes could be reversed. That is to say. but the fact that it has not been found feasible provides support for the second law. were possible to deal with systems involving only a few molecules. it is highly improbable that any appreciable unequal distribution arise spontaneously (cf. theory an increase of temperature. cycle. the spontaneous conversion of heat into work. Macroscopic Nature of the Second Law. at different levels.132 heat into work by THE SECOND LAW OF THERMODYNAMICS means of an isothermal. The second law of thermodynamics 24a). work.g. An insight into the 18e. heat. it cannot be stated that it is impossible for a spontaneous process to reverse itself spontaneously. this is not contrary to the second law of thermodynamics. i.
the efficiency is equal to W/Q. namely that of a reversible engine. W W W . machines for the conversion of heat into work.18g CONVERSION OF HEAT INTO WORK 133 systems of this type which are the basis of human observation and experience. part of this heat is converted into work. thus. 18f. The effifor a machine the of continuous conversion of heat into work is thus ciency always less than unity. often referred to as the "source". However. if a device could discriminate between two different types of gas molecules.("hot") and slowmoving ("cold") molecules. Carnot (1824). is the maximum possible for the given temperatures.. and the remainder is returned to the heat reservoir at the lower temperature. similarly. The fraction of the heat absorbed by a machine that it can transform into work is called the efficiency of the machine. it would be possible to produce spontaneously a temperature gradient in a gas. Q and A highly important discovery in connection 18g. if heat Q is taken up from the source. in other words. no exception to the law has yet been observed. of course. or substances. that is invariably less than Q in a continuous conversion process. Conversion of Heat into Work. and Experience shows. reservoir at the higher temperature can be converted into work. provide the difference of energy potential that is necessary for the conversion In order to carry out this conversion. The principle he enunciated. but two such reservoirs. If a device were available which could distinguish between fast. that a portion only of the heat taken in from the "sink". with a directive influence. with the problem of the efficiency of heat engines. was made by S. or rather the improbability.e. electrical work is associated with a difference of electrical potential. vided the machines function in a thermodynamically reversible manner. it must be associated with a difference of potential or. for example. at different temperatures. that the first law of thermodynamics will still be applicable. generally known as an In a heat reservoir at constant temperature there is electromotive force. from the reservoir at the higher temperature. of reversing spontaneous processes is based on the inability to deal with individual molecules or small groups of molecules. the fact that no such devices are known is in accordance with the second law of thermodynamics. which is the reverse of diffusion. The work that can be done by falling water. no directive influence. is due to the difference in potential energy at the upper and lower levels. the efficiency is independent of the working substance. is the work done. or mode of operation. The Carnot Theorem. referred to as the It is seen. a partial unmixing. probetween two given temperatures have the same efficiency. i. In order for any form of energy to be available for the performance of work. Similarly. it depends only on the temperatures of the source and sink. which is derived from the second law of thermodynamics. could be achieved. it will be shown that this particular efficiency. It will be understood. therefore. in agreement with the statement of the second law of thermodynamics. for the energy difference between is returned to the lower temperature reservoir. heat is absorbed of heat into work. Incidentally. aay be stated in the following form: All reversible heat engines operating In other words. It has long been realized that the impossibility.
it will be assumed thai there exist reversible heat engines I and II. doing work and giving up the remainder at Ti. work done by the system is positive and that done on the system is negative. but having different efficiencies. is given by Heat transfer at Work done =  Q{ W  Qi W '. the combined hypothetical. reversible machine. 10. having work done upon This it. l FIG. i.. without leaving changes elsewhere. taking in heat at TI. two W W W W . and so it must be concluded that the two reversible mar chines I and II cannot have different efficiencies.e. without producing any external changes. whereas II functions in the reverse manner. returning a quantity Q 2 which is greater than Qi. I II Heat Heat transfer at transfer at Work done T2 = = T\ = Qz W Q\ Heat Heat transfer at Work done transfer at  W The net result of the complete cycle by the two reversible engines. it follows that and Q{ is equal to Q 2 Since Qi is equal to Q 2 so at is equal to the to that the heat absorbed is TI Qi Qi W. and giving up heat at TV* is permissible since the machines are assumed to be reversible. to the sink at T\. similarly. functioning in cycles. Let the machines be coupled together so that I operates in a direct 7 manner.e. machine II functions as a refrigerator (see 18j). is able to convert completely into work the whole of the heat taken up from a reservoir at the temperature TI. bringing them both back to their initial states. and gives up the remainder Q 2 machine II. working between the same two temSuppose that in each cycle the peratures. of the heat Q* taken in at T* into work. on the other hand. 10 and represented below.. taking up heat at 7 2 Hot Reservoir T. equal work done by the engine. machine I takes in heat Q 2 from the source at T^ converts an amount = Q\ to the sink at TV The into work. The various heat and work changes in each complete cycle of the combined machines are then as indicated in Cold Reservoir T In Fig. . Proof of the Carnot theorem accordance with the convention earlier ( 7b).134 THE SECOND LAW OF THERMODYNAMICS In order to prove the Carnot theorem. is supposed to convert a smaller amount = Qi. This is contrary to the second law of thermodynamics. The Carnot principle W W 9 W * In other words. i. That is to say. heat absorbed by the system is taken as positive and heat liberated as negative.
that completely adiabatic processes can be carried out when required. Wi = #r 2 ln^a * (18. thus permitting reversible processes to be performed. sometimes referred II to as an "indicator diagram/' as in Fig. The external pressure is that it is infinitesimally less mole of gas. it is assumed tures. It is supposed that there are available two large heat reservoirs which remain at constant temperaFurther. adjusted so v. to the work done In : (18. occupying a volume V a is placed in the/ heat reservoir at the higher tempera. Since all reversible heat engines operating between the same two temperatures have equal efficiencies. the leaves or no heat enters but since the expansion. the gas is ideal. (cf . by surrounding the cylinder with a perfect nonconducting jacket so that no heat enters or leaves the system ( lOa).2) II.. 11. the temperature . the work done Wi is given by equation (8.1) The heat Q 2 taken up from the reservoir must be equal 9d). The cylinder of gas is removed from the reservoir at T and is surrounded by the nonconducting jacket. and the temperature of the gas FIG. The one which lends itself to simple thermodynamic treatment makes use of the cycle described by S. system. than the Volume always gas pressure. i. Pressurevolume is infinitesimally less than that of the reserchanges in Carnot cycle In this manner.4) . thus. The path Since of the process is represented by the isothermal curve A B in Fig. In this hypothetical heat engine the working substance is 1 mole of an ideal gas.21).18h CONVERSION OF HEAT INTO WORK 135 same two temperatures of the equality of efficiency for all reversible cycles working between the is thus a direct consequence of the second law of thermodynamics. Carnot (1824).e. and hence by equation (9. for all others will have the same efficiency. viz. the gas is expanded voir. infinitesimally slowly. I. isothermally and reversibly until its volume has increased to Vb. for 1 ture. T% (upper) and TI (lower). The Carnot Cycle. 18h. 11. it is contained in a cylinder fitted with a weightless and frictionless piston. 11. The Carnot cycle consists of four stages which can be represented on a pressurevolume diagram. it is sufficient to consider any convenient machine of this type. and adiabatically.. so that the gas can be expanded Work is done in reversibly. The cylinder containing the mole of ideal gas. respectively.
the external pressure being maintained infinitesimally greater than the gas pressure. The process is represented by the isothermal path CD The work done is given by in Fig. III. 11. TFn. Wu . The gas is then compressed adiabatically and reversibly along DA until the initial state A is regained. The cylinder is removed from the heat reservoir and the nonconducting jacket is replaced. which is that of the lower temperature heat reservoir. At the same time the quantity of heat Qi. As a result of the four stages just described the system has returned to its original state. (18. because work is the heat reservoir at T\.4) Win will be negative. it v*yi .ro .5) where Cv has the same value as in equation (18.3) and (18.136 THE SECOND LAW OF THERMODYNAMICS ( 18h must fall lOa). of done on the gas in the compression. since for an ideal gas it must be independent of the volume or pressure. y c (18. the final volume being V* WmRTiln^. versibly. while and follows from equation (10. so that a reversible cycle has been completed. by equations (18. and Wiv..RT* In Q + RTl ya * In ^ yc lie (18.3) ideal gas. this is. will be returned to Since is Vc greater than Vd.TI and v . Wrr = Cv(Ti  !T 2 ).5).5) that D C and B on another. The reversible expansion is continued until the tempera ture has fallen to Ti.6) Since lie in one adiabatic curve. The work done is given by equation (10. Cv would represent the mean value.TO. If the heat capacity were not constant. The path is indicated by the adiabatic curve BC. thus. IV. and the temperature of the gas infinitesimally greater than that of the reservoir. exactly equivalent to Win. The total work done is the sum of the four work terms Wi. the value of course. the final volume being c V . The work done is given by . . the temperature The state D in stage III is deliberately of the gas rising from T\ to T 2 chosen so that it lies on the same adiabatic as A.CV(r. but since TFn and Wrr are seen. where Cv is the heat capacity of the (18.3). it follows that W Wm WA Wi + Win . to be equal but of opposite sign. The nonconducting jacket is now removed and the cylinder is placed The gas is compressed isothermally and rein the heat reservoir at Ti.8). assumed constant in the given temperature range.cv (Ti .
and so it is desirable that the upper temperature should be high. perature of the sink.e. . and The lower the temis independent of the nature of the working substance.RT W = RT. pressure. hence. pressure. T* is 265 C.428. by equations is (18.8) In accordance with the Carnot theorem efficiency of any ( 18g).In^ \^ V V l a a B(T. 538 K. V b Va = V.=Ti 373 308 = 0.Ti)lnJi.7) work definition. i.6) found that . the greater will be the efficiency of the machine. Va By total (18. hence . so that . _ T . for a given temperature of the source.174. i. the efficiency of the hypothetical Carnot engine 1. l (ii) At 50 atm. Similarly.7). Compare the theoretical efficiencies of a steam engine operating between the boiling point of water at (i) 1 atm. (18. (i) At 1 atm.18h CONVERSION OF HEAT INTO WORK 137 and consequently Fd Fa = Vc V. the boiling point of water is 100 C.. (ii) 50 atm. AO The possible increase of efficiency very marked.e.2) and (18. is 265 C. Ti ^ is Efficiency Ti   538  308  0. the efficiency is determined only by the temperatures of the two heat reservoirs acting as source (jP 2 ) and sink (T\). assuming the temperature of the sink to be 35 C in each case. for a given temperature of the In sink. ' Vd it is Upon substitution of this result into equation (18. for sink not convenient the to be below it is atmospheric temperapractice This ture. and is 308 K as in (i). 373 K. this expression gives the reversible heat engine operating between the temperatures T\ As is to be expected. 308 K. the efficiency will be increased by using a high temperature source... the efficiency of a heat engine is equal to the ratio of the done in the cycle to the heat $2 taken in at the upper tempera W ture. i. and this represents the upper temperature Tz] the lower temperature TI is 35 C..e.. fact underlies the use of high pressure steam or of mercury in boilers for and TV power production. Problem: The boiling point of water at a pressure of 50 atm. Efficiency = T 2 ..
9) in at the lower temperature T\ is equal. It follows. ya Ti) In ^vd (18. Refrigeration Engine. but opposite in sign. that is to say. therefore. but of opposite sign. as the Carnot cycle.8) shows the efficiency to be This is in agreement with the conclusion reached earlier ( 18d) that zero. there can be no conversion of heat into work in an isothermal cycle. it follows that the efficiency of a reversible heat engine operating between two given temperatures is the maximum possible for those 18L ties of temperatures. that in the Carnot reversible cycle the work done by the system at T 2 is the maximum possible for given expansion from A to B (Fig.RT. for by continually absorbing heat from the vessel at the lower temperature its temperature can be maintained at this low level. by equation (18. to the work done by the heat engine. It is evident. or lowered further. to that involved in stage III of the Carnot engine. Q! .R(T*  TO In ^ . therefore. the work done in the cycle is that involved in the isothermal stages.RTi In . In  (18. whereas the work done on the system at Ti is a minimum for the compression from C to D. It was seen earlier ( 8c) that in a given isothermal expansion the work done by the system is a maximum when the expansion is carried out reversibly .4).8) are of interest. it is possible to operate it in the reverse direction. and this may be written in the form work on the machine it reversible. similarly.R(T.10) . understood from a consideration of the Carnot engine in 18h. hence. The work done on the refrigeration engine is given by equation (18. the machine is functiongive out heat at the upper temperature. giving some out at a lower temperature. Hence. 11). and doing work in the process. taking up heat at a higher temperature. Maximum Efficiency of Heat Engine. the cycle is an isothermal one. must be equal.. of reversible the T\ engine unity. Since the cycle is by doing can be made to take in heat at the lower temperature and In other words.7) with the sign reversed. In the foregoing treatment the Carnot cycle has 18j. that the total work done by the system is the maximum for the Since all reversible engines have the same efficiency specified conditions. is to be must be heat zero. so that The heat Qi taken W . only if the lower temperature is the absolute zero. ciency the whole of the heat taken in at the higher temperature can be converted Two into work second case in a cycle. ing as a refrigeration engine. One of the essential propera reversible cycle is that it has the maximum efficiency of any cycle That this is the case may be operating between the same two temperatures. been used as a heat engine. The work done on the refrigeration engine. using a Carnot cycle. the work done on the system in an isothermal compression is a minimum when performed reversibly. Since the work terms in the adiabatic stages II and IV cancel one another. The 7 is that in which T\ and 7 2 are equal. in this event equation (18. if the effispecial cases of equation (18.138 THE SECOND LAW OF THERMODYNAMICS I8l First.
12).. to 25 C. Suppose . or the upper increased.e. and approaches infinity as the absolute This fact has sometimes been expressed in the phrase "the zero is attained.. (18  U) and consequently. If any stage of a refrigeration cycle were irreversible. the total is 87. and of the work done on the engine. _ W = T *~ 1 1 Q. (18. increases rapidly as the temperature TI is diminished. The possibility of utilizing the efficiency of a reversible engine as the basis of a temperature scale was suggested by William Thomson (Lord Kelvin) in 1848.e. ings at 25 up to the surroundings? The heat of fusion of ice is 79.e. the coefficient of performance of the refrigeration engine.. It follows. it is evident from equation (18. unattainability of the absolute zero of temperature". The heat given up at the higher temperature is the sum of the heat absorbed at the lower temperature. temperature even if this is only very slightly above that as the temperature of a system is lowered the amount of work required to lower the temperature further increases rapidly... i.~ at C.. so equation (18. is given by W Tt T Tl t ' Q. x How much heat. and so this quantity of heat must be transferred from C.18k CONVERSION OF HEAT INTO WORK 139 The ratio of the work done on the machine to the heat absorbed at the lower temperature.12) that an infinite amount of work would be necessary to transfer heat to an upper The maximum work obtainable from a heat engine is perature K. i. that is. more work than that represented by equation (18. If the latter temperature were to be the absolute zero.12). 79. 1 g. in equation (18. by equation (18. i.8 cal. of Problem: Calculate the minimum amount of work in ergs required to freeze C by means of a refrigeration engine which operates in surroundwater at C. similarly. therefore.12) would have to be done to transfer the given amount of heat between the same two temperatures.18 X 10 7 3. 273 K ( = Ti). i. 7. 18k.e.8 cal. The Thermodynamic (Kelvin) Temperature Scale.18 it is X 10 7 .1 cal. increases as the lower temdecreased.05 X 10 8 ergs..12) Just as the Carnot (reversible) cycle gives the maximum proportion of work which can be obtained by a machine operating between two given temperatures.30 cal. Since T 2 T\ increases at the same time as TI is decreased. the ratio (T* Ti)/Ti. g. T. it can be seen from equation (18. in calories.12) that the minimum amount of work which must be done in a given refrigeration process increases as the refrigeration temperature T\ is lowered. so that the work required 7.30 X 4. 298 K ( = T$\ hence.12) represents the minimum amount of work necessary for removing a quantity of heat Q\ from a reservoir at T\ and transferring it to a reservoir at the higher temperature T*. is given ~ To convert into ergs is W= necessary to multiply by 4.
one hundredth part of the range between the ice point and the steam point at 1 atm.15) and (18. that Ls. and the identity of equations (18. pressure ( 2b). it follows that way of %^ Q'2 = ?L=Jl. if Qt is the heat transfer for the reservoir at the higher temperature and Qi is the amount of heat transferred at the lower temperature. . that is. In order that temperatures on the two scales may coincide exactly it is only necessary to define the size of the degree so as to be the same on both scales. and independent of the thermometric substance. In view of the identity of the ideal gas scale and the thermodynamic scale defined in this manner.140 THE SECOND LAW OF THERMODYNAMICS 18k a reversible machine operates between two given temperature reservoirs. The condition for the zero of the Kelvin scale may be derived by setting 61 in equation (18. hence Qz Qi is the quantity of heat converted into work. then the respective temperatures on the thermodynamic (Kelvin) scale are 2 and 0i. i. so that the zero of the thermodynamic scale is the lower temperature of a reversible cycle with an efficiency of unity. this result is only possible if the lower temperature is the absolute zero on the ideal gas scale of temperature.13) the ratio of the two temperatures is defined in a manner indeany particular thermometric substance (cf. given by s In this  1' (18 . From this fact. #2 (18. W. so that equation (18. temperatures on the former scale.15) equal to zero. the result is seen to be ^=1 V2 (fortfi0).14) may be written as This expression defines the efficiency of the reversible heat engine in terms of the Kelvin temperatures. the temperature of each reservoir on the thermodynamic (Kelvin) scale is then defined as proportional to the quantity of heat transferred to or from it in a reversible cycle. it follows that the Kelvin scale and the ideal gas scale are really the same. 2b). Disregarding for the moment the signs of the heat quantities. pendent By inverting each side of equation (18.13) and subtracting the result from unity. This is the justification for the use of the symbol " K" (degrees Kelvin) for the socalled absolute temperatures based on the hypothetical ideal gas thermometer ( 2c). may be regarded as absolute. one capable of converting heat completely into work.14) When referred to a heat engine. Q 2 is the heat taken up at the higher temperature and Qi is the amount returned at the lower temperature.e. As seen in 18h.. like those on the latter.8).
1) and consequently. the total heat absorbed is Q 2 Qi. therefore. and following all the cycles down successively to J5. these cycles equation (19. it is expression for W is substituted in equation (18. which represents the reversible The latter cycle under consideration.3) . for all the Carnot cycles equivalent to the general reversible cycle ABA. Combination of Carnot Cycles. leaving only the path indicated by the zigzag The larger the number of outline. it can be seen that all the paths inside the area enclosed by the carves A BA cancel each other. The work done in the cycle must be equal to the total heat absorbed ( 7c). for convenience in deriving the Kelvin scale of temperature. 12. 12 by a series of isothermal and adiabatic curves the closed curve . cycle (19.2) may be regarded as being made up of a number of Consider. Any reversible cycle Carnot cycles. ABA cycles taken in this will the resultant manner the closer path correspond to ABA. may thus be regarded as equivalent to the contribution of an infinite number For each of of small Carnot cycles. hence. In a Carnot cycle. so that + W W If this = Q2 + Qi. Although in 18k.2) shows that the is Volume Fia. the numerical values only of Qi and Q 2 were considered. and back again to A.19a ENTROPY 19. for example. so that a number of Carnot cycles are indicated. Cyclic process as succession of Carnot cycles sum of the two Q/T terms involved zero. seen that (19. since the former is taken up at the higher temperature and the latter is given out at the lower. it follows that o. imagine drawn across the diagram. where Q 2 has a positive value and Qi has a negative value.8). the cycle represented in Fig. it should be recalled that by convention ( 7b) Q is the heat taken up by the system. 141 ENTROPY 19a. (19. Starting from A.
3) in cycle L ^r  0. isothermal stage occurring at the temperature T. duplicate the process the form ABA./T terms between A and B.*.SA = AS. reversible changes which make up the reversible cycle ABA. (19. is given by the sum dS = 2=: . volume and temperature. The values of these summations are thus determined by the states A and B.4) where <?. reversible.6). that is. and the other back from B to . thus. It may be possible to go SB A*B . since the path B > A is the same. represents the infinitesimally small quantity of heat absorbed at the temperature T in each of the small isothermal.142 THE SECOND LAW OF THERMODYNAMICS 19b where the summation includes two terms for each of the individual Carnot Since an infinite number of small Carnot cycles are required to cycles./T terms between A and B. This function or property of the system is called its entropy (Greek: change) in * Since the paths within the area ABA cancel. A cycle E^Z^+S^O. (19. increase of the function S accompanying the change in state from is AS. qnv. In every to paths. and its value. thus. or of the corresponding summation from B to A. which depends only on the state of the system. by the pressure. * A>B * (19.5) B+A 1 from A to B by a number of different reversible A by the same reversible path BA. . it follows that the value of the first summation must be independent of the path from A to B. the g^y. and are independent of the manner in which the system was brought to these states. provided only that it is In general. values are effectively those for the isothermal stages of the path ABA itself. as seen by equation (19. appli19b. may be divided into two parts. cable to the complete (reversible) cycle ABA. it can be seen that the summation of the reversible. where qre v. therefore.* The summation in equation (19. For each of these small stages it is therefore possible to write of the is the value of the function in the state A.5) must hold.4). and SB in the state B.7) where dS represents the accompanying increase of the function S. Definition of Entropy.6) where SA The A to B qnv. one for the path from A to B. It is thus possible to express the value of each summation in terms of a function S. must be independent of the reversible path. it is convenient to write equation (19. and since the second summation on the right of this equation will always be the same. (19. always returning case the result represented by equation (19. is the heat absorbed by the system in an infinitesimal.
the Incidentally. For example. like the energy. A$2. Another consequence of the entropy being an extensive property is that when a system consists of several parts. The entropy of a system. like dE. nite quantity. the total entropy change is the sum of the entropy changes of the individual portions. and this quantity is of from A to the path completely independent B.8) that stage. In an infinitesimal stage of an appreciable process the entropy increase dS is given by equation (19. i. regarded as a thermodynamic property in the sense considered in Hence. is a complete differential.riAS* (19. Qi . since A/Si at the lower temperature is equal to Aj. For an appreciable change the entropy increase is defined by equation (19.j. depending on the path taken from A to B. Either of these relationships gives the quantity  . i. the increase of entropy is given by the summation of the terms between A and B.7) as the heat gw. However. q^JT There is a simple relationship 19c. shall be reversible. the entropy is not easily defined directly.8).6) as the (algebraic) sum of all the q^. where Q\ is the heat returned to the reservoir at the lower temperature T\.1QC tlie ENTHOPY 143 given state.2) or (19. and having no special thermodynamic significance as far as the system is concerned. Since the heat is taken up reversibly. taken up isothermally and reversibly divided by the absolute temperature T at which it is absorbed. the increase of entropy of the system accompanying the change from state A to state B has the definite value SB SA. tion (19. and so it is best described in terms of the entropy increase accompanying a particular process. if the amount of matter is doubled. it may be 4d. dependent upon the amount of matter in the system. like the energy. it is important to remember that if a system changes from A to B in an irreversible manner. and hence is not available for conversion into work. the heat quantities required for the same change of state will also be doubled. Because the entropy. Entropy Change and Unavailable Heat. dS. between entropy change and the heat which is rejected at the lower temperature It can be readily seen from equain a heat engine that is of practical significance. by equation (19.9) Qi/Ti is equal to Qi/Ti./T. Since the entropy in any state depends only on that state. is a singlevalued function of the state of the system. Q*/Tt is the increase of entropy of the system in the heat absorption It follows. qnv .e. therefore./T terms between the initial and final The only condition applicable to the path is that it states of the system...e. is an extensive property. where the gw/s refer to the succession of isothermal changes when the process is performed reThe sum of the q/T terms for an irreversible process is an indefiversibly. from equation (19.2) that for a reversible cycle (19. This fact adds considerably to the thermodynamic usefulness of the entropy function. so that Q\ may entropy decrease equally be represented by TiA&i. it may be reversible or irreversible.8) Qi=r. and the entropy will clearly increase in the same proportion.
and since the efficiency is less than for a completely reversible cycle. since the latter takes in heat when the former gives it out. the heat Qi( rev. Entropy total entropy to its original Change in Reversible Process. this case. water..). Hence. hence. of course.. therefore.*r .) is absorbed.g.2) is then V L* r. greater since the efficiency is less. therefore. 19d. for example. cycle * This result refers only to the substance or substances infor the system. It has been shown in 18i that the efficiency of a reversible engine is a maximum for the given working temperatures. and vice versa. In (19. the surroundings. change of a system must be zero." In a reversible process.> <?i<wv. IQe. the heat quantity gwv.10) where ASz is now the increase of entropy accompanying the reversible absorption 7 of heat in the temperature range from 7 2 to T' 21 instead of at T* alone. as expressed by equation (19. sometimes called the "working substance. grcv * 4r ^ * ^ _ m~ 1 i n u i the heat Qi being rejected at the (approximately) constant temperature T\. In every reversible process. since it In a complete cycle the has returned exactly thermodynamic state. in which the heat Qwn. at every stage. from T* to T^\ the appropriate form of equation (19. e. the alternative form Qi = TiASi could be used. i. the temperature of which differs only infinitesimally from that of the system.g." and it is necessary now to consider the "surroundings. the change in entropy of the surroundings will be equal to the entropy change of the system. the efficiency of a cycle involving an irreversible stage must be less than that of a Carnot cycle. as in the previous case. cluded in the system. takes place in an irreversible manner. it follows by the heat + . provided T\ is constant. neither will undergo any zero. taken up by the system at any stage is supplied reversibly reservoir. the sum of the entropy changes of the system and its surroundings will be In a complete reversible cycle.9). The remainder of the cycle may be supposed to be the same as for a Carnot cycle.4). that the higher temperature (T%) stage. Entropy Change in Irreversible Process.. Suppose. but of opposite sign.e. The work done is given by Q2(irr. f e. In actual practice. Hence. For a nonreversible cycle the proportion of heat that is unavailable for work is. is not all taken up at the one temperature T 2 but over a range of temperatures. resultant change of entropy. as in equation (19. the heat absorbed by the working substance. Incidentally.) being given out reversibly.144 THE SECOND LAW OF THERMODYNAMICS 19d of heat that is returned to the reservoir at the lower temperature in a reversible cycle in terms of the entropy change.
or. ~^r 1 + QT &A nr ^ o* < r\ 0. The increase of entropy when the surroundings are brought back to their original state. and hence the entropy change during this process is equal to qw.13) Since the heat is absorbed in an irreversible manner. This can best be ascertained from the change of entropy when the surroundings are restored to their original state.1)] Q2(irr. but will depend on the particular path taken.13) becomes A+B EQirr. would be less than zero. ENTROPY equation (19.* o. The initial state of the surroundings can be restored by adding the various amounts of heat involved in the qi TT terms at the appropriate temperatures. after the process A B. the required entropy change must then be equal in magnitude to this quantity but of opposite sign. therefore. 19b). y"'* + y^ < 0 (19. is taken up reversibly. B+A I where gw. A*B Z . irrespective of the fact that they were not supplied reversibly to the system during the stage A > B. the first summation in equation (19. which involves one or more irreversible stages. and the completely reversible path B A according to the arguments presented above./T terms./T terms is actually less than the increase of entropy of the system. .14) In an irreversible process A > J5. is the sum of the qin. equation it is seen that (19. By the definition of the entropy change of the system [cf.SA  D ^~ > 0. reversing the signs throughout. therefore.) . SB . the summation of the q\ rr . A>B z JL + z B+A < . Consider a perfectly general cycle ABA made up of a path A > B. In order to obtain the entropy change. T\ T\ . (19. these heat quantities are added reversibly (cf. .13) will not be definite. The entropy change of the surroundings in the irreversible stage A B must now be considered. therefore. the sum.6)]. or the q/T terms for a series of infinitesimal stages.) 145 + Ql(rev.12) In general./T. for a cycle which is not completely reversible. and hence. . and hence equation (19. (19. of all the Q/T terms.19e that [cf. over the whole cycle.
of its surroundings. In a complete cycle. to an isolated system of constant energy (cf be seen later that if the energy (and volume) of the system remained constant in an irreversible process. reversible or irreversible. however. this. etc. as suggested above. . that is to say. e. or spontaneously occurring. actually or in principle.e. its entropy would increase. It should be clearly understood that in the latter event the total entropy of the system and its surroundings remains unchanged.14).. 19f..g. the net entropy change in this process is zero. Irreversible Processes and Degradation of Energy. but the entropy of the surroundings simultaneously increases by a greater amount. will then be an increase * Many changes which are naturally spontaneous . is accompanied by a gain of entropy of the combined system and its surroundings. is completed by the re any ABA >A. and hence the whole cycle must be accompanied by a gain of entropy. in the solidification of a supercooled liquid. so that there is a net increase of entropy. Any net increase in the entropy of the system and its surroundings. quite apart from that It often happens that the entropy of the system. t It is sometimes stated that the entropy of the "universe" is increasing. It follows. implies a knowledge of processes occurring outside the earth and so cannot be justified.. the system returns to its original state. solution of zinc in copper sulfate. it must be concluded that all such processes are associated with a net increase of entropy. can be carried out..e. the working substance. irreversible process because of the associated energy change. actually decreases in a spontaneous. i. that an irreversible process.146 THE SECOND LAW OF THERMODYNAMICS total entropy 19f The irreversible process A change of the system and its surroundings in the * B may thus be summarized as follows: Increase of entropy of system Increase of entropy of surroundings = SB = A^B SA ^ T SA  Net increase of entropy of system and surroundings (ASne t) * SB A*B L %r' T As seen by equation it follows that in system and versible (19. the law may in fact be stated in the form that all processes occurri'ng in nature are associated with a gain of entropy of the system and its surroundings. path jB Since natural. and hence it undergoes no resultant change of entropy.g. processes are irreversible ( 18b). or a cycle of which any part is irreversible. and hence irreversible process there is a net gain of entropy of the If the cycle its surroundings.* From some points of view this is one of the most important consequences of the second law of thermodynamics. therefore. as required by the second law of thermodynamics.^ It should be remembered that the net gain of entropy accompanying an irreversible process refers to the combination of the system and its surroundIt will 6d). this quantity is greater than zero. as in an irreversible cycle. . There is an increase of entropy only when the change occurs spontaneously and hence irreversibly. in a reversible manner. ings. expansion of a gas.
excess of that which is transferred in a reversible cycle. As a result of the irreversible nature of the process. as seen above. often used in engineering problems. where QCx. is zero ( 19d). p. however. is defined by j~ that is. thus. represented by the Saxis. This result gives a fundamental significance to the net entropy increase A net of the constant energy system: the product of ASnet and the temperature at which heat is rejected is equal to the quantity of heat that is "wasted" or "degraded" in an irreversible cycle. therefore. is equal For a given absorption of heat.  TASnet. A B IV II Further. respecOn such a diagram an isothermal path is obviously a straight line parallel to tively. "Chemical Engineering Thermodynamics. TemperatureEntropy Diagrams. and hence AS8urr." 1944. for representing thermodynamic changes in state. It represents heat taken in at the higher temperature which would have been available for work if the process had been carried out reversibly. For a reversible cycle. 1 Cf. It is Entropy because of the constancy of the entropy in a adiabatic process. therefore. ASn rt. has been returned to the surroundings in irreversible cycle an amount of heat e Q . This result gives something of a physical significance to the net entropy increase as a measure of the irreversibility of any . no process the entropy change accompanying any such reversible process must be zero. A reversible. Dodge.e. for the same quantity Q% of heat absorbed at 7 2 . whereas for an It follows. therefore.. the work done in to Qi jPiASnct. 9 + process. If. it has been transferred or "degraded" to a lower temperature where its availability for work is diminished. in a complete cycle. that the term isentropic change being (Greek: same entropy) is often used when referring to a process of this nature. = ASneti <?. zero.15) the temperature T being that of the surroundings. 1 convenient form of diagram 19g. the sink. i. is one in which the two axes indicate the temperature and entropy. 71. = AjSBU rr. .. F. a quantity of heat Q 2 is taken into the system at the temperature T z and Q\ is rejected at the lower temperature Ti then in an irreversible T cycle the heat rejected. in any reversible cycle. the entropy reverse.ENTROPY in the 147 entropy of the surroundings. since in an adiabatic heat enters or leaves the system. that in an irreversible process it is positive. the irreversible cycle is TiAS ne t less than that done in a reversible cycle operating between the same temperatures. III ' a straight line parallel to the Taxis. (19. adiabatic change is. B.
deg. is equivalent to f. Entropy Changes infinitesimal. the heat of vaporization of 1 mole of water at 25 C. or T.2)]]. therefore. (19. for example.. Qrev. liquid to vapor (vaporization). ^+^= r."" is an extensive the of material entropy quantity constituting the property system under consideration must be stated. since the pressed in terms of calories per degree. the heat of fusion. In the case of fusion. at a definite temperature. In this and the following section the entropy changes accompanying certain simple processes will be evaluated../T terms. q = dE + w./T. as in Fig. but it has not been used here because in the treatment of the quantity Qrov. For example. respectively. be determined in a similar manner. (19. isothermal process. since the work done is equal to Q 2 + Gilt can be seen.e.514/298. or transition from one These changes can be carried out reversibly crystalline form to another. or as the sum of the qt *v. 8a).16 . it would be a simple matter to derive the efficiency of a Carnot cycle. the entropy of 1 1 vaporization determined above was given as 35.. cal. A Carnot cycle is Ql=Ql T2 as found earlier [cf. appears as a logical development of the second law of thermodynamics. The stages I. is simply AH//T. heat" accompanying the phase change./T. that if entropy had been arbitrarily defined as Qm.0313 atm. Ti ' equation From this result the efficiency of the Carnot cycle can be readily derived. in stage III. in stage I.g.. and if the process has been carried out at the temperature T 9 the entropy increase. mole" 1 25.5) may be written as .1 mole.26 cal. The entropy of vaporization can AH 25 C is 10. referred to as the entropy of fusion. e. + .514 cal.16) . instead of being an apparently arbitrary function. the system remaining in equilibrium throughout The heat supplied under these conditions is the socalled "latent (cf.16 = 35.. in equilibrium with its vapor at a presSince the temperature is sure of 0. 19b adopted. Entropy Change and Phase Change. This procedure is sometimes 19a./T. III and IV correspond exactly to those described in It is at once obvious from the diagram that the entropy change 18h. II.148 THE SECOND LAW OF THERMODYNAMICS 19h very simply represented by a rectangle on a temperatureentropy diagram. deg. thus.1 It will be seen that the dimensions of entropy are heat/temperature. ]p5ljti. the urst law equation (7. of Ideal For an ><f9i. deg. and hence it is usually ex1 However.moleGas. consequently. the entropy of vaporization of water at 273. is 10. is exactly equal to the entropy change Qi/Ti. or qrev . 13.26 cal. One case of interest for which the calculation can be made very readily is the increase of entropy associated with a phase change. and the adiabatic paths are II and IV. solid to liquid (fusion). the isothermal stages at T 2 and T\ are indicated by I and III. .0 = 298. where $2 is the heat transferred reversibly at the temperaQz/Tz ture Ti. where Qi is the heat transferred at T\. i. 16 K.
191 If the process is reversible.22) state.21) Vi From this expression the entropy increase accompanying any given change in state of an ideal gas may be calculated.22)]. although it is possible to determine it by means of statistical mechanics.(7pln^. by purely thermodynamic methods. Further. it follows from equation (19. dE may be replaced by where CV is the molar heat capacity at constant Qcf./T is equal to the entropy change dS accompanying the given infinitesimal change in state. so that PdV. S = C v In T where s + R In V + * . derived For an appreciable change with 1 mole of an ideal gas. it follows that q r*v. since the quantity of heat <?re r is transferred reversibly.20) The value of this constant cannot be is the integration constant.17).19) gives an expression for the entropy of 1 mole of an ideal gas. equation (9. For a change in thermodynamic 2 . as almost invariably the case for processes considered in chemical thermodynamics.R In P + s' . from equar tion (19.23) analogous to equation (19. as will be explained in Chapter IX.20) that initial state.CP where SQ is T . ENTROPY 149 and the work is restricted to work of expansion.21). qny = dE (19. where P is the pressure of the system. volume. An alternative form of (19. (19. and the final indicated by the subscript 2.17) is . at a constant temperature T. V and it is utilizing the fact that for 1 mole In of an ideal gas Cp Cv is equal to JK.20) may be obtained by replacing by RT/P. readily found that S . general integration of equation (19. thus. equal to s + R In R. and P may be replaced by RT/V. AS = S 2 which is S l . + . it is evident that ds _ For the special case of 1 a mole of an ideal gas. 9e).RlnJ^i i * therefore. w may be replaced by PdV. (19. hence.S 2  Si = C v In +R ^ li In (19. .19) Making the assumption that CV is independent of temperature (cf. (19. AS . equation (19. indicated by the subscript 1.18) thus becomes CydT dS^Cv^f + R^ (19. between an thermodynamic state.
which If this quangives the heat absorbed in an isothermal. (19. an expression for the entropy change. so that equations (19. the condition for a reversible. (19. (10. This is because the entropy change depends only on the initial and final states.g. when an ideal gas expands (irreversibly) into a vacuum.7). A/S is positive.23) reduce to AS r . alone. the expansion is accompanied by an increase of entropy of the system. isentropic.R In ^ R In p (19. can thus be derived from entropy considerations.e.. no heat is taken up from the surroundings ( 9d). the results are applicable to any change in thermodynamic state. reversible process. is obtained. 19 j. Incidentally.5).CVln J7 i 19j For a change of temperature at constant volume. the entropy increase of an ideal gas is seen .24) whereas. In the isothermal expansion of a gas.e.25) It should be noted that although the foregoing equations are ultimately based on (19.18).3). and not on the path between them. process. i. and hence AS should be zero. In a reversible. (10.6) and (10. Consider a number of ideal gases.23) gives ASP . by equation (19. consequently. the entropy remains constant. Entropy of Mixing. e. The characteristic equations for a reversible. adiabatic process. identical with equation (19.150 THE SECOND LAW OF THERMODYNAMICS from equation (19. For an isothermal process.21) equal to zero. that is to say.26) The same result could have been derived directly from equation (9. TI and T* are identical.26). the final volume F2 is greater than the initial volume V\ and. that this equation.26). adiabatic The process can thus be obtained by setting equation (19. of the gas. incapable of interacting with one another in any way.21) to be 2 ASr .. tity is divided by the constant temperature T.. result is which is identical with equation (10. however. i. irrespective of whether it is carried out reversibly or not. It must not be forgotten.21) and (19.21).CplnJ^J i (19. for the same temperature change at constant pressure. and so the entropy In this case the net entropy increase is of the latter remains unchanged. adiabatic. which applies to a reversible process. like the others for entropy change derived in this section. is independent of the manner in which the process is carried out. placed in a vessel in which they are separated . equal to the increase in entropy of the system.
30).conditions. each kind is present to the extent of J X f j^. and since the total constitutes threeThe fourths of the hydrogen.31) a total of (19. given by equation (19. There are nine kinds of ortho molecules. the in general. V + .g.19j ENTROPY 151 by partitions.XX(CV In T + R In N. Although equation (19. so that the gases become mixed. hence.27) the temperature being the same throughout.29). the result Replacing (19. the total pressure of the mixture same as that of the individual gases before mixing.27) the mole fraction ( 5b) of the given gas in the mixture.*.28) and (19.20) as ). and the entropy S* 2 Suppose that all the partitions are Each gas now occupies the total is then represented by ). by NF.R . the number of moles of any gas. the result is ASm = .In it*. and is the total entropy Si of the system. the mixing defined by equation (19. volume it occupies. + R In . of ideal gases will he the . while the latter occupy only one. ? where N Vi  * .32) is always positive.In N< =. If n t is. volume V of the system.32) has been derived here for a mixture of ideal gases. Si  n*(CV In T + R In v. Calculate the entropy of mixing of the ten different kinds of hydrogen molecules. of two or more gases. equations (19. its logarithm is negative. It is of interest to note that since the mole fraction N t of any gas in a mixture must be less than unity.28) the separate gases were each at the same pressure before mixing..30) St of the . mole fraction of each of the nine forms of orthohydrogen is thus fa.31) 1 mole upon dividing equation by the n total of the mixture of ideal gases is obtained number of moles n.R N< In N. e. at low temperatures the molecules of the former occupy nine closely spaced rotational levels. by . is accompanied by an increase of entropy. .2>(CV In T + R In V + (19. is (1929) is in (19. Problem: Molecular hydrogen normally consists of three parts of orthohydrogen and one part of parahydrogen. hence ASm as In other words.) The increase of entropy resulting from the removal of the partitions and the mixing gases. in accordance with equation (19. thus. it can be shown that it applies equally to an ideal mixture of  liquids or an ideal solid solution. The entropy of mixing for (19. where n< is the number of moles of that gas and n is the total number of moles in the If system. = . removed.known as the entropy of miring A m is equal to /S 2 S\. 41 the ratio of the initial volume t>< of any gas to the total volume V is equal to n. by diffusion. + (19. (19. Since there * Under these . which is the sum of the is entropies of the gases in the separate compartments.R XX..32) assuming no change of temperature or total volume upon mixing./n.
and hence an increase of entropy upon fusion is to be expected. A simple illustration is provided by the melting of a solid. b. or vice versa. is one of great value in many cases. The conversion of mechanical work into heat. have become mixed in a random manner.p. therefore. In A) ASm . This result will be utilized in Before closing this chapter. and for the one para term it is J. the spontaneous conduction of heat along a bar of metal means a more random distribution of the kinetic energies of the molecules.i In J] = 2.32). is of the latter case. has been suggested as the working substance in a .152 is THE SECOND LAW OF THERMODYNAMICS 19k only one kind of parahydrogen. shows that they are associated with an increased randomness of distribution. 70.1 #[9^ 24 n.. b. because of the relatively large extent of order still present in liquid water above its melting point the entropy increase is smaller in the former than in the . For example. for the nine identical ortho terms the mole fraction is j^. or mixed with biphenylene C). deg. accompanied randomness a knowledge of the Similarly. as seen earlier ( 18e).. Thus. As seen in 19h. is associated with the change from ordered motion of a body as a whole to the disordered or random motion of the molecules. it is also useful from the qualitative standpoint. Similarly.p. Apart from its quantitative aspect. The concept of entropy as a measure of randomness.4 C.1 mole. 254 C) alone.. The subject will be taken up in greater detail. the greater will be the entropy C is 5.26 cal. deg. EXERCISES The use of biphenyl oxide (m. + . the molar entropy of fusion of ice at 1 1 1 mole" while that of benzene is 8. the greater the increase of disorder accompanying fusion. (m. The entropy of mixing is obtained from equation (19. Entropy and Disorder. 288 1. It seems reasonable.mole"" at 5.p. which will be considered later. 87. In general.1 increase. deg.27 cal.. it is appropriate 19k. this is equal to the heat of fusion divided by the temperature at which melting occurs.p. from a somewhat different point of view. There is obviously an increase of disorder in passing from the solid to the liquid state. An examination in Chapter IX. the diffusion of one gas into another means that the molecules of the two gases. which were initially separated. viz. entropy change often provides information concerning structural changes accompanying a given process.39 cai. there being ten terms in the summation. to refer to an interesting aspect of entropy which throws some light on the physical significance of this apparently theoretical property. of the various processes which take place spontaneously. and which are accompanied by a net increase of entropy. to postulate a relationship between the entropy of a system and the randomness or degree of disorder in the given state. for it is frequently possible to estimate whether a given process by an increase or decrease of entropy from a consideration or disorder in the initial and final states.208/2 4. its mole fraction is just J. but a general indication may be given here.
gas undergoes throttled expansion ( lla). 10. Assuming reversible behavior. units.0 mm. Show for an adiabatic change derived + . Mercury vapor at 357 C and 1 atm. Show that it is possible to calculate the temperature at the end of each stage. to form a mixture at the total pressure p. Assuming the vapor to behave ideally. is carried out as follows: (i) isothermal expansion at 100 C to volume 37. how much work in ergs would have to be done for every kcal. consisting of 21 mole nitrogen. It has been suggested that a building could be heated by a refrigeration engine operating in a reversed Carnot cycle. A reversible Joule cycle consists of the following stages: (i) an expansion at the constant pressure Pz. each at pressure p. cycle. so that the entropy change of the system could be evaluated. oxygen and 79 mole pressure. If air. of heat liberated in the building? 5. on the other side of the throttle. 2. what would be the entropy change per mole of air? Ideal behavior may be postulated. The process is irreversible. At this 10. (ii) an adiabatic expansion to a lower pressure Pi. work is done upon it. deg. Is the sign in accordance with expectation? 7. isothermal stage and the efficiency of the cycle. 357 C). calculate the entropy of ethanol vapor at 1 atm. pressure. (i) water.4 cal. pressure is heated to 550 C and its Calculate the entropy change in the conventional pressure is increased to 5 atm. Suggest how the change from supercooled water at 10 C to ice at the same temperature and pressure could be carried out reversibly. (iii) a compression at the constant pressure Pi. 4. and the heat of vaporization is kcal. Determine the net change in entropy of the system and its surroundings. mole' 1 . could be separated into its pure constituent gases. Carnot cycle.22). 1 53 Consider the advantages and disadvantages with respect to the use mercury (b. and prove that with an ideal gas as the working substance the efficiency is of (ii) given by W =1 Q where Q is the heat taken up in stage (i) of the cycle. The entropy of liquid ethanol is 38. on one side and 20 atm. and then heat is given up to the building at 22 C. (iii) isothermal compression. pressure at 25 C.] 9. Determine the work done in each (iv) adiabatic compression to the initial state. [TJse equation (19. at 1 atm. Justify the statement that the solidification of a supercooled liquid is accompanied by a decrease in the entropy of the liquid but a greater increase in the entropy of the surroundings. is R N l n N P er mole of mixture.19 temperature the vapor pressure is 59.EXERCISES heat engine. (iv) an adiabatic compression which Draw the indicator (PV) diagram for the restores the system to its initial state. 8. A vapor being treated as an ideal monatomic gas. An ideal S % % that equations (19. at constant temperature.p. each at 1 atm. the 6. at the same temperature. Suppose the engine. takes up heat from the outside at 2 C. 11. for the same purpose. 3. and so the entropy change must be calculated by imagining the same change in thermodynamic state to be carried out reversibly. Show that the entropy of mixing of a number of ideal gases.23) lead to the various conditions in lOb. (ii) adiabatic expansion to volume 67. the pressure being 200 atm.21) and (19."1 mole"1 at 25 C. in which the initial system consists of 1 mole of an ideal gas of volume 7.
9)]. the volume being the same in each case. (20.\ dT)y/ \dTjy' (dE/dT)v is equal to Cv.5) . this becomes dSv } dS equation (4. from equation (20.1) is of general applicability. [cf. it is seen that C /ri ri 164 .2) that dS ^ If constant Cr (20. S dE and since it follows *s\ /(^. (20.3) volume conditions are understood. the result may be stated in the form dSv and = ^ dT = C d v T In T. the heat capacity at constant volume. provided only that the work involved is work of expansion.e. when dV i$ = dEy/T or zero. ' TEMPERATURE AND PRESSURE RELATIONSHIPS The equation (19. For the entropy increase accompanying a change in temperature from Ti to T 2 at constant volume.. dS = ' (20. both By and the general rules of partial differentiation E being functions of T and 7.18). and So is the hypothetical value at the absolute zero. Variation of Entropy with Temperature. i. For an infinitesimal change at constant volume. integration consequently gives (S S ) v = C <dT= T C v d In T.4) where S is the entropy of the system at the temperature T.CHAPTER VIII ENTROPY RELATIONSHIPS AND APPLICATIONS 20.
5)].78 X 10* I 2 cal.9) identical with (19. This gives the value of the integral in equation (20. former.20 + + . per g. pressure.25). from 300 K to 800 K Dividing through the expression for Cp by 10 T. or Cp is plotted against In T.9) As before.78 X . equation (20. or 'dS arguments exactly similar to those used in deriving equation (dH/dT) P is equal to Cp. the values of Cp/T are plotted against T. deg. nT. if Cp can be expressed as a function of the temperature. it is found that ~ + 133 X + 6. for temperature changes at constant pressure.24). atom" 1 CP = 6. In the sure. for example. and T2 (20. atom. is given by the expression temperature range from 71. it follows that at constant pressure H + dH P = dEP + PdV.8) T *T.1).20a TEMPERATURE AND PRESSURE RELATIONSHIPS 155 If Cv is independent of temperature this expression becomes identical with equation (19. graphical and analytical. Problem: The heat capacity at 1 atm. becomes An important use of equation (20. it is found that of (20.. and hence the increase of entropy for the change of temperature from TI to TV Alternatively. if Cp is independent of temperature. the heat capacity at constant pressure. By means and utilizing the fact that (20J) /on 7 ^ Hence.9). by means of equation (9. in the to 560 C.3). is equal to E Since the heat content PV by definition [^equation (9. viz. pressure of solid magnesium.~ l g. Determine the increase of entropy. the required integration can be carried out readily.9) is to determine the increase of entropy of a system for a specified change of temperature at constant presTwo procedures are possible. and the area under the curve between the ordinates representing T\ and T 2 is measured. (20.24). it is evident that dHj> is equal to TdSp.33 X IQr+T 6. and hence from (20. for an increase of temperature at 1 atm.
.4) and (20.3) with respect to volume. atom' increase l 1 deg. deg. at constant volume.33 X X 10* + 6.g. by entiation of equation (20. in particular.8) and (20.TdS and by applying the condition be expressed in the form dE. require modification if there is a phase change. it should be noted that equations (20. must be added to the values given by the foregoing equations. that dTdV For complete differentials. is 2 immaterial.~ l g. increase of entropy accompanying the phase change. by equation 00 / ( ^ 20 _ ~r + + 1.5). it is seen that PdV . (2011) ^ } differ Bearing in mind that CV is equal to (dE/dT) v it is readily found.33 10^  300) X J X 6. within the given temperature range. Upon rearrangement of equation (20.324 = thus 7.156 ENTROPY RELATIONSHIPS AND APPLICATIONS (20. Attention should be called to the fact that the equations derived in this section are quite general in the respect that they are not restricted to gaseous They are applicable to liquids and solids. this equation may Upon differentiation with respect to temperature.12) . at constant pressure. and (20. vaporization or change of crystalIn cases of this kind. (20.083 is + 0. so that 3 S/dTflV T dTdV such as dS and dE.11) thus leads to / ict \ /ir\  .9). X 10 4 2 = The entropy 6.07 cal. the line form.9).07 cal. 20b and hence. as derived in 19h.78 2 1 . fusion.~ g. as well as to gases. the result is dTjv dVdT \dV . at constant volume. Howsystems. ever. trations of this type will be considered in " 20b* Variation of Entropy with Pressure and Volume. [(800)  (300)~ ] 7. atom"" . of constant temperature.665 + 0. combination of the result "just obtained with equation (20. e.20 In 1.78 X X (800 lO4 !7 \ ') ' dT 6. the order of differentiation is identical with d*S/dVdT and d*E/dVdT with d*E/dTdV.1). Some illus23b.
the result is and hence the entropy change S 2 Si may be obtained by plotting the values of (dV/dT)p at various pressures against the pressure. analogous to equation (20.7). and then equation (20. for example.16) can be solved analytically. this is combined with equation the result is dH = TdS At constant temperature + VdP. . it is possible to determine the variation of entropy with Upon rearrangement of equation (20. an expression for (SV/dT)p may be obtained as a function of the pressure by means of a suitable equation of state.10). \ Cf IT i (20. gives H = E + PV. it is (20. and thus evaluating the integral graphically. the latter is equal to R/V. VdP 9 which defines dH = dE and if + PdV + (20. and integration between the pressure limits of Pi and Pz. recalling that Cp is equal to differentiating with respect to pressure that found dTdP T dTdP' result and comparison with the preceding equation leads to the Since (dV/dT} P can be obtained either from PVT data. General differentiation of the relationship the heat content. or from a suitable equation of state.1).15) pressure at constant temperature. at constant temperature.14) and differentiation with respect to temperature at constant pressure gives /\ dTjp From equation upon . V=T(~) + (~) v \ OJr t *p .20b ^<> TEMPERATURE AND PRESSURE RELATIONSHIPS 157 that the variation of the entropy with volume at constant temperature can be derived from the easily accessible quantity (dP/dT)v For an ideal gas.13) this takes the form.19) at constant temperature. so that * dV) T This is V* identical with the form taken by equation (19. Alternatively. dPdT \dP \dPj T dPdT (dH/dT)p. (20.
to represent .)  S(l atm. is given by * S*(l atm.17) could be evaluated graphically. it is evident from the equation of state PV = RT that (dV/dT) P is equal to R/P. and in this connecFrom this equation tion the Berthelot equation ( 5f) has been employed.). The integral in equation (20. in general.158 ENTROPY RELATIONSHIPS AND APPLICATIONS 20c 20c. Entropy Corrections for Deviation from Ideal Behavior. has been written in place of S*(l atm.. where it behaves ideally. An asterisk is used. is given by equation (20. and hence the entropy increase from the very low pressure P* to 1 atm.) = Since the actual gas may be regarded as behaving ideally at the low pressure P*.16) as / constant temperature being understood. viz. and S is the observed entropy of the actual gas at 1 atm. the required entropy correction to be added to the observed entropy value /S(l atm. it is found that ** ~~ dT and hence equation (20.) is then obtained by adding the two equations given above.17) ' ~l I i i_ 27 PT*\ 32 P T*)' t becomes "~ ~ s = 27 32 s\ a system in the postulated ideal state.16) is to determine the correction which must be made to entropy values obtained for real gases to allow As will be explained in Chapter IX for departure from ideal behavior.) and *S*(P* atm. S*(l atm. but in practice it is more convenient to use an equation of state. this is referred to as the standard entropy of the gas. One of the most useful applications of equation (20. it is possible to determine the entropy of a gas at 1 atm. The increase of entropy of the actual gas from 1 atm. For an ideal gas.5 . The correction is obtained in the following manner. but it is desirable to express the result in terms of an ideal gas at the same pressure. pressure.)  S*(P* atm.8 = where 5. pressure to a very low pressure P*. pressure. the quantities S(P* atm. the usual symbol for the standard entropy.) .) may be taken as identical.
lie. liquid or gaseous.19) that dE\ ^ a^ dV) T y' This result gives a physical significance to the pressure correction term in the van der Waals equation (cf.5 atm.18). it is seen that for is it PV dP\ = R dTj v and introduction V of this result into equation (20. same mole"" 1 . The value of Pc must be For nitrogen. consequence of this equation arises in connection with the ideal gas law = RT\ for an ideal gas.~* . which was postulated earlier ( 9d). Te is 126.0)* _ . Exercise 11)..20d TEMPERATURE AND PRESSURE RELATIONSHIPS 159 the very small pressure P* being neglected in comparison with unity. units.32 K. for the gas behaving ideally at the same pressure.19) gives (**\ =0 \dVjr of the The constancy energy content of an ideal gas. Problem: What is the correction to be added to the observed entropy of 1 mole of nitrogen gas at 77. viz.0 expressed in atm.32)3 0. . pressure in order to obtain the standard entropy $.109*.19) gives a relationship between pressure." mole" the value of R is 1. pressure to allow for departure from ideal behavior? and P e is 33. deg.10) and (20. so that the correction This result will be employed in 1 1 usually expressed in cal. (dP/dT) v is equal to R/(V 6).5 X (126. deg. solid. volume and temperature which An interesting applicable to all substances.32 K and 1 atm.12).217 cal. a direct consequence of the application of the second law of thermodynamics to the equation of state for an ideal gas. By \ (20. this equation gives (20. is thus ume. 23c. since this unit has been used in the derivation of equation When T is 77.S+ X (77.109/Z is equal to 0. 20d. also Chapter IV. Thermodynamic Equations is / nr> \ of State. there tion of state. irrespective of the volconstant at temperature. The second term on the righthand side thus gives the correction which must be added to the observed entropy S of the gas at 1 atm. and hence it follows from equation (20. For a van der Waals gas.987 term 0. K S Since the entropy in the is ~~ S + 27 ft 8288. obtained what is called / \77 combining equations a thermodynamic equa(20.
TJ\ dp p2  /J ' )  (20 22)  The change of heat content for a given pressure change can thus be evaluated from If heat content data are to be corrected for departure from .. derived from equation (5.e. iTT \ (20.e. deal behavior. 1 20e. pressure.e. in conjunction with a conventional equation of state. Stand.21) it can be shown where I 7 . pressure and the same gas when behaving ideally at 25 C. .15).he critical constants. and T is 25 C.. as stated earlier.20) may be used.20) (6E/dV)T. without difficulty that 9 RT. in atm. as in 20c. (20. sure change.7 atm. or other. however.. can be readily shown to be zero. i. taking R as >e K H 1 See. and of (3V/dT)p. or actual PVT data. (20. Problem: Calculate the difference in the heat content of 1 mole of oxygen gas atm. Te is 154.T dP. J.. by equation (20. the pressures PI and P 3 must expressed in the same units as Pc . if the values of Y. For real gases. H* is then the heat content of the gas at this Since the heat content of an ideal gas is indepressure when it behaves ideally. this is not the case.. but for gases an equation of state may be employed. are inserted in (20. pendent of the pressure.. Variation of Heat Content with Pressure. In the present case P 2 is set 2 is then replaced by H*. it 1 H 2 gives the required corrected value. For oxygen. and equation (20. 407 (1939). independent of the pressure.20) By rearrangement of equation Pi and and integration between the pressure it is limits of P 2 at constant temperature.14) obtained by the combina and (20. to determine the change of heat content accompanying a given presThis is of special value in connection with heats of reaction. Nat. thus. and jqual to zero. The integral in this equation may be solved graphically from PVT data.21) H\ and H z are the heat contents of the given substance at the temperature and pressures Pi and P 2 respectively.22). if available. Res. the ideal gas value. the Berthelot equation is useful For gaseous substances. when the changes of heat content are determined for actual gases at 1 atm. at very For an ideal gas.. found that IT. is like so that the heat content low pressures. .  *i = V. for example.16 (or 298. (dH/dP)r. Hence. Rossini. but the data are required for ideal behavior.3 and P is 49. 298. i.160 ENTROPY RELATIONSHIPS AND APPLICATIONS is 20e Another thermodynamic equation of state tion of equations (20.19). i. given in a preceding section. P 2 is set equal to zero. Here again. Pi is 1 atm. Bur. 22.2) K.
or if approximate results are adequate..2) a This difference is small in comparison with the experimental errors in measurements of heat of reaction. PV = KRT. M f . by equation T =_ \dT/ P P \dT) f ' (20. .23) becomes .22) is not very reliable when the pressure difference P 2 Pi is large. see Gilliland and Lukes. involving the use of reduced quantities and the compressibility factor ( 5i). as stated in 12b. 5e). Such a diagram id represented in Fig. however. deg. 161 1. it is probable that equation (20. mole" 1 thus. it is sometimes required to know the difference between the heat content If PVT data are available. It is consequently.21) may be used directly.987 X \ = 128X49. Eng.21).. tion (20. . _ i (2Q 24) The values (Fig. 7T2. therefore. Because of the approximate nature of the Berthelot equation of state. is simple and convenient. it is readily found that Vand hence. 25. n m Hi 9 sss X 1. Utilizing the definition of the compressibility factor K. that is. In connection with the study of highpressure gas reactions. as a first approximation. 880 (1933). 14. equaof a gas at high pressure and at zero pressure. ibid. and replacing T on the righthand side by 8Te and P by 7rP c where 6 and IT are the reduced temperature and pressure (cf. a universal function of and TT. 32.. of (d*/d0) r can be derived from the generalized compressibility chart If the pressure p2. mole" 1 . 4) i. integral can be evaluated graphically.7 1. be neglected in most cases.66 cal. respectively. it can. 957 (1940). Ind.s 1 Watson and Nelson. but if they are lacking. a generalized treatment. K is. ~ (298. that for a definite reduced temperature and reduced pressure.987 cal. at constant temperature. Chem. For experimental study of the variation of heat content with pressure.e. ' (20 23)  Dividing both sides by T.24) becomes As seen is in 5i. 2 may be replaced by the ideal gas value H* 9 so that and hence the H equation (20.20e TEMPERATURE AND PRESSURE RELATIONSHIPS . therefore. is taken as zero.~ l moie~ l the result is obtained in cal. it evident. equation (20. // 2  #.25) has the same value for all gases. the righthand side of equation (20. possible to construct a generalized diagram giving the (approximate) value of (H* H)/T for any gas with the reduced pressure as coordinate and the reduced temperature as parameter.
(20. ibid. ibid.27) with respect to entropy.. Md..2 0.2 \ 0. Chem. T) /S If p. Two and which are applicable to constant entropy. 64 (1940). 34. 396 (1940). Maron and Turnbull.26) is zero. and the ' and Bliss.PdV.e. processes can be derived in a similar manner. i.* 1. Edmiater.15). however. and (20. whereas at constant entropy. 28. Adiabatic Relationships. Cf..6 0.e. 14. 32.H)/T curves 20f.0 L 1.1 1.26) is differentiated with respect to volume. when dS a (20. 32. Ind. when dV is zero. analogous to (20.3 0.06 1. it is evident that at constant volume.ENTROPY RELATIONSHIPS AND APPLICATIONS 20f It may be remarked that a reduced form of equation (20..17) and a corresponding generalized diagram have been developed. at constant entropy.. abatic.16) or (20. 1112 (1936). they will not be given here.12) i. 544 (1942) Robiawn . Generalized (H* . As they are not widely used. relationships.27) equation (20. York.4 0..e. reversible adi Writing equation dE = TdS .. (20. Eng. at constant volume.8 1 2 Reduced Pressure 34 (*) 6 8 10 15 20 30 40 FIG.1) in the form (20. dS/v i.1 0.
it is From equation (20. Systems of this kind. The second condition is based on the postulate that the work done is work of expansion only. P . or differ only by an An important application infinitesimal amount from. in the and with respect to entropy. The four equations (20.13). however. which may consist of one or more phases. must be borne in mind. is given by difference and hence. and (20. AH\ (20. and constant entropy. General Applicability of Results. where is the pressure of the system (cf This means that the system 19i. homogeneous or heterogeneous.12) to heterogeneous systems will be given in 27b. at constant entropy.TdS the restrictions of constant pressure lead to A JJ \ dH ^ f + VdP. of any homogeneous system of constant composition.15). Two conditions. the pressure inside the system must either be equal to. are known as closed systems. is.2 la ENTROPY AND HEAT CAPACITY RELATIONSHIPS found that  163 results equated.29) Upon case. of equation (20.30) are frequently referred to as the Maxwell important to note that these results. Difference of Heat Capacities. ENTROPY AND HEAT CAPACITY RELATIONSHIPS 2 la. as well as the general equations of state (20. are applicable to systems of all types. 21. / (dH dS (as T and (?!) F.20). dH . must always remain in equilibrium with the external pressure. 20a). so that there is no loss or gain of matter in the course of any thermodynamic change. .28) It is relations. The mass of the system is assumed to be constant. first case.19). that. differentiating with respect to pressure. utilizing equation (20. It was shown in 9c that the between the heat capacities at constant pressure and constant volume. and that it is equal to PdV. in other words. 20g.12). respectively.30) (20. (20. it is seen that and equating the (20. the external pressure.19) and (20. at constant pressure. in the second results.
=s Cp in Cv Rj and agreement with equation (9.P 4. (dP/dT) v is equal to R/V^ ie.1). J) 6 'T' V* ' D \ \  ar/y is y~6^ J? ^^ . either solid. P/T. RT V and hence. at constant pressure.1). or to a homogeneous system containing definite amounts of two or more substances. and (dV/dT) P is JR/P. the van der Waals equation multiplied out to give PV and. and hence Cp Cv can be determined. Even without these data.29). the values of (dP/dT)v of (dV/dT) P can be obtained from PyJP data..164 ENTROPY RELATIONSHIPS AND APPLICATIONS 21a This result is applicable to any single substance. hence by equation (21. and omitting . so that may be replaced by RT/P abP in the correction terms v  *?_ JL p Differentiation of this expression with respect to temperature. a qualitative indication of the results to be expected may be derived from an equation of state.2) into (21. 2 0\ f01 ^ 21 . however. For a van der Wools gas. liquid or gaseous. the result is V^ZT^^ri p PV ^ py " " f As a first a/PV and approximation. For a real gas.2 > In order to evaluate (3V/dT)p in a convenient form.3) gives b  _ dbP dV\ V T 6 2a 3abP RT* Introducing this result together with equation (21. for example. dividing through by P. V ab/PV*. yields \ It is readily /dV\ " _R + dT) P P a R& a " 2abP found by arrangement of the previous equation that R = V p T and combination with (21. For 1 mole of an ideal gas. A + y n .
2 la ENTROPY AND HEAT CAPACITY RELATIONSHIPS of the smaller terms. (The actual value is approximately 1.. is 1 deg. higher a values.6) with that obtained above from (21. the atm. pressure given Problem ^Compare the value of Cp Cv for nitrogen at 25 C and 200 atm."" mole"" .937?. equation (21. 2 X 1. as a first approximation.) At low temperatures and high pressures the value of Cp Cv can become much larger than for an ideal gas. hence. . the difference between Cv and R does not increase continuously with the pressure. and is most marked at lower temperatures. Problem: Calculate CP van der Waals a being 1. 2 2 given in liter atm. equal approxivery mately to 2JS. P should be in atm.5). that for a real gas the value of CP Cv is greater than R.e. therefore. for these have.0820.39 Since a 1 Cv liter 2 for nitrogen at 25 C and 200 atm. . Without going into details. it may be noted that a similar treatment based on the Berthelot equation of state gives the result (27 1 + T i5'Kf5 3 applicable over a limited range of pressures. and subsequently decrease with increasing pressure. pressure. by equation (21. in a linear manner with the The difference between pressure. At 20 C.4). mole" 2 . However. As the pressure is increased this becomes of increasing imporCv should tance. the maximum.. mole~ . pressure.5). The reason for this is the tion (21.39 X 200 1. it is seen that 165 some Except at low temperatures and high pressures. and it is evident that at sufficiently high pressures Cp attain a maximum. and i.5) gives R in literatm. It is evident. 0. The results obtained directly from actual PVT data are in qualitative agreement with this conclusion. the difference increases.9/2. Cp Cv and R is evidently greater for easily liquefiable gases. in general. the so that last term may be neglected. is attained with nitrogen gas at about 300 atm. as implied Cp 3abP'2 /R z T* term in equaby equation (21.
93/2 from equation (21. Ind. either in Cv values for a number of graphical or analytical form. 20e). which may be compared with 1. 37. and Te is 126.2 K. 4 21b.1) may also be expressed in terms of the reduced temperature. and hence equation or dTjv Upon \dTjp \dPr it introducing this result into equation (21. pressure and volume..5). Rev. For a homogeneous system of constant mass the volume V is a single valued function of the temperature and pressure. The thermodynamic equation (21. Difference of Heat Capacities: Alternative Expression. 2245 (1931). liquids and gases. 88.2) J 1. and P is 200 atm.. The quantity ( ) V \dl /P is equal to the coefficient of (cubical) thermal ex) V( \dF JT pansion a of the substance constituting the system.Cv p I 27 X Q. It is then possible to construct a generalized diagram for Cp Cv applicable to all gases (cf..8) is convenient.e. 373 (1940). 38. 40. 32. and the compressibility factor.1) has been used to determine the difference in the heat capacities of solids. Edmister. 6 Deming and Shupe. i..26. .0 K. Phys.5 X (298.0) 3 X 200 1 3 [ "M6 X33. 45. 490 (1914). and 4 == is the Schulze. 638 (1931). Eng.5 atm.166 ENTROPY RELATIONSHIPS AND APPLICATIONS when T is 21b 25 C. Chem.. J. For nitrogen Pc is 33.1) follows that This equation has been utilized in connection with PVT data. For solids and liquids another form of equation (21. 321 (1941). An alternative form of equation (21. and so it is possible to write " For a process occurring at constant volume (21.. Chem. equation (21. to determine Cp 6 gases over a considerable range of temperature and pressure.7) becomes dV is zero. Phys. Chem.6) gives CP . Roper. Z. 3. rcf. 848 (1932).76/2. phys. hence 298.
deg. X 298.7) for (dS/dT) P . it is found upon *'().g. the atomic 1 weight divided by the density. temperature and pressure.93 g. conditions.2 K. atom" 1 .9) that using the values given for a and /?. This equation has been used for the determination of the heat capacities at conThe quantity (dV/dT)p is the rate stant pressure of both liquids and gases." 1 g. Lummer and Pringsheim. The other of thermal expansion and this can be measured without difficulty. Appendix). ibid. is called the adiabatic temperature coefficient. 64. it can be readily seen from equation (21 . 298. Cv will be in cc.785 X 10~ 6 atm.9) This equation has been found especially useful for the conversion of heat in particular... 107 compressibility coefficient hence.e. (1898).atm. i. rearrangement that . For a simple system. Eucken and Mticke.. 681. Joule..159 cal. i. . 54 2705 (1932). if this is expressed in cc.~ g.57/8. e. B18. phys.2 X 63.e. .~ l . adiabatic.atm. e. Am...93 l 0. Mag.e." 1 and atomic weight 63. it follows that dP Utilizing equation (20. and observing the temperature change.e./(?). g.g. . 62.2 X 10~ 6 deg. Determination of Heat Capacity. Phyrik. 1162 (1927)..93.0242 cal. P _ CV = (49. 49.57 X X l(F r X 8. It can be determined by allowing the fluid to expand suddenly.0242 deg. the coefficient of expansion a is 49. Chem. so that and hence. atom" 1 Since 1 cc. ibid. In the present case V in equation (21 . Dixon and Rodebush. the values pressure Problem: For metallic copper at 25 C. Chem. over a known pressure range.9) is the atomic volume. 655 Z.785 0. Phil. a single 21c. 696 (1940).2 X IP" 6 ) 2 0. the entropy is dependent on two thermodynamic variables.~ l and the compressibility coefficient /3 is 0. only... Calculate the difference in the atomic heat capacities at constant pressure and constant volume. (Table 1. 17. Ann. since it applies to constant entropy. substance or a homogeneous mixture of constant composition. Burlew. orTV  (21. Soc. 63.. measured at constant (atmospheric) to at constant volume ( 17a).57. Richards and Wallace.2iC ENTROPY AND HEAT CAPACITY RELATIONSHIPS j8.. (3T/dP)s. CrCvcapacities of solids. by the method used in 21 b. it follows that at 25 C. the density is 8. /. . and hence adiabatically. i.15) for (dS/dP) T and (20. factor. 6 364 (1859). 167 (1932). 690. . is equivalent to Cp 0. cc. atom" i.
^1 mole" 1 for the same increase to gases. but it is usually applied For an ideal gas. deg. a simple matter to derive an expression for the influence of pressure on heat capacity. If the constants in a patisfactory equation of state.e. deg.12). the value of Cp for nitrogen increases from 6. (21. The values of (d*V/dT2 ) P for a given gas at various pressures can be derived from PVT measurements. 1091 (1930). At ordinary temperatures. and equating the it is found that dTdP T\dP) T  This equation holds for any homogeneous substance. the BeattieBridgeman z 2 equation.15). and equation (20. The treatment may be illustrated in a simple manner by utilizing the van der Waals 7 7 See ref. at constant pressure. 36. at constant temperature. the heat capacity Cp may be regarded as virtually independent of pressure. exhibit marked variations of the pressure (cf. the heat capacity increases by about 2 cal. is given by an expres At a sufficiently low pressure. is / dS\ ^Cp T \dTJp dS\ 9 with respect to pressure. it is evident from the equation PV = RT that (d~V/dT*)p is zero.11).1 mole"* 1 at 200 atm... where the gas behaves ideally.7). 5. however.g. by graphical integration CP Cp can then be determined for any desired pressure. also.. (d V/dT ) P could be expressed analytically as a function of the pressure. Hoxton..e. represented by P*.12) at a constant temperature T. at 70 C. e. especially at low temperatures. and hence the heat capacity should be independent of Real gases. if available. . ~_ = / dV\ results. this pressure may pressure be taken as the lower limit of integration. heat capacity with pressure. then  CJ rl>. The actual change of heat capacity with pressure sion obtained by the integration of equation (21. for example.168 ENTROPY RELATIONSHIPS AND APPLICATIONS 21d It 2 Id. were known. P)T \d!F/p' with respect to temperature. Variation of Heat Capacity at Constant Pressure with Pressure.8 at low pressures to 12. i. Phys..1 cal. however. of pressure. 9e). and then integrated in accordance with equation (21. Upon differentiating equation (20. i. and if the upper limit is any P at which the heat capacity at constant pressure is Cp. Rev.
12). deg.. 33. tions are in agreement with the results obtained by the application of PVT data to equation (21. using (i) the van der Waais equation (ii) the Berthelot equation. and also with the limited experimental determinations of heat 8 capacities at high pressures. . cal..13) may be neglected. Worthing. Since 1 literatm. Phys. Rev. (i) R must (7p F * CP P 0. 22. become appreciable. and taking P* as zero.""1 mole""1 .2 the change in heat capacity should be 0. 217 (1911). it At moderate temperatures and pressures the second term on the righthand side of equation (21.. the value of Cp should thus increase in a The rate of increase should be less the higher linear manner with the pressure. Chem. atm.""1 mole" 1 and equation (21. and at sufficiently high presThese qualitative expectasures Cp should reach a maximum and then decrease.082 X (298) 2 0. It ENTROPY AND HEAT CAPACITY RELATIONSHIPS was seen in 21 a that for a 169 van der Waals gas cf. X 1. when Cp Cp is a linear function of the pressure. is equivalent to 24. especially at low temperatures. P in atm. 100 atm. i.12) it is found that This result. and mole units.39 X 100 the second term being negligible.13) then gives. From the Berthelot equation of state in conjunction with (21."""1 mole"" 1 .038 literatm. equation (21.92 X 10~~2 in therefore be in literatm.e.12) ****' QabP Assuming a and follows that 6 to be independent of the pressure. Ind. deg. With increasing pressure the effect of the second term will the temperature. Eng. Problem: Calculate the change of CP for nitrogen when the pressure is increased to 100 atm. 1060 (1930). as might be expected. a is 1. For nitiogen..39 and b is 3. _ 2a 2abP (d*V\ \dT*)p so that from equation (21. at 25 C. with T = 298 K. Mackey and Krase.93 cal. 2 liter. is reliable at moderate temperatures and pres sures..3)3 dT and hence = ~  . .2 Id equation. deg.
3) and (20.  }p (2i.~ mole.f The first term on the righthand side is obtained from equation (20.""1 mole"*1 . equation (21.047 literatm. 24. respectively. necessarily give a good approximation for the derivative of the function. 880 (1933): see also. 25.H* T dT equation (21. at least first approximation.1 cal.5 X (298)' .. 1C) may was seen earlier ( 20e) that (H H*)/T is a function of the reduced temperaand pressure of a form applicable to all gases [cf.082 X (126) 8 X J 100 32 X 33. 1353 (1932). (The experimental value is about 1. and the second term from the slope It ture as a of the plot of (H H*)/T against 6 (or In ^). at constant temperature. Variation of Heat Capacity at Constant Volume with Volume.0 cal. Eng. ibid. dT dTjp \dTjp I H H* to at and refer heat contents an the appreciable pressure P where. Watson and Nelson. deg. I nd. ail the values being at the reduced Cp is required. 3 .""1 mole" 1 . Upon introducing the mathematical //*) // dl(H  H*)/T1 dl(U  H*)/T] d In T dT = d(H . ref. it is possible to derive a Cp involving the reduced temperature and pressure. this conclusion may be open to some objection.5 attn.17). general relationship for Cp The simplest method of approach to this problem is to utilize the familiar definition of CP as (dH/dT) P . deg.15) gives CpcpThe temperature T may be hence din T is equal to din consequently be written as ^=~ + { 0. constant.25)]. 9 pressure corresponding to the pressure P at which Cp 21e. 9 Dodge. and equation (21.. hence the same must be true for Cp Cp. on differentiation. By means can be of equations (20.1 equivalent to 1. equation (20.11) obtained for the variation of Cv with volume. as before. this t Since a good approximation for a function docs not. 1 ^"afrV".) As in the case of other thermodynamic properties. and at a very low result pressure. 0. Chem. hence.. in accordance with equation (21.14) gives CP _ r* p ~ This is X 0. deg.170 (ii) ENTROPY RELATIONSHIPS AND APPLICATIONS Taking 21e Tc as 126.25) or its equivalent (Fig.0 K and JP 81 as 33.12).i6) expressed as since QTC where is Tc ^ is the reduced temperature. which is related to the is variation with pressure. 14). a relationship analogous to (21.
at any temperature. tion of CP Cv with pressure. For a gas obeying the Berthelot equation or the BeattieBridgeman equation (d*P/dT*)v would not be zero. large volume V*. respectively. constant pressure and volume. that this variation is small. but for a real where C* The gas this is not necessarily the case. an analytical method.4) and (21.22a THE JOULETHOMSON EFFECT 171 which. should thus occur at about the same pressure as that for CP. and hence some variation c f Cv with pressure is to be expected. is zero for a van der Waals gas.2) This expression is based upon thermodynamic considerations only. it is liquid or gas. Cv is independent of the volume (or pressure). hence. as given by equation (11. hence.. at any temperature.20).. The JouleThomson this section MJ. may be used. it may be considered here because the results are based on one of the thermodynamic equations of state derived in 20d. THE JOULETHOMSON EFFECT Coefficient. and hence Cv integration. Although the subject matter of has no direct connection with entropy.T.11) and (21. as well as for an ideal gas. The values of (d*P/dT*) v can be derived C*can be obtained by graphical from PVT measurements..5). and so for most purposes the heat capacity of any gas at constant volume may be regarded as being independent The maximum in the ratio 7 of the heat capacities at of the volume or pressure.e.. shows this to be true.12). chief application of these equations. however. possible to write or (22.e. 22a. gives c. as is to be expected. like (21.T.T is the constant heat capacity at low pressure. for a fluid. and hence is exact. where (dH/dP)r may be replaced by the JouleThomson coefficient. Cp/Cv.e.CP.c* . alternatively. i. may thus .e. i. is to gases. It is of interest to note that (d*P/8T2 )v 22. i. Cv should also be independent of the volume (or pressure) In this event. both of which are based on the van der Waals equation. it can be readily seen that since (d^P/dT^v is zero. It is probable. the effect of pressure on CP is equal to the variain the former case. viz. is MJ. upon integration. to this extent the material may be regarded as a consequence of the entropy concept. similar to that described above. referred to earlier ( lOe).13).. For an ideal gas. (dT/dJP)//.. i. the JouleThomson coefficient. Comparison of equations (21. In equation (20.
for example. Ind. Chem. Doming and Shupe. V must be the molar volume. for nitrogen . . the value of the dimensionless quantity (T/V)(dV/dT) P was found to be 1.~ .2). see also. For a van der Waals gas.0. and the molar volume is correct. it is seen from the results in 21a that T (**) \dTjp and hence 3a6P =F6+*L^ RT T(*?\ The equation (22. V and CV under the given conditions. Benedict. Chem.199 at 100 atm. Eng. satisfying the equation PV = RT under all conditions.21 cal. ( > At very 10 low. 34.) For an ideal gas.. (dV/dT) P is equal to V/T.0413 literatm.~ l mole" 1 cient of nitrogen under these conditions.T. 638 (1931).172 ENTROPY RELATIONSHIPS AND APPLICATIONS 22a be determined by inserting experimental results for (dVfdT)r. Since /UJ.~ l mole" 1 . Chem. 1112 (1936).. from equation (22.21 X 0. 8. Phys.64 X 28. the specific volume was then 8. Soc. deg. 448 (1935). Phys. 41. atm. use of an equation of state for a real gas. or zero. g. 544 (1942).64 Calculate the JouleThomson coeffiml. l 1 usually expressed in deg. pressure.2) may be put in the form if Cp is the molar heat capacity. CP is 8.2) for the \dTJp _v_. however. Edmister. /. Chem. 37. Rev. therefore. The values derived in this manner have been found to agree closely with those obtained by direct experiment. it will be convenient to have V in liter mole" and CP in literatm. Am.~ l and Cp was 8... and hence and is (The direct experimental value is 0. Eng. Perry and J.1 . .. 10 Problem: At 20 C. deg. 1189 (1935).1 mole. it follows. 59..143 atmr1 . this coefficient is usually not zero even at very low pressures. the last term in the parentheses is negligible Henman.. when ideal behavior That this is the case may be seen by making is approached in other respects.?a 3abP /g'T coefficient RT JouleThomson 2a thus becomes . 1189 (1937). Maron and Turnbull. 48. For a real gas. 28. deg. that the JouleThomson coefficient is always zero. Ind. the equation is then seen to be dimensionally The molecular weight of nitrogen is 28.0 X 10~3 liter. Equation (22.
1 1 deg.39 and 3.) 22b. the Joulecoefficient at low pressures.082) X (293) 0. since a and b vary with temperature and pressure. taking CP as 8. Press.0 299.7 .7 40 .4).92 2 X 10~ 2 2 X 100 J (0. atm.082 = (This is .22b THE JOULETHOMSON EFFECT 173 and then (22' 4) Except in the Thomson special circumstances when 2a/RT is equal to 6. equation (22." 1 equation (22. Problem: Calculate the JouleThomson coefficient of nitrogen gas at 20 and 100 atm. The JouleThomson Inversion Temperature.mole' .1 in fortuitously If atm. the values generally employed (Table I) being based on critical data.6 277.117. hence at 20 C (293 K). X 293 x ~ 3 iu X 1. where the JouleThomson coefficient changes sign from positive to negative or vice versa ( lie). C 20 60 100 180 220 300 376 330.1 mole~ l and CP is 8. C Since a and b are usually given in liter. The results are approximate only.167.21 cal. 1.3) gives.21 X 0.2 . is not zero.7 . If the van der Waals a and b are known it is possible to obtain an indication of the value of the JouleThomson coefficient at any given temperature and pressure by means of equation (22. For a van der Waals gas.." 1 .5 .. deg..143 is employed.39 ft _ 3. equal to zero. with P equal to 100 atm.T..082 literatm.142 atm.6) JK* TABLE XIV. 8.0413 2 X .~l mole~ l .0 212.3). pressure. 1.0413 literatm.T. the result is 0. deg. .0 C . equation (22.22 atm. viz.68.3) gives the condition as 20 ' 3a6F  (22.162.92 X 10~ 2 R is 0.21 0.4 . 1 JOULETHOMSON INVERSION TEMPERATURES FOR NITROGEN Inversion Temperature Upper 348 Lower atm.156. The condition for the JouleThomson inversion temperature.4) good agreement with the experimental value of 0. can be obtained by setting /ZJ.134.39 X 3.5 158. and mole units. as given by equation (22.5)  rib (22..2 235. X 1 MJ.
and are plotted (full line) in Fig.2) equal to zero. 48. the condition for the inversion temperature T is then seen to be ^ F0. fall is positive. outside the curve the coefficient is A generalized expression for the JouleThomson inversion temperature may be obtained by the use of a reduced equation of state. 15.8) 450 (1935). volume and temperature are expressed in terms of the corresponding reduced quantities . (22. Phya. 11 For all temperatures within the curve 600 1*200 20 60 100 200 Pressure 300 Atm. in general. as stated in lie. JouleThomson inversion curve for nitrogen the JouleThomson coefficient companied by a negative.. equation (22. (22. for every pressure. By setting equation (22. If the pressure. FIG. Reo. . 15. two values of the inversion temperature T. 4> and 0.** Roebuck and Osterberg.7) since C/> is not zero. and hence there will be.174 ENTROPY RELATIONSHIPS AND APPLICATIONS 22b This equation is a quadratic. a throttled expansion being acof temperature.7) becomes *(). The experimental values obtained for nitrogen gas are recorded in Table XIV.
i. e. they are. or Fig. these would be 94. i. 888 (1910).16). 15. it is possible to eliminate and thus obtain a general relationship between the reduced inversion temperature and pressure applicable to all gases. Provided w is less than 9. ^ is then unity.10) and (22. reduced inversion temperaturepressure curve. K .. the temperature should then be 3TC. Further.5 and 850 K..11) By combining equations (22. 15.10) then gives the two reduced inversion temperatures fa for the particular reduced pressure *.0 (22. at very low.5 atm.e.22b THE JOULETHOMSON EFFECT the reduced form of the van der Waals equation (5.. that dO /* If this result is 3ir< 3 ~ 9* + 6 ir is introduced into equation (22. The curve derived from equations (22.75 Tc and 623 K. Such. By choosing various values of the latter from to 9. and 313 K. insertion of these values in (22.. information would be of value in connection with the liquefaction of the particular gas. so that the maximum For nitrogen.10) and (22.11) yield results that are not exact. PhilSMag..11). pressure. According to equation (22. by equation (22. at constant reduced pressure. it is found that and substitution pressure. the data can be obtained for a generalized. 9 X 33. useful when direct measurements have not been made. T is 126. the maximum value of the reduced pressure for which inversion is possible is 9.10) gives the two values of the reduced inversion temperature as 0. pressure for the observation of a JouleThomson inversion should be 9Pe .e.11) gives two real values of <f> for each value of in. 3 X 126. and should be 3. which should be applicable to any gas.5 atm. and 6.11) is shown by the broken line in Fig. of this value for 6 in (22.11).9). 15 indicates that the reduced equation for a van der Wools gas is qualitatively correct.9) follows upon differentiation. by equation and Pe is 33.75T.e.11). 554 (1906).8). they provide an indication of the range within which cooling of a given gas by the JouleThomson effect is possible. 175 From 34l)80. The experimental values are 376 atm. insertion of these two ^'s in equation (22.0 or 378 K. zero. 11.10).g..9) gives for the corresponding reduced ' (22.75 and 6. K K "Porter. solution of equation (22. . compared be 0. i. <f> can be either 0. it (22. but is not quantitatively accurate. nevertheless. and eliminated by means of (22. 19.5 or 301. so that the actual (absolute) temperatures should For nitrogen.10) and (22.75. This fact is brought out more clearly by considering some actual results..5 or infinity. with the (extrapolated) experimental values of about 103 Although equations (22." Comparison of the two curves in Fig.
Derive an expression for S 9 standard entropy and S is the experimental entropy at 1 atm.~ l mole"1 . it is possible to express equation (20. 8. for any thermodynamic change in state. and the heat of vaporization at the normal boiling point (184 C) is 6. per mole of oxygen. using equation (20. respectively.100 cai. 14 to determine the change in A// for the reaction )Nt(0) $Hj(0) NHi(0) as a result of increasing the pressure from a low value. at the same tempera21a. where H\ and #1 are the heat contents at pressures P\ and P*. 1436 (1938)].6 C).07 + 3.32 (cf. from 25 C to the melting point (113. /.20). at 450 K.8 cal. 11. sponding entropy change is given by AS for a gas. determine the correction for the deviation from ideal behavior of the entropy of chlorine gas measured at its boiling point (239. in cal. What other information would be required to calculate the change of pressure.0 and 18. to 200 atm. S for a van der Waals gas.) 6.0 cai. virtually zero. Determine the increase in entropy of nitrogen gas when it is heated from 27 C to 1227 C at 1 atm. mole" 1 . pressure. Chem.740 cal. Exercise 7. Am.. deg. as well as the pressure? 12. Soc. problem 20c). deg. Suggest a method for determining 9. 7. Give the complete derivation of equation (20. in cal. heat content if the temperature were changed.5 cal. and show that the heat content of a gas which satisfies the equation PV RT at all temperatures and pressures is independent of pressure.~ mole" . 60. (Use CP data in Table II. g. at K in 77. Show that. is given by 1. deg. The heat of The heat capacity of the liquid fusion at the melting point is 3. 5. Calculate the difference in ture. where 8 is the 3. respectively. Derive an expression for 2 H\ for a van der Waals gas. accompanying the compression of 1 mole of ethane at 50 C from 30 atm. and the heat of fusion as 79. nitrogen gas 4. at 1 atm. the corre. Determine the increase of entropy accompanying the change of 1 mole of iodine from solid at 25 C to vapor at 184 C. 14 estimate the change of heat content. and 100 atm. 10."1 at C. By means of Fig. mole"" 1 l 1 is approximately constant at 19. at the same temCalculate the value of S 9 S for perature. to 300 atm. By means of the expression based on the Berthelot equation. Chapter VII). at 1 atm. 2. Describe the construction of a generalized chart for determining the (approximate) change of entropy of any gas with pressure at constant temperature.3). pressure (cf. Utilize Fig.~ mole [Frederick and Hildebrand. Show H + . The heat capacity of solid iodine at any temperature t C.21 X 10~4 (*  l 1 25) cal. CP = 13. determine the change of entropy 10 C at accompanying the spontaneous solidification of supercooled water at 1 atm. in general.21) and the results in the heat content. at 25 C. using equations (20.16) in the reduced form applicable to any gas.176 ENTROPY RELATIONSHIPS AND APPLICATIONS EXERCISES Give the complete derivation of equation (20. defined by P V = xRT. Taking CP for ice and water as 9.7).0 K) at 1 atm.. pressure.17) and (21. at 1 atm. pressure. that by the use of the compressibility factor K.
derive for a van der Waals gas has a of an expression maximum gas at 25 C. and 25 C. By means of equation (21. and CP 20. Cp/Cv . that for any homogeneous system.25 cc."1 ) the density is 0. The coefficient of cubical expansion a of sodium at 20 C is 21. By means Cv which Cp perature. Am. 1184 (1924)].6 X 10~ 6 megabar"1 (1 megabar deg. gas. Give the complete derivation of 18. Verify equation (21. Phys.) pressure is about 300 atm. deg.8) explain how a generalized (reduced) chart for Cv could be constructed. van der Waals equation applicable at moderate pressures (Exercise 16. mole"1 and Cp is 8.18). 15. Utilize equation (21. atom of solid sodium at 20 C. assuming the carbon monoxide to behave as a van der Waals 25. deg. equation. deg.(dP/dV) s /(dP/dV) T . and the value that would be expected if the gases behaved ideally. Show that this is essentially the basis of the Clement and Desormes method for determining 7 for gases [equation (10. of equation (21. By using equation (22.984. 2245 (1931)]. Chem. 177 Estimate the difference between A# for the reaction H 2 (0) + iO 2 (0) for the actual gases each at 1 atm. making use of the result obtained in the preceding exercise." 1 mole" 1 [Deming and Shupe.96 cal. 38.91 cal. Chapter II) can also be written as PF = RT f AP where A is a function of the temperature.. Determine the value of the JouleThomson coefficient for the conditions in the preceding exercise.3 X 10" 6 1 is 15. cc. 46." and the compressibility coefficient = 10 6 bar = 10 6 dynes cm.EXERCISES 13. 24. 14.. (K). Rev.6). 21.13) to find the pressure at which CP is a maximum for a van der Waals gas. Calculate the JouleThomson coefficient of carbon monoxide at 25 C and 400 atm. Why is this identical with the pressure at which Cp Cv Determine the pressure at which Cp for the pressure at value at any given tema maximum for nitrogen What is the value is mum If CP for nitrogen is 6.2) in conjunction with the compressibility factor derive a simple condition for the JouleThomson inversion temperature of a gas at any (reduced) pressure in terms of the variation of K with the (reduced) temperature. the molar volume is 76.97 g. equation (21." 1 [Eastman. L i Show that under these conditions (dC/>/dP)r = T(d^ A/dT )p and hence derive of in terms van the der Waals an expression for CP constants. form of the van der Waals equation (Exercise 7. . a maximum? .4). J. Cv is CP Cv at this pressure? (The experimental Cv is then approximately 4 cal. Cp 23. CP simplified t The 19." 1 mole" 1 calculate the maxivalue of Cp/Cv for this gas at 25 C. Soc. 17. pressure. given that (T/V)(dV/dT) P is 0. Calculate CP Cv per g. Chapter II).""1 mole" 1 .11)].5) can be derived directly from the simplified 7. Show that equation (21.. 22. et al. Prove Reech's theorem. and determine Cp at this temperature by using the Debye heat capacity = H 2 O(0) .
1. 42. but for the present it should be taken to represent substances in the pure solid state. 42. 23b. to the exclusion of solid solutions and amorphous substances.1) is zero for a pure solid substance. ibid. Cross and Eckstrom. Gibson. hence SQ in equation (23. ibid. /.. or Cp is plotted against In T. Chem. 1 : . Planck (1912) made a suggestion concerning the value of S Q which has become known as the third law of thermodynamics. ibid. however. Gibson and Giauque. Entropy at the Absolute Zero. now chiefly of historical interest. Nernst (1906).. ibid. 10. The values of Cp/T are then plotted against T. (23. 2554 (1917).CHAPTER IX ENTROPY: DETERMINATION AND SIGNIFICANCE 23. For this reason. a and at the substance given pressure. for the whole range of tempera1 Lewis and Gibeon. Rev. 2. The first and second laws have led to the development of the concepts of energy content and entropy. 18. 445 (1933). i. any pressed by means of the relationship fcf. J..303 log T. 47. THE THIRD LAW OP THERMODYNAMICS 20a that the entropy It was seen in 23a.. equation (20. it leads to no new concepts. line substance" will be more clearly understood later ( 24m). M. Pauling and Tolman. it is a generalization which leads to conclusions in agreement with experience. Eastman and Milner. and hence is a "law" in the scientific sense of the term. 1542 (1920). and does so become in the case of a The exact significance of a "perfectly crystalperfectly crystalline substance. Following the development of the "heat theorem" of W. from these in the respectively. Parks and Latimer. 45. 287 (1942). The socalled third law differs.. t 178 . Am. see also. it merely places a limitation upon that respect the value of the entropy. Chem. In its broadest form the law may be stated as follows Every substance has a finite positive entropy but at the absolute zero of temperature the entropy may become zero. Experimental Determination of Entropy. some writers hesitate to refer to it as a law of thermodynamics. 93 (1923).1) t/ where So is the hypothetical entropy at the absolute zero. According to the third law of thermodynamics the entropy of a pure solid may be taken as zero at 0K. Soc.. 2148 (1925). 257 (1936). 1533. 39. If the value of So were known it would be possible to derive the entropy at any required temperature from heat capacity data. such as glasses.. Chem Fhys. Nevertheless.e. could be extemperature T. The problem of evaluating the entropy of such a solid therefore resolves itself into the determination of the heat capacity at a series of temperatures right down to the absolute zero. 1529 (1920).8)] of . Eastman.
1 AgCl(s) Na(s) Br 2 (/) Ag(s) I 2 (s) Mg() K() Cu(s) * Hg(f) Pb(s) 9. one for each crystalline form.0 27. the difference to 10 or between these two quantities is so small at temperatures from 15 as to be quite negligible. of transition AH t /T t) where AH is the molar heat of transition and T t is the transition temperature ( 19h). It will be noted that the Debye equation gives Cv whereas Cp is required for the evaluation of the entropy by equation (23.6 47.5 C C Al (diamond) (graphite) 0..7 10. e. the observations are carried to as low a temperature as possible.3 20. the area under the curve between the melting point and any particular temperature.* ENTROPIES OF SOLIDS AND LIQUIDS IN THEIR STANDARD STATES AT 25 C IN CALORIES PER DEGREE PER G.5 15. the entropy of the solid at this temperature is then obtained by the procedure described above. the substance whose entropy is to be determined is a liquid at ordinary temperatures. K. which is equal to A/f//Tm where AH/ is the molar heat of fusion and Tm is the melting point. the results are then extrapolated to data can be represented by a Debye function ( 17c) and the characteristic can then be temperature 6 can be calculated. must be included in the entropy calculations.1).58 1.8 22. . To obtain the entropy of the liquid at the melting point it is necessary to add the entropy of fusion.g.1 16.23b ture. e.9 18.6 6.5 17.97 NaF NaCi(s) NaBr(s) KCl(s) KBr(s) KI(s) 13. since both T and (dV/dT)p as will be shown below ( 23d). ATOM (OR PER MOLE) Elements Compounds Fe(s) Zn(s) 6.36 12. This may be seen from equation (21.75 PbCl 2 (s) MgO(s) Al 2O(s) ZnO(s) 23. for the liquid. or Cp against In T.2 7. the area under the curve from K to any temperature T then gives the entropy of the solid at this temperature. 1 atm.4) which is applicable at low temperatures.2 27. However.2 7.5 10.4 For further data. up to the boiling point. it is first necessary to make measurements on the solid form up to its melting point.g.6 24.77 6. the values of Cv down to obtained by equation (17.75 15.95 36.0 32. the heat capacity curve for the solid will consist of two (or more) In cases of this type the entropy portions. as is frequently the case. All the information is now available for the determination of the entropy of the solid at any temperature up to which the heat capacity is known. since THE THIRD LAW OF THERMODYNAMICS 179 S is zero.1 Agl() Hg 2 Cl 2 (s) H O(0 2 19. 9 t TABLE XV.. see Table 5 at end of book.1). at which the heat capacities were measured.. then gives the corresponding entropy increase which must be added to the value at the melting point. the heat capacity determinations cannot be made right down to the absolute zero. In many cases the 10 or 15 K. and at the constant Since pressure. If . for K K example. The entropy of the liquid at any higher temperature may now be obtained by plotting Cp/T against T. If the solid undergoes a polymorphic change (or changes). approach zero as the temperature becomes smaller.55 12.
The Debye charactertemperature 6 was found to be 68 from low temperature heat capacity TABLE XVI.729 2.3/63. mole"1 .U.61. At 35.. i.e. mole"" . 394 (1936). 172.31 Total solid nitrogen. M.536 E.14 (melting point) by graphical integration 1 Fusion. the heat of transition being 54. in terms of the centigrade degree. and numerous papers in the J.U. and the standard entropies. mole*1 . 1932.239 36. S.. also 350 (1932). 1.3 cal.71/35.9 cal. for organic substances. 2. and the quantity 1 cal. and this was utilized to determine the enof the at 10 K.e. S..61 35. see Kelley.034 1. The method may be illustrated .9 cal.332.3 cal.32.729 E. tion A//V /T&. These values for the enthe of added to are the tropies phase changes entropy contributions of the two solid states and the liquid obtained by graphical integration of the experimental Cp/T values against T in the usual manner. mole""1 The melting point of the higher temperature crystalline form of nitrogen is 63.. mole"" 1 . Bur. i. at 1 atm.458 6. etc.U.32 K. Mines Bull.e. mole" /63. 2 As stated earlier ( 19h). 434 (1941).728 17.U.~! the temperature being on the usual absolute scale.239 E. so that the entropy of vaporization is 1. Some Organic Compounds/' 1938. is then added to the entropy of the liquid to give that of the gas at the normal boiling point. see G.71 cal. The complete i. Chem. is often referred to as an entropy unit and abbreviated to E. etc. Latimer.14 K. and the heat of fusion is 172.71 cal. deg. moleV77.61 the solid undergoes a change of latter tropy 1 crystalline form. For substances which are normally gaseous..32 K K K K 0. mole"1 to 10 from Debye equation 10 to 35. it is necessary to follow the procedure outlined above for the solid and the The entropy of vaporizerliquid states up to the boiling point of the latter.332. The is the heat of vaporization 2 For entropies of inorganic substances. Soc. "The Free Energies of Am. pressure (cf. THE ENTROPY OP NITROGEN GAS AT Process ITS BOILING POINT E. boiling point of liquid nitrogen is 77. 54.61 (transition point) by graphical integration Transition.9/77. entropies are usually expressed in terms of calories per degree. "The Oxidation States of the Elements. atom (for elements) or per mole (for compounds). giving an entropy of fusion of 172. mole"" . 14 63.536 5. 17.. 23c. istic by the experimental results obtained for nitrogen. For such substances the standard states are the pure solid or pure liquid at 1 atm. where AHV is the heat of vaporization and T* is the boiling point.32 (boiling point) by graphical integration Vaporization. Huffman.589 2.180 ENTROPY: DETERMINATION AND SIGNIFICANCE 23c Some actual experimental data will be quoted below (sec Table XVI). W. at 25 C. . 1332. derived from heat capacity measurements are recorded in Table XV. .14. M. but for the present sufficient indication has been given of the procedure used for determining the entropies of substances which are solid or liquid at ordinary temperatures." Parks and H.U. Entropies of Gases. pressure. 12e). the entropy measurements on K of transition is thus 54. U. per g.14 to 77. moleV35. and 1 1.61 to 63.
Tests of the Third Law of Thermodynamics. this is the standard state of the gas. using partition functions.53 298. e.g.23d THE THIRD LAW OP THERMODYNAMICS 8 ..36. .. the entropy change can be derived analytically.16 K. pressure is 36. is given by equation Si (20. such as heats of reaction.89 E.U.16 9. the correction for nitrogen gas at its boiling point was found to be 0. 36. at constant (atmospheric) pressure.e. in the usual manner ( 20a) by graphical integration over this temperature range. yield results..~L Addition of this quantity to the observed entropy.e. mole""1 1 gives 36. i. pressure is found by statistical methods to be 9. sufficiently accurate measurements of gaseous heat capacities down to the boiling point have usually not been made. /. 23d. 55.. pressure to give the value for an ideal gas at the same pressure was calculated in 20c. If the heat capacity can be expressed as a function of the temperature over the required range. .31 E. i. so that the standard entropy of nitrogen gas at 1 is 36. A few ap. If TI is the normal boiling point and T* represents the standard temperature. 4875 (1933). Soc.. which are in agreement with experiment. are usually in complete agreement with those derived from statistical considerations. and so the entropy contribution of the gaseous state.. after the calculation of entropies by statistical methods.36 E. K * Giauque and Clayton. when combined with other data.. it would be possible to evaluate the increase in entropy between the boiling point and the standard temperature. For reasons which will become clear later. viz. i. as an ideal gas. it is the practice to record the entropy of a gaseous substance in terms of an ideal gas at 1 atm. which.U. the contribution of the gaseous state to the total entropy. This aspect of the subject will be taken up later in the book (Chapter XIII). such as those in Table XV. As seen in that section. point to 298. 181 it is seen that the entropy of gaseous results are recorded in Table XVI 1 nitrogen at its boiling point at 1 atm. is derived from heat capacities obtained from partition functions as described in Chapter VI. assuming ideal behavior. particularly equilibrium constants. Am. One important fact is that entropies calculated on the basis of the third law. In the meantime other verifications of the third law of thermodynamics will be mentioned.217 cal.53 E. mole" for the standard entropy of nitrogen gas at its boiling The additional entropy of nitrogen. from the boiling point. at 1 atm.TJ.U.  Si = r*^ i j Tl dT = f Cpd in T j Tl f2  t 23 2)  However.9). has been described.e. The correction to be applied to the observed entropy at 1 atm.. K + . The ultimate test of the postulate that the entropy of a perfect solid is zero at is that it leads to entropy values. Chem.U. moleIf precise heat capacity data were available for the gas. as described in 20a. in the manner described above. 45. 298. deg. 25 C.31 B. 16 K. pressure. moleThe standard entropy values of a number of gases will be given later.
Soc.29 . with a The entropy of the high temperature form (a) definite transition point. at some temperature above the transition point may. J. The entropy contribution of the aform from the transition temperature to the chosen temperature is then obtained from heat capacity measurements on the oform. ref 4. mole~l to 15 K. 'Keltey. a summary of the results being given in Table XVII. with two low temperature modifications (ft and 7).29 K.43 K K 0.495 2.U.43 K) to the entropy obtained from these results was then added the entropy of the transition to the aform. 1400 (1929). In the second method (II). Phya. I THE ENTROPY OF SOLID PEtoSPHINE AT 49. J.757 8. yform (Debye) 15 to 30.800 Total Total 8... Am.136 K K K 0.. Stephenaon and Giauque. e. 6 In the first method (I). and the entropy at this temperature may then be determined in the usual manner. Chem.647 4. (1937).338 4. To this is then added the entropy of transition. in some cases.185 0.29 to 49. both of which change into the aform at the transition points The entropy of the aform at 49. first three lines of Table XVI). and the entropies obtained by the two methods have been found to be in close agreement.29 30. has been obtained in two ways based on the third law of thermodynamics.43 and 30. 5. heat capacity measurements can be made on the form (ft) stable below the transition point. 51.. thus giving the entropy of the of orm at the transition point (cf. An interesting test of the third law is possible when a solid is capable of existing in two or more modifications. TABLE XVH. but these are readily explained by the "imperfect" nature of the solid ( 24m). SO. enantiotropic forms. 1 Stephcnson and Giauque.127 heat capacity measurements were made on the form up to the ft > a transition point (49. . cyclohexanol and phosphine. measurea transition point (30.182 ENTROPY: DETERMINATION AND SIGNIFICANCE 23d parent discrepancies have been observed.. 149 (1937). sulfur. be obtained in two independent ways.43 (graphical) E. so as to give the entropy of the form at 30. First. respectively. 4 The results with phosphine are particularly striking. and the entropy of the aform is then obtained directly from these data.43 K E. Chem. can then be determined from very low temperatures up to temperatures above the normal transition point.29 (graphical) Transition 7 * a at 30. 145 .U.29 K). ments were made on the 7form up to the y to this was added the entropy of the transition. thus giving the entropy of the latter at 49. i. Measurements of this kind have been made with a number of substances. The second procedure is to cool the oform rapidly below the Its heat capacity transition point so that it remains in a metastable state.43 K. The increase of entropy of the latter from 30. Eastman and McGavock.29 K.43 (graphical) Transition ft * a at 49.e. 0form (Debye) 15 to 49.g. tin. mole""1 II to 15 K.041 3. ibid. for this substance exists in a high temperature (a) form.43 K of 49.
it is probable that the entropy of each solid is actually zero at K. 2305 (1926). According to the third law of thermodynamics. the entropy of a solid becomes independent of the pressure. silica. one globe contains a gas. Chem. in other words. so that the rate of expansion of a solid with temperature should become K. but it is probable that such is the case. this provides the justification for the statement made earlier ( 23b) that the difference between values of Cp and CV for a solid becomes negligible at low temperaIt should be pointed out that what has been proved above is that tures. Some light may be shed on this matter by means of the theory of probability. J. according to the second law of thermodynamics. in the usual manner. there are two similar globes. was possible between the entropy Am. Soc. that provided there are present a large number of molecules. the gas will distribute itself uniformly through the globes. equal to  S). 24a. calcium fluoride and iron disulfide. This does not prove that the entropy is actually zero. then. but in view of the fact that similar behavior has been observed with a variety of substances. do. whereas the other is evacuated. hence.g. copper. in fact. 24.p (for T= 0).15). there is a very strong probability. . diamond. separated by a stopcock. An analogous relationship. t 48. Suppose that the whole system consists of a single molecule Buffington and Latimer. which permits of quantitative development. The value is not necessarily zero. Strictly speaking. both elements and compounds. Experimental observations have shown that the values of zero at (dV/dT)p for a number of solids. ap6 proach zero as the temperature is lowered. as in the experiments of GayLussac and Joule ( 9d). amounting almost to a certainty.. It is evident from the data in Table XVII that the agreement between the entropies obtained by the two methods is excellent. will now be considered between the entropy and the "probability" of a system. silver. Entropy and Probability. If the stopcock is opened. By equation (20. this agreement proves only that the two crystalline modifications (8 and 7) of the solid have the K.24a to 49. STATISTICAL TREATMENT OF ENTROPY It of was seen in 19k that a correlation a system and the extent of order or disorder. e.43 STATISTICAL TREATMENT OF ENTROPY 183 K was then derived. (dS/dP) T is =o (dV/dT) P and consequently . (dS/dP)r approaches zero at the absolute zero. it follows that crystal should be zero at K dPr. sodium chloride. aluminum. Incidentally. Suppose. as assumed in same entropy at Table XVII. the entropy of a perfect at all pressures. from heat capacity measurements on the <*f orm in this temperature range.
and probabilities WA and WB> respectively.. On the other hand. it follows f(WA ) +f(W*) f(WA X that . In general. i. It is possible to state. Nevertheless. equal tof(WA ) and SB \&f(WB ). that If there is to say. 24b. The BoltzmannPlanck Equation. at constant temperature. provided the system contains an appreciable number of globes. molecules. then it should be possible to represent S To ascertain the nature of this function. are two similar molecules in the system. the foregoing calculations deal with an extreme case of nonuniform distribution. all W + . even at such is about 10 value of The problow pressures as 10~ 6 atm. that the probability of the virtually uniform distribution of a considerable number of molecules in the space available is very large.184 only.SA + SB f(WA X WB ). is the sum SA S B hence.. therefore. it may be concluded that the probability that the molecules of a gas will remain in one part of the space available to them is extremely small under ordinary conditions. being additive ( 19b). all spontaneous processes represent changes from a less probable to a more probable state. N . 2 In general. SAB Since SA is .e. The probability that the molecule will be found in one particular globe at any instant is thus $. N . If 5 is the entropy and is the probability of a particular state. and since such processes are accompanied by an increase of entropy. it is possible to show by means of the theory of probability that the chances of any appreciable spontaneous fluctuation from a uniform distribution of the gas throughout the whole available space is so extremely small that it is unlikely to be observed in millions of years. S = f(W). there is one chance in two of this condition being realized. the probability of a virtually uniform distribution of the gas is large. . Of course. the probability of this distribution is \ or () tem containing molecules the probability that all the molecules will remain For a globe having a volume of one liter the in the original globe is (i) y 22 at ordinary temperature and pressure. The spontaneous process in which a gas. If the systems are combined the probability of the resulting system is the product WA X WB. it would still be of the order of 10 16 in will the after remain the that the molecules original globe stopcock ability This is also the probability that the is opened is thus extremely small. consider two systems having entropies SA and SB. as a function of W. it is to be expected that there may be a connection between the entropy of a system in a given state and the probability of that state. whereas the entropy. To sum up the situation. for a systhus. fills uniformly the whole of the available volume is thus associated with a large increase in the probability of the system. there ENTROPY: DETERMINATION AND SIGNIFICANCE 24b is an equal probability that it will be found in either of the two assuming them to have equal volumes. it can be readily shown that there is one chance in four that both will be in a given globe at the same time. molecules will return spontaneously to the one globe after having been distributed uniformly throughout the two globes.
24d STATISTICAL TREATMENT OF ENTROPY this condition it is obvious that the function 185 logarithmic. Planck (1912) have shown that it may be taken as zero. sometimes called the "thermodynamic probability. may be noted that "thermodynamic probability" is not a probability in the ordinary is but proportional to the latter. and so the thermodynamic probability of the system is determined by the number of ways. to be described shortly.2) There is no complete proof of this expression. This conclusion is in agreement with the third law of thermodynamics. (24. 24d. Such solids are not perfect crystals in the sense of the K. is independent of the volume.1) is not obvious. Consider a single molecule contained in a vessel which can be divided into two equal parts by means of a shutter. consistent with the given energy."" Boltzmann constant. is to calculate the entropy of isothermal expansion of an ideal gas. but the considerations presented by L. 24c. To satisfy so that must be it is possible to write S = where k is . therefore. thus IF is unity. may be realized. the i. . It will be seen later that there are certain solids in which the molecules may be arranged in different ways in the crystal in the vicinity of the absolute zero.e. the (24. (24. in the The complete calculation of specified thermodynamic state. where The value of the constant term in equation (24. the gas constant per single molecule. and consequently it is to be regarded as being in the nature of a reasonable postulate relating the entropy of a system to its probability." may be defined as the total number of different ways in which the given system. in which the molecules can occur in the volume occupied by the gas. For such a gas the energy content. equal is the Avogadro number. energy (heat) X deg. In a system consisting of a perfect solid at the absolute zero. and hence by equation (24. but in the meantime some general aspects of the subject will be considered. in fact. that is. and they are arranged in a definite manner in the crystal. to R/N.2) in connection * It i. Entropy of Expansion of Ideal Gas.2) the entropy should be zero. and their entropies are not zero at Similar considerations apply to solid solutions and to glasses. It would appear. at constant temperature." so that its value may be determined. third law of thermodynamics. Significance of Thermodynamic Probability. Boltzmann (1890) and M.1) a constant which must have the same dimensions as entropy.* this probability can be carried out by the methods of statistical mechanics. 1 It will be seen shortly that k is. If at any instant the shutter is closed. k In W + constant.. The problem that now arises is that of ascribing a precise significance to the "probability of a system in a given state. all the molecules are in their lowest energy state.k In W. that under such conditions there is only one way in which the system may be realized. A simple application of equation with the interpretation of thermodynamic probability. This quantity. so that the BoltzmannPlanck equation takes the form N S .
or the number of ways of realizing.3) the system consists of 1 mole of gas. in unit volume. at constant temperature and energy.186 ENTROPY: DETERMINATION AND SIGNIFICANCE 24e chances of the molecule being present in one part is onehalf that of it being in the whole vessel. AT is the Avogadro number. energies which are virtually equal. the N system is (aV) Suppose an isothermal expansion is carried out in which the volume of the If the corresponding entropies are Si and $ 2 ideal gas is changed from V\ to F 2 and the probabilities are W\ and W*. and / momenta. J. and the general form of the BoitzmannPlanck equation can thus be justified. II. the exact state of the molecule could be represented by a point in this imaginary phase For all molecules with external and internal configurations and space. Fowler and E. within certain very narrow limits. a system can be carried out by the methods of statistical mechanics. the probability of a single molecule being found in any volume is proportional to that volume.26). the total probability of. If a hypothetical space. assuming Boitzmann constant. the gas constant per single molecule.2) that the entropy change accompanying the process is given by . "The Principles of Statistical Mechanics/' 1038.2) with identical with equation (19. M. Mayor. as indicated above. If a is the thermodynamic probability. Glasstone. called a unit cell. "Theoretical Chemistry/' 1944. Since the same probability is applicable to any one of the N molecules present in the given volume.. The evaluation of the total probability of 24e. A. having 2/ axes could be imagined. see R.e. "Statistical Mechanics/' 1940. For the isothermal expansion portional to VN of the ideal gas the probabilities are seen to be pro 9 so that OS 2  Si)r = A: 1 \ = If A. In general. i. and. . the probability for a volume V is then aV. where / is the number . the representative points will be found within a particular small volume. C. 7 For further discussion. R. . E. &ATln V" (24. By specifying the numbers of molecules cule. but it is sufficient to present them in general outline here. Tolman. Statistical Mechanics. the number of ways in which a single molecule can occur. The details of the arguments are somewhat involved. known as phase space. it follows from equation (24. Mayer and G. in the phase space. 7 The state of any single molecule can be completely described by specifying the values of / positional coordinates of "degrees of freedom" of the moleequal to three times the number of atoms it contains.3) that to be the This result is seen to be for the isothermal volume change of an ideal gas. S. Guggenheim. "Statistical Thermodynamics/' 1939. The identification of k in equation (24. it follows from equation (24.
the condition of every molecule in the system is defined. is given by the number of be realized. . The development of quantum statistics has shown that this expression The first arises because there are requires modification in two respects. in the sense defined the different possible cells are indicated by the numerals 1. to each energy level. If g* is.. when determining the total number of ways a particular state can be realized. the observable Each distribution of the molecules among the properties. cules in the system. an exchange of molecules between different unit cells will not affect the macroscopic state.5) by N\.JSt . such as pressure. 9 ... and . are treated as distinguishable. necessary to divide equation (24. the numbers of representative points in each of these cells are it 2. . t . However. above. 1 Nil N*l Nil (246) ^ } . and so on. This determines the macroscopic state of the system. in general. so that the result is IFgt.. . energy. . possible ways of arranging a total of distinguishable articles in a number of groups. permissible unit cells corresponding to the same macroscopic state of the system is known as a microscopic state.!. . Thus. their sum being equal to N. it is inconsistent with quantum mechanics.. . number states whose are so close together that they a of energies frequently behave classically as a single state. of the system. with. The total number of microscopic states then represents the number of different ways in which the given system can this is its thermodynamic probability. and so the total number of microscopic states. so that there are Ni in the first.4) is due to the fact that the classical concept of distinguishability of the molecules is found to be In order to correct for this. i. or unit cell. N% in the second. the (24 ^ 4) } W = NilNtl . the number of different microscopic states in the cell is thus increased by a factor of g^\ Applying this correction to each of the cells. Ni in the ith group. . . equation (24. as stated in 16b. .. as indicated by its observable properties. there will be a choice of states for each of the Ni molecules. this multiplicity must be taken into account. there must be ascribed a statistical weight.4) for the probability becomes The second change necessary in equation (24.246 STATISTICAL TREATMENT OF ENTROPY 187 whose representative points are to be found in the different unit cells in the phase space. the molecules. Ni In classical statistics. . The evaluation of the number of ways of realizing this result is N arrangement is a relatively simple mathematical problem. Nil . the statistical weight corresponding to the ith cell. If . in general. which is equal to the probability of the system. . . etc. although identical. the total number of moleNi Nt.. for every possible arrangement of the other molecules in this cell.e. .. For a system of identical molecules..
Upon taking logarithms of equation (24. (24. very large. + AT. .6).  AT. It is then possible to make use of the Stirling approximation for the factorials of large numbers. .7). in AT. the various numbers Ni. BO that the treatment does developed here and in the preceding section. Since the evaluation of the entropy by equation (24. This expression may in be substituted in equation (24. In Ni  .Ni In AM = NtlnN* . so that (24. two different forms of quantum statistics. .2) requires a knowledge of In W. namely the BoseEinstein statistics. . .188 ENTROPY: DETERMINATION AND SIGNIFICANCE This expression 24f classical treat may be regarded as a consequence of the ment modified by the requirements of quantum statistics. i.6).e.9)* * It is of interest to (24. the result is 24f. have been developed. . Statistical Calculation of Entropy. which are applicable to photons and to atoms and molecules containing an even number of elementary particles. and recalling that Ni + AT* Hh Ni is equal to the total number N of the molecules in the system. In W= (N l }ng l + Ntlng*+ +N i \ng i + ) (24. at the temperature T was given by equation (16. However. It was seen in 4 possessing energy 16b that in an ideal gas the number of molecules AT.7) If the system consists of a very large number of molecules. . and the FermiDirac statistics.. it is seen that . thus. this quantity will now be considered.4). .8) w= EAT.V.N In 2 In AM = N. . The value of given by the latter may thus be taken as representing the probability of a W given state of a system of N molecules. as is the case are also under normal conditions. but it is important to note that at all temperatures and pressures of chemical interest the final expressions may be reduced to a form equivalent to equation (24. Upon adding these quantities. not involve any arguments other than those . note that this equation can itaelf be derived from equations (24. JV 2 A^. protons and neutrons. electrons.5) as T .6). AM * NiluNt . These give somewhat different results for the total number of ways in which a given state can be realized.5) or (24. in gi  EAT. \ AT. which apply to electrons and to atoms and molecules containing an odd number of elementary particles.
kNlnN . S .R. it is convenient to write this equation what different form by utilizing the Stirling approximation some ln#! = so that NluN  N.8) it is seen that .Bin + r + R. so that the general expression for the entropy of an ideal gaseous system is found to be W . hence. kN is equal to the molar gas constant R. and is the molar entropy. In fff I / 1 \Q V gitr** \r i_ \r i^ _ and by combining this result with equation (24.8). that fcT alnQ\ kT \ dT ) v from equation (24.R In Q  N N.kN = R In N . result is inserted for the second Ni in the term the latter Ni In N^ becomes i = *T Ni 1 . fl In R In % .24f STATISTICAL TREATMENT OP ENTROPY 189 If this where Q is the partition function of the given molecular species. Skl*W = kNlnQ + RT(?^} \ *T A If N is then S the Avogadro number. I #*i = and hence. .11) in a For certain later purposes. utilizing AToto N*i+~+N<u+~ = E go equation (16.(dlnQ\ +kN. therefore. thus. fcln#! Since . (24.10) may be substituted in the The value for In BoltzmannPlanck equation. The summation # t < is given by equation (16. fcr It follows.6).
190
it
ENTROPY: DETERMINATION AND SIGNIFICANCE
24g
can be readily shown that equation (24.11) becomes
from the foregoing results, e.g., equations (24.11) and (24.12), statistical mechanics with the BoltzmannPlanck equation it is possible to derive a relationship between the molar entropy of any gas, assuming it to behave ideally, and the partition function of the given Since the partition function and its temperature coefficient may species. be regarded as known, from the discussion in Chapter VI, the problem of In order to calculating entropies may be regarded as solved, in principle. illustrate the procedure a number of cases will be considered. 24g. Entropy of Monatomic Molecules The SackurTetrode Equation. A monatomic molecule has no vibrational or rotational energy, and so the
It is seen
that
by combining
:
only contributions to the partition functions are those for translational energy and for possible electronic states. The translational partition function is given by equation (16.16), and if the electronic factor is Q it follows that for a monatomic gas
t
where
the volume occupied. Assuming Q e to be independent of temwill be the case for the majority of substances at not too high as perature,
is
(
V
temperature
16f),
then
and hence the molar entropy
(24.11) as
of
an
ideal
monatomic gas
is
given
by equation
(24.13)
S  R
where
In
& (2T
fc)3/2
V
+
f /?,
V is now the molar volume.
= K Sr>
i
I
by RT/P,
Since the gas is ideal, so that another form of equation (24.13) is
s\
\ **
V may be replaced
n
"if
<*
J
***
These are alternative expressions of what equation, derived in a somewhat different
is
known as the SackurTetrode manner by O. Sackur (191113)
and H. Tetrode
If
(1912).
8
P and
the universal constants R, IT, k, h and are separated from m, T, Q, which are characteristic of the system, equation (24.14) becomes
[i In
N
S 
m +  In T 
In
P+
In Q.
+
In R(2*k/h?)*'*/N
+ f ].
Sackur, Ann. Physik, 40, 67 (1013); Tetrode, Stem, Physik. Z. 14, 629 (1913).
t
ibid., 38,
434 (1912); 39, 266 (1913);
24g
STATISTICAL TREATMENT OF ENTROPY
191
The treatment of units is here the same as that employed in connection with the translational partition function in the problem in 16e; m, k and h are in c.g.s. units, and if P is in atm., R in the In R term should conveniently The actual weight be in cc.atm. deg.1 mole" 1 of the molecule may be is the ordinary molecular weight. replaced by M/N, where Making these substitutions and converting the logarithms, it is found that
M
.
m
S =
for the
2.303/2(2 log
M+
log
T
log
P+
log
Q 9
0.5055),
(24.15)
molar entropy, where P is the pressure in atm. It is of interest to compare equation (24.15) with (19.22), derived earlier for an ideal gas; since CP for an ideal gas is equal to f R these two expressions are identical in form, the constant s' Q which cannot be derived from purely thermodynamic considerations, involving the molecular weight of the gas, its electronic multiplicity and a numerical constant. If the pressure P in equation (24.15) is taken as 1 atm., the entropy is that of the particular substance behaving as an ideal gas at this pressure, and hence represents the standard entropy S Q (20c). By taking R as 1.987 cal. deg."" 1 mole" 1 equation (24.15) then gives the standard molar entropy of the gas in these same units; thus,
, ,
S =
1
4.576(f log
1
,
M + f log T + log Q.  0.5055),
1
.
(24.16)*
It is thus a very simple matter to in cal. deg.""" mole" i.e., E.U. mole"" determine the standard entropy of a monatomic gas at reasonable temperaIt should be noted that the electronic factor Q is always included tures. in the expression for the entropy, but it was usually omitted from the corresponding equations in Chapter VI in which the partition function was related The reason for this is that the latter to the energy and the heat capacity.
involve (d In Q/dT)v only, and if Q e is constant, as it usually is, it makes no It will be seen from equation contribution to the energy or heat capacity. (24.11), however, that the entropy depends on In Q, as well as on the temperature coefficient; the actual value of Q e , or rather of In Q e , must consequently be included, even if it is constant.
Problem: Calculate the standard entropy
of
atomic chlorine at 25 C.
The atomic
or molecular weight, actually the
mean
iso topic weight, is 35.46;
this gives the value of M; T is 298.2 K, and Q, may be taken as 4.03, as calculated in the problem in 16f, the temperature variation being neglected. Hence, by
equation (24.16),
S =
=
The
25
is
4.576(f log 35.46 39.4 cal. deg.~ l g.
+
$ log 298.2 atom~l
.
+ log 4.03 
0.5055)
C
calculated standard entropies for a number of monatomic gases at are recorded in Table XVIII, together with the entropies obtained
factor 4.576, which is frequently encountered in thermodynamic calculations, 1.987, where 2.303 is the factor for converting ordinary to natural 2.303 log x, and 1.987 is the value of in cal. deg."1 mole"1 . logarithms, i.e., In x
*The
equal to 2.303
X
R
192
ENTROPY: DETERMINATION AND SIGNIFICANCE
9
24h
For from heat capacity measurements, as described earlier in this chapter. these particular elements the ground states are all singlet levels, so that Qe is unity in each case.
TABLE
XVIII.
CALCULATED AND EXPERIMENTAL ENTROPIES OF MONATOMIC GASES AT 25 C
Calo.
Gas Helium Argon
Exp.
29.2 E.U. mole~ l 36.4 40.0 38.4 41.3 41.8
Cadmium
Zinc
30.1 E.U. mole" 1 37.0 40.1
Mercury Lead
38.5 41.8 41.9
24h. Polyatomic Molecules.
in the
Since the partition function appears only
form
of its logarithm in the general equation (24.11) or (24.12) for
the entropy, it is permissible, as with the energy and heat capacity, to consider the total entropy as the sum of the contributions associated with the various forms of energy. As stated in 16d, this procedure is approximate, although very little error can be involved in the separation of the translational contribution and also the electronic contribution if the molecules are almost entirely in the ground state, e.g., at normal temperatures. Tn this event, equation (24.14), (24.15) or (24.16) gives the sum of the translational and electronic entropies for any type of molecule, monatomic or
polyatomic.
The complete partition function of a polyatomic molecule may now be represented by the product Qt X Q, where Q is the translational, including the electronic, factor, as derived above, and Q; is the combined rotational and vibrational, i.e., internal, factor. Since In Q is then equal to In Qt In Qiy equation (24.12) may be written in the form
t
+
t
S= S
+S =
<
(k
In
^
is
The
expression in the square brackets in equation (24.17), which
of the
same form as (24.12), gives the combined translational and electronic enThe contropies, and that in the parentheses is the internal contribution. dition of constant volume has been omitted, since the rotational and vibrational partition functions are independent of the volume of the system (cf
.
included in the is concerned, it is immaterial which term contains the !, but there are theoretical reasons, which need not be considered here, for including it in the expression for the translational entropy. Since k In Q? is equivalent to R In Q<, because kN is equal to R,
It will be noted that the 16h, 16j, etc.). translational term. As far as the final result
Nl has been
N
9
Lewis, Gibson and Latimer, J.
Am. Chem.
Sor., 44,
1008 (1922); Rodebush and Dixon,
ibid., 47,
1036 (1925).
241
it
STATISTICAL TREATMENT OF ENTROPY
193
follows that the total rotational
is
and vibrational contribution to the
entropy
given by
Si

12
In Q<
+ RT
^.
(24.18)
results, Q< should be the combined rotational and vibrafunction derived from the actual energy levels of the moletional partition For most purcule as obtained from spectroscopic measurements ( 16k). poses, at ordinary temperatures, very little error results from the separation of Qi into the product of two independent factors, viz., Qr and Q, representing the rotational and vibrational partition functions, respectively. Because equation (24.18) involves Q in logarithmic terms only, it follows that an expression of the same form can be used to give the separate rotational and vibrational entropies. Thus, if Qi is replaced by Qr the result is S r, the rotational contribution to the entropy, and similarly the vibrational
For accurate
,
The sum contribution S, is obtained by using Q v for Q< in equation (24. 18) of Sr and S derived in this manner represents S, which added to St, as given by equation (24.14), etc., yields the total entropy. 161 that the contribution It was seen in 241. The Vibrational Entropy. 4 to the partition function of each mode of vibration of frequency co cm." is l = to 1.439co/r. Jicu/kT e~*) 9 where x is equal given by a factor (1 The vibrational entropy is represented by the appropriate form of equation (24.18) as
.
not a difficult matter to show that the contribution to the molar entropy of each mode of vibration is
and hence
it is
S.

^r e* 1
In (1

6T).
(24.19)
The terms
i.e.,
in equation (24.19) can be readily obtained for any value of x, Acw/fcr, by means of the tables of Einstein functions mentioned
(
earlier
If
16j).
relatively large, as is the case at moderate temperatures for many diatomic stable molecules, which have large vibrational frequencies, e* becomes very large and 6~* is very small. It is seen from equation (24. 19) that This is true for hydrogen, deuterium, in this event 5, is almost zero. oxygen, nitrogen, carbon monoxide and hydrogen chloride, for example, at temperatures up to about 370 K. For these molecules, it has already been seen ( 16j) that the vibrational contribution to the energy and heat capacity If the vibration frequency o> is is also negligible at such temperatures. or the relatively small, temperature fairly high, the value of S* as given by not is negligible; this is the case, for example, with chlorine equation (24.19) even at ordinary temperatures. Molecules containing more than two atoms invariably have at least one vibration with a low frequency which makes an appreciable contribution to the entropy at all reasonable temperatures.
3
is
194
ENTROPY: DETERMINATION AND SIGNIFICANCE
24j
Before considering the contribution to the 24j. Nuclear Spin Entropy. entropy of a molecule associated with its rotational motion, it is necessary to refer to the subject of nuclear spin and its effect on entropy. When discussing the evaluation of energies and heat capacities from the partition function in Chapter VI, the nuclear spin was deliberately neglected. This procedure is justified by the fact that the nuclear spin contribution to the partition function is a constant factor, independent of temperature, except However, as emphasized possibly in the vicinity of the absolute zero. earlier in another connection, the expression for the entropy involves In Q itself, in addition to its temperature coefficient, and consequently the nuclear spin factor must be included. For each atomic nucleus having a spin quantum number i, the contribution to the partition function is a factor
It follows, therefore, from equation 1 at all reasonable temperatures. In (2i 1) for every nucleus in (24.18) that the nuclear spin entropy is the molecule. To obtain the total entropy of a molecule the appropriate
2i
+
R
+
In (2i 1) terms tion, rotation, etc.
R
+
must be added to the contribution
of translation, vibrar
Since atoms retain their nuclear spins unaltered in all processes except those involving orthopara conversions, there is no change in the nuclear spin entropy. It is consequently the common practice to omit the nuclear spin contribution, leaving what is called the practical entropy or virtual entropy.* It is of importance to note that, except for hydrogen and deuterium molecules, the entropy derived from heat capacity measurements, i.e., the thermal entropy, as it is frequently called, is equivalent to the practical entropy; in other words, the nuclear spin contribution is not included in the former. The reason for this is that, down to the lowest temperatures at which measurements have been made, the nuclear spin does not affect the experimental values of the heat capacity used in the determination of entropy by the procedure based on the third law of thermodynamics ( 23b). Presumably if heat capacities could be measured right down to the absolute zero, a temperature would be reached at which the nuclear spin energy began to change and thus made a contribution to the heat capacity. The entropy derived from such data would presumably include the nuclear spin contribution of R In (2i 1) for each atom. Special circumstances arise with molecular hydrogen and deuterium to which reference will be made
+
below
(
24n).
At all temperatures above the lowest, the rotational partition function Q r of a diatomic molecule, or of any linear molecule, is given to a good approximation by equation (16.24), i.e.,
24k.
r
The Rotational Entropy.
<rh*
noted, incidentally, that the practical or virtual entropy also does not include the entropy of mixing of different isotopic forms of a given molecular species. This quantity is virtually unchanged in a chemical reaction, and so the entropy change of the process is unaffected by its complete omission.
*It
may be
24k
where /
(
STATISTICAL TREATMENT OF ENTROPY
195
ber
is the moment of inertia of the molecule and <r is its symmetry numInsertion of this result in equation (24.18) gives the 16h, 161). rotational contribution to the molar entropy of a linear molecule,
&  B In
4 + R,
(rhr
(24.21)
If the recognized values are inserted for since d In Q r /dT is equal to l/T. the universal constants T, k and h, in c.g.s. units, and if R is taken as 1.987 1 it is found, after converting the logarithms, that cal. deg.~ l mole"
,
Sr 
4.576(log /
+
log
T 
log
<r
+ 38.82) cal.
deg
1
2
.
mole,
1
(24.22)
the moment of inertia being still in c.g.s. units., i.e., g. cm. This expression l gives the molar rotational entropy in conventional E.U. mole~ for any diatomic or linear molecule.
Problem: Calculate the total standard entropy of nitrogen gas at 25 C, using
data in Tables VIII and IX.
Since the ground state of molecular nitrogen is a singlet level, Q is unity, and the molecular weight being 28.00, the combined standard translational and electronic entropy, the latter being actually zero, is given by equation (24.16) as
M
o
= =
4.576(1 i og 28.00 35.9 E.U. mole~ l .
+
1
flog 298.2

0.5055)
The vibrational frequency is 2360 cm." (Table IX), and hence x, i.e., 1.439w/T,
is 11.4.
Insertion of this result into equation (24.19) gives a value for S v that is The vibrational contribution to the entropy of molecular negligibly small. nitrogen at 25 C may thus be taken as zero. 10" 40 g. cm. 2 (Table VIII), and <r is 2, since The moment of inertia is 13.9 the nitrogen molecule is symmetrical; hence, by equation (24.22),
X
Sr =
=
The
35.9
i.e.,
4.576[log (13.9 9.8 E.U. mole"" 1 .
X
10~40 )
+ log 298.2 
log 2
+ 38.82]
C
is thus the sum of entropy of nitrogen gas in its standard state at 25 9.8 E.U., i.e., 45.7 E.U. mole*" 1 , which may be compared with the thermal, 23c. third law, value of 45.89 E.U. mole"" 1 given in
total
and
(16.34)]
For a nonlinear molecule, the rotational partition function may be taken with sufficient accuracy as
'
[cf.
equation
( (
OT'
.
and
since d In
Qr/dT
is
\/T,
it
follows from equation (24.18) that
+ jR,
(24.24)
where A, B and C are the moments of inertia of the molecule. Extracting the constants and converting the logarithms, in the usual manner, it is
196
ENTROPY: DETERMINATION AND SIGNIFICANCE
241
found that
Sr for the
4.576(i log
ABC +
f log
T1
log
<r
+ 58.51),
(24.25)
molar rotational entropy in
cal.
1 deg. mole"" .
Problem: Calculate the rotational contribution to the molar entropy monia at 25 C.
,
of
am
and 4.33
Sr
From Table X, the three moments of inertia are 2.78 X 10~40 2.78 X 10"40 X 10^ g. cm.2 a is 3 and T is 298.2 K, so that by equation (24.25),
,

4.576[i log (2.78 X 2.78 11.5 cal. deg.~l mole"1 .
X
4.33
X
10")
+
f log 298.2

log 3
+ 58.51]
ciable, the
It is seen that the rotational contribution to the entropy is quite appreamount increasing, in general, with the size of the molecule and
the masses of the atoms, since these cause the
relatively large.
moments
of inertia to
be
24L Comparison of Third Law and Statistical Entropies. If the vibration frequencies and moments of inertia of a molecule, which are often available from spectroscopic measurements, are known, the standard entropy of any gaseous substance can be evaluated with a fair degree of accuracy. By the use of combined rotational and vibrationai partition functions, derived directly from the energies in the various levels ( 16k), more precise entropy values are obtainable. In the great majority of cases the entropies obtained by the statistical method, based on the BoltzmannPlanck equation, are in complete agreement with those derived from heat capacity measurements, utilizing the third law postulate of zero entropy K. There are a few cases, however, where some disfor the perfect solid at crepancy has been observed; these are carbon monoxide, nitric oxide, nitrous oxide, hydrogen, deuterium, water and organic compounds, such as ethane, in which the
internal rotation
will
is
restricted
(
16m).
The various types
of discrepant behavior
now be
considered.
24m. Random Orientation in the Solid. For carbon monoxide, nitric oxide and nitrous oxide, the thermal entropy, based on the third law of thermodynamics, 1 is found in each case to be about 1.1 cal. deg."" 1 mole" less than the value given by the statistical method. This result suggests that the entropies of the respective solids are not zero at K, as required by the third law, but that they are actually A possible explanation of this fact is to be found in the about 1.1 E.TT. mole"1 similarity between the two ends of the respective molecules, so that the alternative
.
arrangements
CO
OC
NO
ON
NNO
ONN
can occur in the crystal lattices. Instead of all the molecules being oriented in one direction in the crystal, two alternative arrangements are equally probable. The crystal is, therefore, not "perfect" in the sense required by the third law, and hence it is not correct to take the entropy as zero at K. If the distribution of molecules between the two possible orientations were completely random, the probability of the state, as defined in 24c, would be two, and the entropy should
240
STATISTICAL TREATMENT OF ENTROPY
1 1
197
be R in 2, i.e., 1.38 cal. deg. mole"" , instead of zero for the perfect crystal. The observed discrepancy of 1.1 E.U. mole"" 1 indicates that the arrangement of the two alternative orientations in the solid is not completely random at the low temperatures at which heat capacity measurements were made. In the three instances under consideration, the correct entropies are those obtained from the partition functions, for these are based on the properties of the gas, and do not involve extrapolation, through the liquid and solid states, down to the absolute zero as is necessary for the evaluation of thermal entropies. Somewhat analogous considerations apply to the entropy of water vapor. The result derived from heat capacity measurements is again lower than the statistical value, and this can be accounted for by random orientation of the water molecules The situation is complicated, however, by the distribution of hydroin the solid. gen bonds in the ice crystal, and by other factors. In this instance, also, the K. The statistical crystal is not perfect, and so the entropy would not be zero at value of the entropy is therefore the correct one to be used in thermodynamic
calculations.
24n. Entropy of Hydrogen and Deuterium. An entirely different phenomenon responsible for the discrepancy between the third law and statistical entropies The thermal value for hydrogen is 29.64 cal. degr 1 of hydrogen and deuterium. mole"" 1 at 25 C and 1 atm. pressure, corrected to ideal behavior, but statistical calculations give 33.96 cal. deg.*" 1 mole" 1 , including the nuclear spin contribution. 2 The latter is R In (2i I) , since the molecule consists of two atoms each with a nuclear spin i; for the hydrogen nucleus i is i, and so the nuclear spin entropy is R In 4, i.e., 2.75 cal. deg." 1 mole""1 If this is subtracted from 33.96 cal. deg."1 mole"1 the result still differs from the thermal value. The responsible factor in The statistical this instance is the existence of hydrogen in ortho and para states. calculations are based on the assumption that orthopara equilibrium is attained at all temperatures, but this condition is not realized in the hydrogen used for heat
is
+
.
,
capacity measurements
(cf.
16i).
Because solid hydrogen at low temperatures still contains the ortho and para forms in the normal proportions of three to one, the entropy cannot become zero K. The actual value is equal to the entropy of mixing, as calculated in the at 1 problem in 19j, viz., 4.39 E.U. mole" x If this is added to the apparent third law value of 29.64, the result is 34.03 cal. deg."1 mole" 1 which is in good agreement with For use in connection with the the statistical entropy, 33.96 cal. deg." 1 mole" 1 entropies of other substances, when there are no changes in the orthopara hydrogen ratio, the appropriate value of the practical entropy is obtained by subtracting the nuclear spin contribution of 2.75, given above, from the statistical value of 33.96 cal. deg." 1 mole" 1 the entropy of molecular hydrogen is thus taken as 31.21 The data for molecular deuterium must be treated in an analogous E.U. mole" 1 manner.
,
, . ; .
24o. Restricted Internal Rotation.
tion of
When there is
restriction to internal rota
of a molecule with respect to one another, as in ethane and other paraffin hydrocarbons, and in alcohols, amines, etc., the calculation of the entropy from the partition functions requires a knowledge of the energy which restricts As stated in 16m, this can be obtained from a comparison of an exrotation. perimentally determined thermodynamic property with that derived by means of
two parts
partition functions. Actually, however, when there is a possibility of restricted rotation the entropy is usually obtained from heat capacity measurements.
198
ENTROPY: DETERMINATION AND SIGNIFICANCE
24p
Nevertheless, where the necessary data are not available, it is possible to make a very satisfactory estimate by the statistical method, the restricting energy being assumed to be equal to that in a related compound for which the value is known. 10
24p. Standard Entropies of Gases. The standard entropies for a number of gases, that is, corrected to ideal behavior at 1 atm. pressure, at 25 C are recorded in Table XIX. 11 They are based partly on statistical calcula
TABLE XIX.*
STANDARD ENTROPIES OP GASES AT 25 C IN CAL. PER DEGREE PER MOLE
IIC1
N
H, D,
Oi
Cl
Br 2 (0)
I a fo)
*
31.21 34.62 45.77 49.00 53.31 58.63 62.29
HBr HI
CO
H O(0)
2
NO
HjS
44.66 47.48 49.36 47.30 50.34 45.11 49.15
CO* N,O
SO,
NH,
CH CH
2
2
CH
4
4
51.06 52.68 59.24 46.03 44.50 54.85 52.48
For further data see Table 5 at end of book.
tions
and partly on thermal data, depending on which are considered more
each case. The values are all practical entropies which may be used in conjunction with those given for solids and liquids in Table XV to calculate the entropy change in a chemical reaction. These entropy changes will be utilized for important thermodynamic purposes in Chapter XIII. Special problems associated with the determination of the entropies of ions in solution will be taken up in Chapter XIX.
reliable in
Problem: Calculate the standard entropy change
at 25 C.
for the reaction
the total entropy of the products is 47.30 (for CO) 31.21 78.51 E,U. From Table XV, the entropy of the reactants is 1.36(C) for the reac16.75(H a O, Z), i.e., 18.11 E.U. The standard entropy change A tion is thus 78.51  18.11 = 60.40 cal. deg." 1 at 25 C.
(for Hi),
i.e.,
From Table XIX,
+
+
EXERCISES
1. Since the atoms or molecules in a solid occupy fixed positions they may be treated as distinguishable; there is consequently only one way of realizing a perfect
ibid., 27, 69 (1940); Wilson, "Treatise on Physical Chemistry," Gladstone, 3rd ed., 1942, Chap. IV (J. G. Aston); for empirical methods of treating molecules with restricted internal rotation, see Pitzer, J. Chem. Phys., 8, 711 (1940); Chem. Rev. t 27, 39 (1940); Pitzer and Scott, /. Am. Chem. Soc., 63, 2419 (1941); Ewell, Ind. Eng. Chem., 32,
tind., 27,
10
For reviews, see
17 (1940);
also,
Pitzer, Chem. Rev., 27, H. S. Taylor and S.
39 (1940); Aston,
778 (1940). 11 See Kelley, ref. 2, Latimer, ref. 2; see also, Thacker, Folkins and Miller, Ind. Eng. Chem,., 33, 584 (1941), Wagman, Kilpatrick, Taylor, Pitzer and Rossini, J. Res. Nat. Bur. Stand., 34, 143 (1945); Wagman, Kilpatrick, Pitzer and Rossini, ibid., 35, 467 (1945); Kilpatrick, Prosen, Pitzer and Rossini, ibid., 36, 559 (1946); for references, see Wilson,
ref. 10.
EXERCISES
solid, i.e., its
199
of
thermodynamic probability is unity. In a solid solution consisting NI molecules of one substance (or form) and N* molecules of another, the system can be realized in Nl/Ni\N 3 different ways, where N is equal to NI + N+ (Note
l
that for a substance in the pure state this reduces to unity.) Show that the entropy of formation of 1 mole of a solid solution from its pure solid constituents, N 2 In N 2), where NI and N 2 are the R(NI In NI i.e., the entropy of mixing, is respective mole fractions [cf. equation (19.32)]. 2. By assuming a solid solution of silver chloride (NI = 0.272) and silver bromide (NJ = 0.728) to have an entropy of zero at K, the thermal entropy at 25 C was found to be equal to the sum of the entropies of the pure constituents. Other measurements, not based on the third law, however, indicated that the entropy of the solid solution was greater than that of the constituents by about 1.1 Account quantitatively for the cal. deg."" 1 mole" 1 (Eastman and Milner, ref. 1).
+
discrepancy. 3. The heat of vaporization of mercury at its normal boiling point (357 C) 1 and the mean heat capacity of the liquid is 6.5 cal. is 13,600 cal. g. atom"" 1 1 deg."" g. atom"" Assuming the vapor to be an ideal monatomic gas and the atoms to be in a singlet electronic state, calculate the entropy of (i) gaseous, (The actual values are 41.8 and 18.5 E.U. g. atom"1 .) (ii) liquid, mercury at 25 C.
,
.
4. Use the tables of entropy data to determine the entropy changes accomKCl(s) = NaCl(a) panying the following reactions: (i) Na(s) K(); (ii) tO,fo) = JH 2 (0)  HCifo) + Ag(); (in) Hg(Z) AgClW 5. From the following data, evaluate the third law molar entropy of hydrogen chloride as an ideal gas at 1 atm. pressure and 25 C. The entropy of the solid 1 is 7.36 E.U. mole" at this temperature transition to another solid at 98.36 The increase of form occurs, the heat of transition being 284.3 cai. mole" 1 entropy accompanying the heating of the second solid modification from 98.36 to
+
+
+
HgO.
+
K
;
.
K, the melting point, is 5.05 E.U. The heat of fusion of the solid is 476.0 From the melting point to the normal boiling point (188.07 K), the mole"1 increase of entropy is 2.36 E.U. and the heat of vaporization is 3860 cal. mole"1 . The mean heat capacity of hydrogen chloride gas from the boiling point to 25 C may be taken as 6.98 cal. deg."1 mole" 1 at 1 atm. pressure. 6. Use the moment of inertia and vibration frequency given in Chapter VI to calculate the standard (practical) entropy of hydrogen chloride at 25 C. Compare the result with that obtained in the preceding problem. 7. Calculate the standard (practical) entropy of hydrogen sulfide at 25 C, using data in Chapter VI. 8. Show that if the Debye heat capacity equation were applicable, the entropy of a perfect solid at very low temperatures should be equal to JCp, where Cp is the heat capacity at the given temperature. What would be the value in terms of the Debye characteristic temperature? 9. By means of the following data for cyclohexanol [Kelley, J. Am. Chem. Soc., 51, 1400 (1929)], which exists in two crystalline modifications, test the third law For form I, the Debye characteristic temperature is 112; of thermodynamics. the increase in entropy of the solid, from CP measurements, from 13.5 to 263.5 is 33.55 E.U. At 263.5 there is a transition to form II, the heat change being The entropy change from 263.5 to the melting point (297.0 K) 1 ,960 cal. mole1 is 5.02 E.U., the heat of fusion is 406 cal. mole" 1 For form II, the Debye temperature is 84, and the entropy increase from 13.5 to 297.0 K, the melting point, is 45.34 B.U. mole"1
158.91
cal.
.
K
K
.
.
.
26) for the entropy change of a"h ideal monatomic gas at constant pressure and constant temperature.) Compare the result with the value which would be obtained from statistical calculations.12 K. using moment of inertia. The should be obtained by assuming entropy contribution at temperatures below 14 the Debye equation to be applicable. Am. 61.25) and (19. deg. The spin of each deuterium nucleus is 1 unit.13) or (24. ENTROPY: DETERMINATION AND SIGNIFICANCE The solid chlorine 1 l following beat capacities in cal. 12. /.14). Normal deuterium consists of two parts of ortho. 11. K . in Chapter VI. follow from the SackurTetrode equation (24. mole"1 . mole" (Add the entropy of mixing to the thermal entropy and subtract the nuclear spin contribution.62 E. 172.200 10.90 B.U."" mole~ have been recorded for [Giauque and Powell.to one part of paramolecules.U. respectively. Soc. Chem. The thermal entropy of normal deuterium was found to be 33. at low temperatures the former occupy six and the latter nine closely spaced levels. etc. 1970 (1939)]: Determine the entropy of solid chlorine at its melting point.. . Show that equations (19. Show that the 1 practical standard entropy of deuterium gas at 25 C is 34.
Further. Since E. there are two other functions.2) AS in equation (25..Q. represented by the symbol A. A = l Ei  TSi and A 2 = E . THE FREE ENERGY AND WORK FUNCTIONS 25a. which utilize the entropy in their derivation. both chemical and physical. AA r = A# r . the heat taken up when the given change carried out in a reversible manner. the increase in the at constant temperature. that are more convenient for use in many instances. Although the entropy concept is the fundamental consequence of the second law of thermodynamics. where Q rev. and S 1$ is the energy content entropy. T is its temperature. Hence A is to be regarded as a singlevalued function of the state of the system.1) A = Ewhere its of the system. and the direction of chemical change.CHAPTER X FREE ENERGY 25. its value being proportional to the quantity of matter constituting the system under consideration. is defined by (25. According to the first law of thermodynamics [equation 201 assuming a . thus. The work function. In order to obtain some understanding of the physical significance of the work function. is given work function accompanying the process by A. T and S are characteristic properties of the system.3) (7.2) is replaced is by Qm. it is evident that the same considerations must apply to the work function.2)]. since E and S are both extensive properties./T. The Work Function. or A = l (E 2 E) 1 T(S 2  /SO AA T = &ET If T&S. TS. then (25.TS 2 2. is (25. consider an isothermal change from the initial state indicated by the subscript 1 to the final state indicated by 2. will be employed extensively in subsequent portions of this book in connection with the study of equilibria. the free energy. One of these. A will also be extensive in character. depending only on its thermodynamic state and not on its previous history. and dA can be treated as a complete differential ( 4e). so that AA T.
. with similar expressions relating F and H. as usual. Second.9) . the results obtained above. is an extensive property.TS + PV. derived from the entropy is called the free energy. Since AA? and AJEr are completely defined by the initial and final states of the system. The second. to the pressure and volume of the system. that in any isothermal. and more generally useful. work is. e. AFP . under these conditions. where (25.202 reversible. (25.1) and (25. H is equivalent to E + PV. the free energy. it follows that in an isothermal process the decrease of the work function is a measure of the maxiwork obtainable from that change in state. It should be noted that any given process. function u*5b. hence. E and H.3) and (25. The Free Energy. . equations (25. First. work performed on or by the system. (25. it follows that F H .TS. is accompanied by a definite change in the value of the work function A. FA + PV. Comparison of equations (25.4) and (25.. the free energy F is seen to be a singlevalued function of the thermodynamic state of the system.kAp + PAY.g.7) that A E A H .&AT  (25. it is evident from equation (25. FREE ENERGY 25b Comparison of equations (25. isothermal or otherwise.1). since (25.8) Like the work function.5) so that the decrease in the A function in any process at constant temperature Since the reversible is equal to the reversible work done by the system. S. by equation (25.7) by equation (9. This definition may be written in two alternative forms which are frequently employed.6) P and V refer. and Q are definite. the maximum work that can be obtained from the given thermodynamic change in state. (25. like A. isothermal process. A is equal to E TS. depending only on the reversible process the values of The work term here includes all the forms of initial and final states. It is this fact which justifies the use of the term "work function" for the quantity defined by equation (25. but it is only for an isothermal process that this change is a measure of the maximum work available. von Helmholtz). For a process taking place at constant pressure.8) reveals an interesting fact of is related to F in the same manner as is to general applicability: It will be seen later that there are many relationships involving and E. although it was at one time called the "free energy" (H.v. In addition.3) Qr~.4) shows that TFn.. provide proof of the statement made earlier ( 8b).5).1).5). and is defined by mum W W F = E . so that dF is a complete differential.
in addition to work of expansion. G.13) and follows that (25.2SC THE FREE ENERGY AND WORK FUNCTIONS is 203 is If. As mentioned in connection with the work function.SdT.14) dA = dE . Randall.TdS . Work Function and Free Energy Relationships. tity is sometimes referred to as the net work. 32. so that by equation (25. see also. in addition! the change constant. N. exclusive of work of and so Ww. 35.15) dA At constant volume. AA is equal to Wn an isothermal one. function. and as the "available energy" (Lord Kelvin). it so that from (25.13) TVS. Gibbs). represents the total reversible work obtainable in the this may include other forms of work. The latter is equal to PAV ( 3g). By work differentiation of equation (25. reversible process. It was seen in of free energy 19i. A = E which defines the (25..e. Lewis and M. * . that [cf. dA v = SdT v or . and hence.10) The quantity v.14). the value of AF for any change is quite definite.e.PAF.g.1). the temperature v.18)J. Chem. 3 (1899).. in which work of expansion.W' nv . e. maximum. 364 (1900). * Lewis. (25. 1' 1923. i. Arts Sti. f as seen above.9) gives  Wm . and is represented by W'w. work other than work of expansion.11) accompanying a process taking place at constant temperature and pressure is thus equal to the reversible. equation (19. It is because the change in F is a measure of the "useful" work that F has been called the free energy. therefore.SdT.. .. so that equation (25. no matter under what conditions the process is performed. i. the maximum net work. phys. that can be obtained from a given change in state. work. Acad. .. W. i. = PdV .. This quanexpansion. (25. "Thermodynamics and the Free Energy of Chemical Subt stances. (25.e. Am. Proc. TdS = dE + PdV.e. Wn  AFp. for The decrease an infinitesimal stage of is restricted to the work done an isothermal. '" 25c.. Z. but only when the temperature and pressure are constant is the free energy change equal to the maximum net work available for the given change in state.T . i. obtainable from the process.10). (25. electrical or surface given change. PA 7 represents the reversible work. 1 It has also been referred to as the "thermodynamic potential" (J.
Such systems may be homogeneous or heterogeneous. equation (25. (25. in 20b. seen later that in some cases a system consists of several phases.16) with (25. must also be operative.SdT. or ffX* and at constant temperature. the change of variable from V to JP.17) and like those obtained are applicable only to closed systems.21) related to V in the same V for P. however. but the total mass must remain unchanged. et seq.204 FREE ENERGY 2Sd and at constant temperature.13) reduces this to dF = VdP . or giving the variation of the free energy with temperature and pressure. (25.TS + PV. dAr = PdVr. 25d. In these circumstances the equations apply to the system as a whole but not to the individual phases. It is found that of (25. and although the mass of the whole system is constant. respectively Differentiation of equation (25.. It must be emphasized that the results derived above. since an increase of pressure corresponds to a decrease of volume. For an isothermal change dF is zero.TdS . liquid or gas.. the second condition stated in 20g. Isothermal Changes in the Work Function and Free Energy.SdT + PdV + VdP. equations (25. and hence. is accompanied by a change of sign [cf. that the system is always in equilibrium with the external pressure. as stated in 20g.20) : and is brings to light another useful generalization A manner as F is related to P.18) and for an infinitesimal stage in a reversible process involving only work of expansion.22) . yields (25. djFV < = VdPr. and may consist of It will be solid. dF = dE .15) becomes (25. F = E . at constant pressure.21)]. changes may take place among the phases.e. Since it has been postulated that the work done in a change in state is only work of expansion. use of equation (25.17) with (25. as noted above. i. equal to Pd V. equations involving A and V may by exchanging A for F and be converted into analogous expressions relating F and P. Comparison of equation (25.19) dF P = SdT P . Hence. or These relationships give the variation of the work function with temperature and volume.6). or vice versa.
2) shows it to be in agreement with the relationship derived in 25a. At constant temperature. but it is not true generally. (25.16) with (25. similarly. /. VdP. and altering the signs where necessary. P*/P\ is equal to Vi/V 2 at constant temperature.8) the result > (25 26)  and. combination of equation (25. In the special case of the system being replaced 1 mole of an n * ideal gas. Upon dividing equation (25./ (25. and usually referred to as the GibbsHelmholtz equation.1) gives (25 27)  These two expressions are forms of the equation derived by J. The GibbsHelmholtz Equations.24) any appreciable isothermal process. P RT/V that this equality applies only to an isothermal process with an ideal gas.26) by T2 and rearrang. it in equation follows that AFr is equal to AAr. between the change in the work function in an isothermal process and the reversible work obtainable. is If the value of is S given by equa tion (25. and hence for (25. The corresponding expressions involving the free energy could be written down by changing P for V.19) gives dF T = VdP. important (25. however. Gibbs (1875) and H.25e THE FREE ENERGY AND WORK FUNCTIONS 205 For an appreciable isothermal process the increase A A in the work function can be obtained by integration of equation (25.23) Jvi Comparison of this result withequutl&Yi (H. so that p = RT\n^^ p Xp* p fip i .20) substituted in (25. thus. Considerable confusion was caused in the earlier development of chemical thermodynamics because of the failure to realize this limitation. but they may be derived in a simple manner. for an ideal gas. von Helmholtz (1882). . as may be seen by replacing and It is to integrating.23) by point out. * 2$e. AA r  (A f  Ai) r = ' 1 PdV. W.25) Since. equation (25.22) between the limits of the initial state 1 and the final state 2. V may be by RT/P.
by subtraction. indicated by the subtent. There are other forms of the GibbsHelmholtz equation which are more frequently employed.206 ing. (25. .TAS.* Further.32) another form of the GibbsHelmholtz equation may be developed utilizing the same procedure as was employed in converting equation (25.Off.16) derive the analogous expression it is possible to AA .8) becomes Fi so that = #1 . respectively.29) there .  equation (25.27). AH and entropy.1) and (25. Similarly.  . The process may be chemical or physical in nature. by means of equations (25. but this condition is usually understood. dividing through equation (25.28). heat content respectively. one of constant mass. etc. i. scripts 1 and 2. of an isothermal process.31) by from (25. T(S*  SO. For the initial and final states. equation (25. from equation and AS represent the increase of free energy.MS + T Still [ 2^] r (25. heat conaccompanying an appreciable process. for the given isothermal process.31) a very useful form of the GibbsHelmholtz equation. these deal with changes in the free energy.TSi F* and F H 2 2 l TS*. the only restriction is that it takes place in a closed system. which is in equilibrium with the external pressure.e.H ) AF = AH . F.31) by * Subscript! might have been included to indicate that constant temperature is implied.20).26) into (25.. but this is rarely used by chemists. "*>If this result is inserted into* . & x r2528 (25 28)  The analogous expression [d(A/T)/dT}r E/T* can be derived from equation (25. (25. T . thus.29) where AF. is obtained (25.. it is readily FREF ENERGY found that an alternative form r ay/rn I *T ] f is 25e __#.
Conditions of Equilibrium. are of general applicability. so that dS = It is. tions of the various forms of the GibbsHelmholtz equation. is to obtain simple criteria of spontaneous processes and of thermodynamic equilibrium which lend themThe result derived in 19e. and do not depend upon the path followed. for only in these circumstances can the various thermodynamic functions have definite values ( 4d). that for a spontaneous (irreversible) process there is a net increase of entropy of the system and its surroundings. dS. upon integration. and not to the net entropy of the system For a reversible change. the essential fact is thai in an irreversible process A > 5. the final results The GibbsHelmholtz equations (25. Hence. Attention may be drawn to the fact that although certain restrictions were mentioned in the course of the foregoing deductions. is equal to q/T. to some extent. on the other hand. in an infinitesimal stage of an irreversible process q/T is less than dS. by definition.34) . This is because irrespective of whether it is carried out reversibly or not. and. as well as other applicafor AF in terms of the temperature. will be taken &H up in later sections. dS > where dS ~ (irreversible process).. If perature ( 12k). (25. will hold for any change in a closed system. The only condition that need be applied is the obvious one that the system must be in thermodynamic equilibrium in the initial and final states of the process.32) and (25.33). is based on equation (19.14). " An important use of the free energy 25f. the sum of the q/T terms for all the isothermal stages is less than the increase in entropy of the system. for example. the resulting expression 207 T2 and may be put in the form This equation represents the variation of AF. therefore. in other words. of the work function. or rather of &F/T. and surroundings.e. ~ (reversible process). to derive an expression This matter. it is thus possible.25f THE FREE ENERGY AND WORK FUNCTIONS rearranging. possible to combine these two results in the general expression dS>.31). selves very readily to practical application. (25. with temis expressed as a function of the temperature at constant pressure. refers to the system alone. i. the values of AF and AH (or AA and AjE?) are quite definite for a given change.
By combining equation (25. i. provided first * Since and are constant.5)]. hence. 34) to (26.e.36) In the event that the external pressure is the only "force. at constant temperature and volume.37) E and V indicate constancy of these properties.208 FREE ENERGY 2Sf where the "greater than" sign refers to an irreversible process." the work is work of expansion. it depends on the initial and final states only and not on the path between them. the "less than" sign If the temperature now refers to the spontaneous (irreversible) maintained constant and no work is done. so that dT and w are zero.37) refers to the gain in entropy of the system alone.35) it follows that i inhere A ^wis SdT. in any process. Again. work and (25. Con when the energy and volume are maintained constant. if dA $0. entirely stances. while the "equal to" sign applies to a reversible process which. dS in equations (25. Compare in this connection the footnote in J 19ef which refers to the entropy of the aystem and its surroundings. process. is done dS 0. hence. solely of expansion. q so that (25. equation (7. 0. the energy content remains constant and no against an external force.V will increase in any change that is potentially spontaneous. (25. since a spontaneous process always represents a closer approach to the equilibrium state under the given conditions. if dE = w = 0. as seen in 8a. i. PdV] the condition that w is zero is then In these circumsatisfied when dV is zero.e. may be written (25.* In other words. but remains unaltered for a small change in the system when it is in a state of thermodynamic equilibrium..35) If. SK. By the first law of thermodynamics. the entropy of a system at equilibrium is a maximum at constant energy and volume. dS > **.38) dA TtV ^ This means that in a state of thermodynamic equilibrium. the volume is constant.14) with (25. E V . under the same conditions a spontaneous process is accompanied by a decrease in the work function. dE and w are both zero. is a succession of equilibrium states. even if it is actually carried out in a reversible manner. the result 0..34) may be written in the form = dE + w [cf. when the work in the form is dT = work and w = 0. the work function is a minimum. the entropy of a system increases in a spontaneous process.36) becomes dS KtV > where the subscripts sequently. (25. equation (25.
Since most chemical reactions and many physical changes are carried out under conditions of constant temperature and pressure. . rather than (25.41) in E and S respectively.11). w in equation (25. which defines the free energy. equation (25. 1 terms of mole of an ideal gas. according as the system changes spontaneously or is in equilibrium. and so equation (25. (25.8) and (24. (25.39) may be written as . 1 mole of a gas which behaves ideally.6).37) or (25. For an appreciable process. where P is the pressure of the system.i> ^ 0.39) is almost invariably used.25g THE PKEE ENERGY AND WORK FUNCTIONS is 209 always in may be re When the work is only work of expansion. . F = #o F * N . Further.35) placed by PdV. Q ^ dS . for the partition functions.42) It should be noted that in this section . at a given temperature and pressure. all spontaneous processes taking place at constant temperature and pressure are accompanied by a decrease of free energy. it follows that for a system in equilibrium. seen that $ VdP  SdT. and hence at constant temperature and pressure. it is combined with equation flF (25.RTlnN Q refers to the partition function. AF Tt /> ^ 0. it follows that for (25. and the system equilibrium with the external pressure.TS + RT. equation (25. Utilizing equations (16. Since dF T r is either IPSS than or equal to zero. thus. PV is equal to RT.18). (25. dE + PdV __ f  TdS ^ dE If this result is + PdV. the free energy must be a minimum. Work Function and Free Energy from Partition Functions. <IF T .39) where the "less than" sign refers to a spontaneous process. such as a chemical reaction.38). For 25g.40) a form in which the condition for a spontaneous process or for equilibrium is frequently employed (Chapter XIII). This conclusion is of fundamental significance. carried out at constant temperature and pressure. to give the conditions of a spontaneous process or of thermodynamic equilibrium. Eo . may be written F = E . for it provides a very simple and convenient test of whether a given process is possible or not.
RT In ^ (25. i.M. is (25.45) yields the result that dz is zero.46) is differentiated with respect to z..e.210 It is seen identical! FREE ENERGY 25h from equation (25. and this may be written in the equivalent form A since Ao . If z is constant. ^ whereas if ) . and (25. a thermodynamic property of a closed system.41) that at K. F and E are and hence equation (25.42) may also be expressed in the form F Fo .48) This result.46) y is maintained constant. N (25. 25h.. they gas. It is of interest at this point to refer to certain general procedures which may be used for the derivation of thermodynamic One of these. at will be used in Chapter XIII in connection with the determination of equilibrium constants and the free energy changes accompanying chemical reactions.. will now be used to derive some thermodynamic expressions. If 2 is a singlevalued function of the variables y and z t e.RT. so that (25. .RT In % . which has been already employed from time to time. so (25. A Eo equal to F PV it is [equation (25. sometimes referred to as the Euler criterion. with reference to the value in the lowest energy state.firingN RT. then equation (25.N.47) with respect to y.47) If equation (25. Thermodynamic Formulae. the results must be identical.43) These equations permit the calculation of the molar free energy of an ideal K.7)]. with z constant. it is possible to write for the complete (exact) differential dx.44) A and E are equal at the absolute zero.45) where M and N are also functions of the variables. is the following. ) \dzjy zero. and seen from equation (25. Since the work content A is hence to that F RT for 1 mole of an ideal gas. relationships. so that dy / dx\ . when T is zero. with y constant.. or the reciprocity relationship. ( ^ (25.42) . dx = Mdy + Ndz.g.
there follow immediately the four Maxwell relation ships. numerous thermodynamic equations can be derived. and the familiar mathematical relationship of the form (cf.PdV dF = .... (i dA\ = Iw } a/ iv dF\ ~&r } . x lv )' and ( By the use of equations analogous to (4. By the use of equation (25. (25.SdT .13). (ii)... . .. viz. a new set of SE \ /SH\ = /dA = from from I ( ..46) or (25... \oi IP (l11 ^ . equations (20. 'dJT By applying this result to the expressions relationships can be derived as follows: (i). such that dX = dY = then by equation (25. from . dE\ (I) and (m) . from(l) ^ V ) ) fl = UTS' \ CrO from / P ( fi ) = ft)r (^X from ( m If X and F are functions of the variables x...SdT + VdP dE [cf.TdS + VdP dA . y and 2. 21b).. L<&/ Lrf/ + + 0:^0 2dx. dT\ /dP\ ^' (asX J5 f / ff . (i) (ii) (iii) (iv) TdS .15) and (25.19).10).25h THE FREE ENERGY AND WORK FUNCTIONS 211 An examination of the present and preceding chapters will reveal four analogous equations which are of the form of (25.13).. .. (iii) and (iv).48). (20.PdV dH .1) or (25.45) these are . (ii) and .9) and (4.. respectively]..47).
and (dy).(dV/3P) T = (dV/dT)p = T(dV/dT) P + P(dV/dP) T = .. experimental determination. first (partial) derivatives.P(dV/dT) P 1 + S[_T(dV/dT) P \ (dV) F (dV) A = V(dV/dT) P  S(dV/dP) T (dA) H (dA) P = (dH)A (dF) A = . P.V(dV/dT)p = CP (dV/dP) T + T(dV/dTY f (dE) s (dH) 3 (dF) s (dA) s (dH) E (dF) K . y and z represent any of the eight variables. is equal to (dz) x the number where is effectively reduced to the twentyeight results given below. variables. A t 8X7X6. The derive use of the Bridgman formulae may be illustrated by employing them to an expression for (dT/dP)u. E. =.T(dV/dT) P J + P(dV/dP) T = .(dS) A = PCP (dV/dP) T/T + P(dV/dT)j.S(dV/dP) T = PCp(dV/dT) T /T + P(dV/dT)% (dS) B . 336.VCp/T + S(dV/dT) P (6S)r = =.V + T(dV/dT).. (6T) P (dV) P (dS) P (dE)P (dH) P (6F)p (dA) P = ======= (dP) p (dP) A (dV) T (dS) T (dE) T (dH) T (dF) T (dA) T (dS) v === = (dT) v (dT) s (dT) E (dT) a (dT) F (dT) A (6E) V (dH) v (dF) v (dA) v = .e.SIV + PtfV/dPW .). P. and F there are possible i. The procedure adopted is to write in a purely formal manner ..VICp .VCp/T (dS) H = .(dE) H = .P(dV/dT) P = . but since (da:). in general. and then to make use of the Bridgman formulae to obtain the appropriate values of (da. Bridgman 1914) has devised a system which permits the derivation of an expression for any of these first derivatives in terms of three quantities which are.. The required results are (dT) H = .S .[_S + P(dV/dT) P J_V . viz. (dx).7 = P(dV/dP) T = CP (dV/8T)r/T + (dV/dT)* P = Cp(dV/dP) T + T(dV/dT)* P . T. x. i.P(dV/dT) p .PECP (dV/dP) T = .PV(dV/dT) P .V[CP . V. + S(dV/dT~) P .(dE) F = .T(dV/dT) P .(dV) s = .(dV)u ==== = 1 = (dV/6T) P = Cp/T = CP. capable of S. (dP) T (6P) V (dP) (dP) E (dP).V .S =.(dH) T . //.(dV) B = . and a large number of relationships among them exist...P(dV/dT) P = CP =. There are actually fiftysix such formulae. . CP .. which is the JouleThomson coefficient ( lib).V(CP + S) + TS(dV/dT) P = .e. (dV/dT) P (dV/dP)r and (dII/dT) P . W.. viz..212 FREE ENERGY 2Sh Since there are eight common thermcxlynamic*.
CHEMICAL POTENTIAL under consideration is a closed one. . Am. that of the general ideas here. 10. for other generalized treatments. Phil. for a homogeneous system. .. 18.e. and of heterogeneous systems containing two or more phases. "Condensed Collection of Thermodynamic Formulas/' 1925. and the amounts of the various constituents present. Roy. . 259 (1907).2) Molar Properties. from time to time... . 129 (1907). . ni. . N.. N. ate well as in the amounts of its constituents. r. .. Chem. The derivative (dG/dn^T. Lewis (1907). . . 3 Consider any thermodynamic extensive property.g.. 'Lewis. and not to the addition or removal of matter. Trans. Chem.. (26. it is necessary to consider open systems. i. Rev..).. the change in the property G is given by stituents.. p.. Partial 26. the temperature. ibid. .n. 43. 5. T . where composition and mass may vary." 1943. i. Tobolsky. entropy. P.. n 2 . Lewis and M. Chem. one of constant mass. free energy. temperature and pressure of the system. see also. . Although the concept of partial molar employed in connection with thermodynamic properties other than the free energy (see Chapter XIX).26a so that CHEMICAL POTENTIAL 213 /n \dp) 2 .. Arta Sri. Lerman.. energy content. Am. 273 (1914). . W. ..1) n2 . Bridgman.. solutions.2. ref. 299 (1935).. 61. the results obtained so far are based on the supposition that the system quantities is v 3 * / 26a. "The Mathematics of Physics and Chemistry. phyaik. P. the partial molar free energy will be used so frequently that the opportunity may be taken to introduce some It has been mentioned. .. 2. In the study of systems consisting of two or more substances. Randall.. such as volume. ni n .. Proc. . are the numbers of moles of the respective con If there is a small change in the of the system. nti . thus.. J. Phya. e. 3. 1.. see also. see Shaw... f(T. 792 (1937) . or summary in Margenau and Murphy. n. Acod.p. as developed by G. Phya. and it is represented by writing a bar over the symbol for 1 Bridgman. the value of which. 43. 644 (1942). /. In this connection the concept of partial molar properties.. pressure. .JLU CP 2 [ \dT as in equation (22. etc. is completely determined by the state of the system. . A234. 233 (1921). The change of any thermodynamic property is then due to a change in the state of the system. . G is a function represented by G = where ni. Z. that is. (26 2) .^ ____ is called the partial molar property for the constituent i. . + . G. ni . Soc. . is of great value. H . 1. Sac.
.. Hence. at constant temperature property and pressure. Gidni + Gydfh + ni. i. *!. . the partial molar property <?< of any constituent may be regarded as the * In general. Puhem (1886).*  + nj& By dO Tt p  Hh nA + (26. of a particular constituent of a mixture may now be considered. W.*. na. FREE ENERGY <?. for a system of . it follows that at a given tem ndGi + ndG* +  + n4Gi +   0. (26.4) If dT and dP which the temperature and pressure of the system are maintained constant. be indicated by the mibeoript N.7) Comparing this result with equation and pressure (26..214 the particular property. by P.p = gives.  Gdrii +   . constant composition WI!A X 26b. Gibbs (1875) and later.. partial molar free energy.p. so that 26b ) */r. However.. . . independently. (26 3)  form . It is thus possible to write equation (26. . a more useful picture is obtained from equation (26. . of 1 mole of that substance to such a large quantity of the system that its composition remains virtually unchanged. at constant temperature it is seen that + GidnJ + (ndG* + Grin*) H ) perature (26. repre~ .X . are zero.e. definite composition. Physical Significance of Partial Molar Property. According to equation (26. sented by the numbers of moles n<.8) which must obviously apply to a system of definite composition. (26. This simple relationship is the basis of the important GibbsDuhem equation ( 26c). first derived by J.P.6) and pressure but varying composition.5). etc. (nidGi general differentiation of equation (26.6).5) upon integration.. it is the increase in the of the system resulting from the addition. so that dG T. (26. as in GT.6) : this states that the sum of for the the n<Qi terms for all the constituents is equal to the total value system of given composition at constant temperature and pressure. such as the partial molar volume.3).2) in the ** . The physical significance of any partial molar property.
and not an extensive one.* be pointed out. the partial molar property is independent of the n's and hence of the amounts of material in the system. It should be remembered. its value does not depend on the amount of material constituting the system. is system It may . of the ratio of the various n's to one another. . It is AC'S thus possible to rewrite equation (26. that is. the partial molar free energy or chemical potential of a constituent of a mixture is = F = t . This same conclusion can be reached by precise mathematical arguments based on the use of Euler's theorem on homogeneous functions.9) P. the derivative of G with respect to n i. Ft for the ith coastituent.6). (26. but only on the composition. n f . . that is. the partial molar property Gi has it is then identical with the molar property <?. that the partial molar property Gi is an intensive property ( 4d). in equation (26. . so that n\G\. t. G. Partial Molar Free Energy: The Chemical Potential. by the definition given above.10) * only a formal significance. for For a system consisting of a single (pure) substance. in view of equation (26. . . that the partial molar property Gi wag equal to the value of Gi for 1 mole of the constituent i in the pure state. Gibbs. . and which is represented by the symbol /* Hence. . however. identical with the function described by J. . . the discussion at present will be restricted mainly to a consideration of the partial molar free energy. . . Gi in a solution is not equal to (? for the pure circumstances. known as the molar chemical potential or. . will be a homogeneous function of degree zero. W. Gi. that is to say. Although the partial molar quantities of various thermodynamic properties will be considered in the course of this book.6). to give G by F. appropriate values of ni. 26c.26C CHEMICAL POTENTIAL 215 contribution of 1 mole of that constituent to the total value of the property (f of the system under the specified conditions. Upon first consideration it might be imagined. and further.. (26. . In other words. It will be seen later that this is only true in certain limited In general.. . the valueT of Gi varies as the composition of the changed. that Gi is not independent of the composition of the system..4). in brief. . This quantity is. n1 . and using dF = . At coastant temperature and pressure the property G is a homogeneous function of the numbers of moles (n) of degree unity. in general. for present purposes.e. replacing for the partial molar quantities. in view of this interpretation. substance. . hence. are the contributions to the total value of the property nzGz> UiGi. at the given temperature and Allowance for the quantity of each constituent is made by the pressure. M. the chemical potential. n^.
8) becomes + ndn + = 0. in equilibrium with the external pressure. equation (26.   .p nidni ^dni + ndn* + this  + M<rfn< + .10) becomes It has been shown previously ( 25c) that for an infinitesimal change in a closed system. dF = VdP .is the partial molar free energy /i t. so that equation (26. with equations If these results (25. one or more of the constituent phases may be open.21) which are applicable to a closed system. and '~ } =V. As indicated earlier. as of course they should be. viz.216 FREE ENERGY 26d In the special case when there is no change in the numbers of moles of the various substances present. dF T. that is to say.5). the change of free energy of each phase (open system) for a small change at constant temperature and pressure is given by equation (26.p is given by the sum of the changes for the individual . In a case of this kind. it follows that for the open system dF = .39) for a system at equilibrium.10). (26.SdT.15) which is one form of the GibbsDuhem equation.20) and (25. etc. especially in connection with the study of liquidvapor equilibria. equating coefficients.p 0. (26. in the sense that there may be exchanges of matter between them. constant temperature and pressure.SdT + VdP + dF T..12) These equations are identical. dn\ t dn%. (26. The condition represented by equation (25. Equilibrium in Heterogeneous System. when the system is a closod one.14). ^/26d. are now substituted in equation (26.14) which is of the When same form as equation (26. it is possible for a system consisting of several phases to be closed. applicable to a system at This equation has many applications. and for the system as a whole (closed system) dFr. such as are involved in distillation.. so that. the partial molar property #. nevertheless.. are all zero. is applicable to a closed system.13) At constant temperature and pressure becomes + /zadn* + + /**fo< + (26.
it follows that dE = TdS .+ +(?)**+ it (26.18) or (25. +  + dm v.. as will be seen in 28a. This result forms the basis of the well known "phase rule '. Although the definition of the chemical potential as the partial molar free energy is the one which is most generally useful in chemical thermodynamics.PdV + dni \ cmi / s. are independent of one another. for they refer to constant entropy and volume. it is possible to write V... which refer to constant values of the n's and hence are effectively applicable to a closed system. it is of interest to show that it can be defined in other ways. dF T. viz. Conse By quently.14). and not to constant temperature and pressure..266 CHEMICAL POTENTIAL 217 If the whole system is in equilibrium.14). pressure. at a given temperature phases. are not partial molar energies.18) dFT.SdT + PdV + VdP i. for the present purpose it is convenient to choose as the coordinates the entropy and the volume.. may be expressed as a function of the thermodynamic coordinates and masses of the constituents. .. that follows from a dE /dE etc  which are alternative definitions of the chemical potentials. and hence at constant temperature and pressure. dT and dP are zero. and hence. comparison of equations (26.n lt .v ni. + (^)*i. like the free energy. It should be understood that (dE/Jdn\)s. +  (26 17 >  utilizing equation (19. .p is zero. (26. respectively. . etc.p Combination of = dE  TdS + PdV.18). by equation (26.16) where the summation includes all the pdn terms for all the phases constituting the system. as seen above.6)]. (26. dn 2 etc.18) . .n and (dE/dV)s. are equal to T and P. . v. 1 26e.x. nt. and 2>t<*n<  0. then gives this result with equation (26. Hence.. it is readily seen that (dE/dS)v. indicating that the property has a wider significance than the partial molar free energy. The energy content of a system. dFr. Alternative Definitions of Chemical Potential. dF = dE .n lf + .19) and (26.13). The t . This justifies the use of the general term "chemical potential". \ oni /s. From the definition of F as E upon TS + PV [equation (25.r ()** .e. there is obtained t differentiation equation (25..TdS .19) Since the values of dn\.
Upon dividing 2 through both sides of equation (26.24) which is a form of the GibbsHelmholtz equation ( 25e). p. (26.24) by T" the result.N (25. p...TS t . Since dF is a complete differential. The variation of the chemical potential of any constituent of a system with temperature may be derived by differentiating equation (26. the order of differentiation is immaterial. it can be the chemical potential may also be defined in other ways. TS. is =5.nt.. analogous to . Variation of Chemical Potential with Temperature and Pressure. by definition. . it is seen that by equation (26.8). !. viz.P. and equation (26. so that This result is analogous to equation (25.22) are equivalent. .. *. shown that _() \ CWi /S.28).21) and (26.. 6f course. in alternative symbols.. . ni t .11) with respect to n. F = the temperature. and hence equations (26. _( \ CWi _/ 26f.20) which is applicable in particular . the results are and the latter being equal to the partial molar entropy. not equal to the chemical potential.. M< = Pi = ff t . \ dn Jr. . partial molar energy content would be defined by (d//dni)r. P. V dtt. If is the expression for the partial molar entropy given introduced. / Tt p. gives H T.. .218 FREE ENERGY and 26f this is..  > .9) with respect to temperature.. or. and differentiation with respect to w t By equation (25. pressure and the numbers of moles of the other constituents remaining constant. . n lt .23) *r(!g) V 01 /p.. to a pure substance. By means of arguments similar to those employed above.
F. moles of constituents with respective chemical potentials MI. e. n*. in the final state..27) If this result is substituted in equation (26. etc. The effect of pressure on chemical potential may be derived by differentiating equation (26. ni.g. the system may consist initially of ni.. thus.28) This result will be employed in connection with the thermodynamics of mixtures of gases in Chapter XII.12) with respect to n t . the system consists of nj.26) be compared with the analogous equation (25. The rate of change of chemical potential with pressure of a particular constituent of a system. MI. is PV = nRT may possible.26) may total number of moles. (26. it is seen that dF dnP so that _ (dfJLi\ \dPj T. which may refer to a chemical or a process. The . etc. at constant temperarture..n lt . liquid or solid solution.6) as niMi If.26).21) for a closed system. a further development of equation (26.26g CHEMICAL POTENTIAL 219 This equation is particularly useful for expressing the variation of the chemical potential with temperature. " it is (26. constituent of an ideal gas mixture. the other n's remaining unchanged. at constant pressure and composition! of any constituent of a gaseous.. physical change. moles of substances + + . is thus equal to the partial molar volume of that constituent. 26g. N =n (26. Free Energy Change in Any Process. a pure substance.P. . A useful application of the chemical potential is to determine the free energy change accompanying any In a completely general case.9) with respect to pressure and (26.N \dni/T. etc. in the equation of state be replaced by the sum of the number of moles of each constituent present in the mixture hence. For a system of ideal gases. The partial molar volume all is then given by differentiating with respect to n. The total fre* n*Mi energy of the system is then given by equation (26. '%) or / which r. at constant temperature and pres sure. ni. I _:.. found that for any  .
40).220 FREE ENERGY 26g whose chemical potentials are state is n'^'i is + n^2 + MI> M2. is 49 X 10~ 6 atm. constitute the basis of the Le Chatelier principle of mobile equilibrium. for the . The free energy the total free energy in the final change accompanying the process thus AF = (n{/4i + niiS +)EXERCISES ("iMi + n^ + ) (26. sult 8. accompanying the appreciable isothermal expansion of a van der WaalS (Use the expression for V in terms of P derived in 21a. i. 1. accompanying the compression of 1 mole of water from 1 atm.) gas. the change of heat content and the entropy change can be obtained from data in preceding chapters. with ft = 0? 5.p 0.. The variation of the volume of a liquid with pressure is given approximately &P) where is the compressibility coefficient and V o is the volume by 7 = 7 (1 at low (virtually zero) pressure. 2. Show that the relationships [d(AF)/dr> = .e. and 25 C l is 1. with the sub stances in their standard states. + + which is equal to S + R for 1 mole of an ideal gas. Using the fact that at equilibrium AFr. which are applicable to any physical or chemical change. The specific volume of water at 1 atm. pressure of each gas.00294 cc. Calculate the change of free energy in cal. etc. prove that . What is the corresponding free enert > change in calories? Is the reaction likely to occur spontaneously.1 at moderate pressures. under the given conditions? 6. Explain how the generalized compressibility diagram (Fig. to 10 atm. For the reaction 2H 2 S(0) SO 2 (0) = 2H 2 0(Q 3S() at 25 C and 1 atm. Estimate the value of AF in Exercise 5 at a temperature of 30 C. for any gas at constant temperature.AS and [d(AF)/dP> = AV.. at 25 C.] 9..29) A number of applications of this result will be found in later sections. determine the free energy change in cal.~ Would there be any appreciable difference in the result if the water were taken to be incompressible. 4) could be used to determine (i) the free energy change.. 7. Show that for a given process the rate of variation of the free energy change AF with temperature at constant pressure is given by [_d(&F)/dT']p AS. (ii) the work function change. what conclusion can be drawn concerning the free energy change accompanying the transfer of water from liquid at 25 C to vapor at 23.76 mm. which is the equilibrium vapor pressure. monatomic gas referred to the value FO in the lowest energy state. (ii) the work function change. 3. at the same temperature? Hence. . Derive expressions for (i) the free energy change. 4. assuming the rate of change of AF with temperature to remain constant between 25 and 30 C. Derive an expression for the change of free energy accompanying the isothermal change of a liquid from pressure Pi to F 2 For water at 25 C. g. [Make use of equation (25. Show that the same recan be obtained from the Bridgman table. Without the use of tables. Utilize the expression for the partition function derived in Chapter VI to develop an equation for the free energy of an ideal.
Combine the result cise 7. The vapor may be regarded as an ideal gas. and that of supercooled water at the same temperature is 2. The equilibrium vapor pressure of ice at 10 C is 1.20). and the same total (atmospheric) pressure. that equation (25./dA Show Derive an expression for (dF/dH)s by means of the Bridgman table. Is the sign in agree ment with expectation? 11.HiO(s) at . 12. . Prove the relationships in equation (26. 10. and 25 C. 14. 15. dF\ and fdF\ .10 C and 1 atm.20) can be used to derive the expression for the entropy of a gas in terms of its partition function. of the preceding exercise with that obtained in Exer Chapter VIII to evaluate the change in heat content for the process HtO(0 . accompanying the change of 1 mole of supercooled water to ice at 10 C. Utilize the Bridgman table to verify the relationships . dH\ 13.140 mm.950 mm. Calculate the free energy change in cal.EXERCISES 221 transfer of 1 mole of liquid water to vapor at 1 atm.
an appreciable transfer.FA is .g. AF it Since this is zero. at a given temperature and pressure.1). will not disturb the equilibrium at constant temperature and pressure. to utilize equation (25.. viz.g. possible pressure. AF = F B . and so they can be treated as closed. without affecting the state of equilibrium. the molar free energy is the same in each phase. liquid. therefore. etc.40). it follows. therefore. sideration. at constant temperature and It is. vapor. and FB is that in the other. Equilibrium Between Phases of One Component cussion hitherto has been devoted to laying the foundations of thermodynamic theory. by equation (27. 223 .F B In other words. that the corresponding free energy change is zero. AF  0. is in equilibrium. whenever two phases of the same single substance are in equilibrium. a large amount of water can be transferred from one phase to the other.1) where the free energy change accompanying the process under conIf FA is the molar free energy of the substance in one phase.CHAPTER XI PHASE EQUILIBRIA 27. a single substance in equilibrium at constant temperature and pressure.. of Consider any system consisting of two phases. thus. solid and vapor.39) or (25. For example. e. Suppose that a small amount of one phase is transferred to the other.. (27. (27. no matter what changes occur within them..g. which is the maximum number that can coexist in equilibrium for a system of one component.40). which have a bearing on equilibria between two or more phases. of 1 mole.. liquid and vapor. e.g. from equation (25. As long as both phases are present..g. the transfer of 1 mole of liquid to the vapor state is accompanied by an increase F B and a decrease FA in the free energy. from one phase to the other. liquid and vapor. follows that when the system . SYSTEMS OP ONE COMPONENT  Most of the dis27a. as a whole. Such systems remain of constant mass. This conclusion can be extended to three phases. e. e. e.. if liquid water and its vapor are in equilibrium. the time is now opportune to consider some applications of the results already derived to problems of physical and chemical imIn the present chapter a number of subjects will be discussed portance. of one or more constituents.2) FA .
VA dP . homogeneous or heterogeneous. it gives the variation of the equilibrium pressure with temperature for any two phases of a given substance. P. in equilibrium with the external pressure. viz. of each component is the same in every phase when the system is at equilibrium. the equilibrium pressure. OPXOfXwhich is applicable to any closed system. The Clapeyron Equation.g. to replace (dP/dT) v by dP/dT . Clapeyron (1834) .S B dT. the vapor pressure..12). where AH is here the molar latent heat of the phase change taking place at the temperature 5P. in place of the molar free energy..e. for any univariant system of more than one component. i. and is independent of the volume. in fact. and hence it is equal to &H/T. E. Since the molar free energy of a given and of a onecomponent system substance is the same in two phases at equilibrium. e. of substance from phase A to phase B. In a phase change there is no work done other than work of expansion.3) becomes dT where AV is the difference of the molar volumes in the two phases. mole..SA dT VB The term AS e. is dependent on the temperature only. dFA = VA dP . dFA = dFB so .19). AS dP SB .SA dT = V BdP . For a system consisting of two phases of the same substance and.S BdT.3) is the entropy increase for the transfer of a specified quantity. and it is permissible to use equation (25. making this substitution. 1 (27. An alternative derivation of the Clapeyron equation makes use of the Maxwell equation (20. for a univariant system.27b SYSTEMS OF ONE COMPONENT 223 It must be remembered that the treatment has been limited to a system If there are two or more components present. seen later ( 28a) that the chemical potential. equation (27. It is thus possible. This expression is a form of the equation first derived by B. it will be of one component. dFA is equal to dFB .x27b.. namely. the system remaining in equilibrium under the new conditions. the change in the free energy must be the same in each phase. . it follows that if the temperature and pressure are altered A B infmitesimally.SA dT Since and dFB = V BdP .g.
Qualitatively. i. in the Clapeyron equation (27. representing the increase of volume in transferring may be taken as Vi The corresponding value of AH.* If AS is the entropy change of the substance is transferred from one phase to the other.5) becomes when any given quantity dP = AS AF dT utilizing the fact that AH TAV ' AS is equal to AH/T. From a knowledge of the volumes (or * It should liquid (or solid) be understood that a system containing an inert gas. increase of pressure will cause the melting point to decrease. Thus. . SolidLiquid (Fusion) Equilibria. The result obtained in this manner is identical with equation (27. and the melting point will increase with the applied pressure. taken as the be may  (27 7) ' respective specific volumes.. the liquid has a smaller density than the solid.. However. (dS/dV) T may be replaced by AS/AV at the given temperature. densities) of the liquid and solid phases. Vi and F. at constant temperature. bismuth and antimony. so that equation (27. that is. . this is usually either 1 gram or 1 mole. then AF F.F. in addition to a pure and its vapor. it is possible to determine quantitatively the variation of the melting point of the substance with pressure.) dP AH.. it may be observed that if Fj is greater than F. AH/ is then the heat of fusion per gram. and AF is the accompanying increase of volume. If F. The quantities AH and AF must refer to the same amount of the substance under consideration.224 PHASE EQUILIBRIA 2^c without the constant volume restriction. substance are in equilibrium at the melting (or freezing) point. notably ice.4). Solid and liquid phases of a given 27c. where AH is the latent heat of the phase change. then AS/AV will be constant at a given temperature. By writing equation (27. is not univariant. dT _ T(Vt .e. so that equation (27. Very few substances. and of the heat of fusion. exhibit this type of behavior. if Vi is smaller than Ft the liquid having the greater density. This is the case for the majority of solids. the heat absorbed. in the same phase change is the molar heat of fusion. at the melting point. hence. then dT/dP will be positive.6) becomes an expression Alternatively. and this may be represented by AH/. for both AS and AF are extensive properties which are proportional to the quantity of material transferred. is the molar volume of the solid phase and Vi is that of the liquid at the temperature T and pressure P.4) in the inverted form is obtained which gives the variation of the melting point T with the external pressure P. 1 mole from solid to liquid phase.4). T is the melting point when P is the external pressure exerted on the system.
be known.7).*1 . hence. and AH/ given above are inserted in equation (27.0075 C for 1 atm. Thus.0242 dT/dP is small. Since Instead of utilizing the Clapeyron equation (27. all indicated forms.~ .0907 cc. It is unnecessary to enter into a detailed consideration of equation (27. for the comments made in connection with (27. In order to convert this into deg. the form stable above the transition point. or densities.) ' {27 8)  where dT/dP is the rate of change of the transition temperature T with the external pressure P. g.1.27d SYSTEMS OF ONE COMPONENT 1 225 Problem: The specific volume of liquid water is 1. and determined at the temperature T. atm. that increase of pressure is accompanied by a decrease in the melting point.0126 cc. point Calculate the heat of transition in cal.0075 atm." 1 Thus. the heat of fusion of ice at this temperature is 79.""1 . so that the melting point of ice (or the freezing point of water) decreases by 0. dT = 273. g. the specific volumes. atm. cc. g. The transition is it at rate of 0. V.7) can be readily adapted to the present case.8 dP . atm.""1 ." and that of ice is 1.2 X (1. cal. tion (27. V ft are inserted directly into equaA7/AP and V will be obtained in cc. atm.0001 .7) to determine the variation of the melting point with pressure. since T is 273. 27<L Equilibrium Between Two Crystalline Forms.2 K. or rather of AT/AP. and a. 0. which is assumed to be constant."" .8 Calculate the rate of change of melting point of ice with pressure in cal. The variation with pressure of the transition point at which two crystalline forms of a solid are in equilibrium is given by an equation of the same form as (27.~l at C. of course.8). Since readily found that the result is required in cal.~ .0001 cc. then and dT _ T(Va dP  V.5 and increases the at 1 pressure C. use may be made of the fact that 0. .~l .1 g. increase of the external pressure.~ l . It is because the specific volume oi" ice is greater than that of water at C. . of the solid liquid phases must.0. atm.0242 cal. all that is necessary is to multiply by the conIf the values given for it is A# .~ l . l deg.0907) X 79. g. 1 readily seen that dT/dP will then be in deg. g. if ft represents the form stable below the transition point." 1 is 3h) . g. cc. If it is the values of Vi.""1 atm. multiplication of the result obtained above by equal to unity (cf this figure will give dT/dP in deg.8). 95.035 atm. AH Problem: The specific volume of monoclinic sulfur (stable above the transition l point) is greater than that of rhombic sulfur by 0. it may be assumed to remain constant over an appreciable pressure range.7). it may be applied to calculate the heat of fusion from a knowledge of dT/dP.1 . Va and Vp are the molar (or specific) volumes of the is the molar (or specific) heat of transition.
which 95. is known." 1 . thus. atm.0 cm.0 cm.035 X 0. pressure is 1664 cc.2 cal. (27 9) The boiling point of a liquid is the temperature at which the pressure of the vapor in equilibrium with it is equal to the external pressure.1 .e." 1 (of mercury)..~*.V (AT/AP) ft ) _ ~ = 368. and P for external (atmospheric) or total pressure. it is possible to calculate the heat of vaporization. g.9). in the form of (27.1 . and Fi measured at the same temperature and pressure. On the other hand. so that equation (27. assumed constant over a range in equation (27. cc. version factor 0.5 .6). AH ^ 27e.368.0242 cal.. Vi. The procedure is similar to that described in the quantity * The volumes F. the vapor pressure. what is the same thing. g.226 PHASE EQUILIBRIA is 27e equal to unity. . it gives the rate of change of vapor pressure f of the liquid with the temperature. g.0126 0. for the rate of change of boiling point or of vapor pressure. Alternatively.~ l atm. at + 1 ~~ T(V a . Since A#v V . cin. 273.0242 3. LiquidVapor (Vaporization) Equilibria. dT/dP and Vi should be mean values. the boiling point being 100. the variation of vapor pressure with temperature. if the equation is inverted. but it is convenient to obtain the result first in deg. of vaporization of water to be constant at 539 the temperature at which water will boil under a pressure of The specific volume of 77. hence.2 Hence.) ' ..7 K. if the variation of boiling point with pressure or. the Clapeyron equation is used in the forms of both equations (27."" 1 and that of liquid cal. are sometimes called the "orthobaric volumes.10) ' Fi) may be utilized for various purposes." t The symbol p will be used for vapor pressure (and for partial pressure). V is the molar (or specific) heat of vaporization.00 C at 76. dT These equations T(V V  V (27. v of temperature.6) becomes dT _ T(VV ~' dP F. where F and (or 1 gram) of liquid to the vapor state is equal to Vv * Vi are the molar (or specific) volumes of the vapor and liquid. water vapor at 100 C and 76."" 1 . the Clapeyron equation gives the variation of the boiling point T of a liquid with the external pressure P. g. i.4) and The increase of volume AF accompanying the transfer of 1 mole (27. respectively.7 X 0. calculate Problem: Assuming the heat water is (approximately) 1 cc.5 cm. for example. As applied to the equilibrium between a liquid and its vapor at a given temperature and pressure. respectively.. This is required in deg. it is possible to determine dT/dP or dp/dT.9) may be replaced by A!F/AP. if the latter is available.
Vi.9) and (27. the use of V vt Vi and A//. this V V becomes 1 dp ^ . .0242 539 27.0."*1 converts this into deg.9). 373. i. derived by R. as is the case in connection with equations (27.37 C. taking T as 100. . the required boiling point at 77. where v is the molar volume of the vapor and p is its pressure at the temperature T. RT 2 (27.2 X (1664  1) X 0. the number of cm.0 cm. SYSTEMS OF ONE COMPONENT 227 problem in 27c.37 cm.. \j near the critical point. hence. in the external presin of 76 the cm.12) } ^ sometimes referred to as the ClausiusClapeyron equation. cc. A particular advantage of the ClausiusClapeyron equation is the readiness with which it can be integrated.12) between the temperature limits of Ti and T* and the corresponding vapor pressures pi and for it was first * For the heats of vaporization of a number of common liquids.e. it has the advantage of great In the calculation of dp/dT (or dT/dP) from a knowledge of simplicity.2 K.* or vice versa. Vv may be written as dp _ ~ Further. is small in comparison~ with thatrof the vapor. pVv = RT. by equation (27. it is not necessary to use the volumes of the liquid and vapor. as may be expected. Although the ClausiusClapeyron equation is approximate. Aff p'dT *L RT 2 ' dT This expression is ^. i.^Fi.0242 cal. given above yields AT/AP in deg.equation (27.11). the results are less accurate than those derived from the latter expressions.0 cm. of mercury equivalent to 1 atm..37 C.10) sure.9 atm.e. If the temperafa 27f. so that an increase of 1. atJjie same tempfiraturlTancr presVi inay be replaced i>y Vv ."" .27g cc. and multiplication by 0. Integration of the ClausiusClapeyron Equation. The ClausiusClapeyron Equation. so that the ideal gas law may be assumed to be applicable.1 Thus..e. in regions well below the critical point. integration of equation (27. Hence vicinity sure.10). pres1 sure. the heat of vaporization. pressure is 100. Substituting RT/p for v in equation (27. However.~l . see Table 2 at end of book. if the heat of vaporization is assumed to be independent of temperature. the result is 0. and then. causes the boiling point to rise by 0. the vapor pressure is relatively small. 27g. atm. AT = AP = 373.~l . the volume of the liquKJ^jLe*.. for it neglects the volume of the liquid and supposes ideal behavior of the vapor. thus.0 C. Clausius (1850). in the course of a comprehensive discussion of the Clapeyron equation. cal.""1 atm. If this is divided by 76. i.
gives In p = til + constant. Alternatively. mole.0 C being 76.6 cm. (27.228 pj. is f pi recalling that 4. deg. of the ClausiusClapeyron equation (27.9 cm.e. In equation (27. 18.12).2 /' Since pi has been expressed in cm. Problem: The mean heat of vaporization of water in the temperature range Calculate the vapor pressure of water at between 90 and 100 C is 542 cal.. assuming AHV General integration to be constant.0 g pi = 542 X 18. mole" 1 . p* is 76.2 4.. this becomes  C.. 27h.2 \ 373. g.12). deg.. Pi = 52. 76. X .15) or.). A#. It follows. At 100.576 ! 2 factor (2."" 1 90. after converting the logarithms. vapor pressure. the value obtained is actually a mean for the given temperature range. is 542 which will be taken as the value of 2%. by equation (27.mole~ and hence. deg. the value at 100. equation (27. therefore. i. IP is 1 1 converting the logarithms and expressing R in cal. i.2 K. the vapor pressure at one temperature (or boiling point at a given pressure) can be calculated (approximately) if that at another is known. mole" .e. p\ will be in the same units. as was assumed in the integration of equation (27.0 cm. . against the reciprocal of the absolute tern .987.13) becomes If A#. gives PHASE EQUILIBRIA 27h 1 1 l expressed in cal.987 cal. Vapor PressureTemperature Relationships.0 cm..1 since the molecular weight is 18. A//v is the molar heat of vaporization of water in cal. Hence. then R will be 1.e. 1.02 / 373.14). (27.1 mole"1 .576 \ 363. . that the plot of the logarithm log p.2 K. (The experimental value is 52.16) where of the C is a constant.02.02 cal..2 X 363. if a mean heat of vaporization is available."* mole" so that the heat of vaporization in cal.14). equation may be used to calculate the heat of vaporization if the vapor pressures of the liquid at two adjacent temperatures are known... Because A/f is not really independent of temperature. i.0 C. therefore.576 arises 4. 373.303) from the product of the logarithm conversion This and the value of R.0 C. in cal. it is required to find pi at Ti equal to 90 C or 363.
peraturo. Because A// v is not constant.21) possible by differentiation to derive of the temperature. dp/dT. in agreement with observation on a number of liquids. i. are constants for the given liquid. Thus. (27. Kirchhoff (1858) and similar to the equation proposed emIt is seen. that others. 1/3T.27h SYSTEMS OF ONE COMPONENT 229 A/7. allowance should be made for the variation of the heat of vaporization with temperature. however.19) This expression. therefore. 0. viz. over an appreciable temperature range the plot of log p against 1/T should not be exactly linear. A// may probably be expressed as a power series function of the absolute temperature. AH V = A# + where proximation <*T + PT* +  . equation (27. and the Clapeyron equation (27. R.20) where A.. which is equal to p X din p/dT is determined from (27.e. RT + jf H /y (27. sure data can be expressed with some accuracy as an empirical function of the temperature. etc. By heat of vaporization at any temperature can then be calculated. the . ail terms beyond the linear one may be neglected.21)./4.10) is used.. Thus. integration gives In p =is of tfi5 in T + constant. the orthobaric volumes Vv and V\ of vapor and liquid must then be known. but as these have no obvious thermodynamic basis or significance they will not be considered It may be mentioned. a. pirically B and C are constants. (27.17) As a first apA/Jo.576. in order to extend the range.. This procedure.16) is applicable over a restricted range of temperature. (27. however.18) and if this result is substituted in equation (27. assumes the applicability of the ideal gas law to the vapor. should be a straight line of slope the slope of this plot can be used to obtain an approximate indication of the mean molar heat of vaporization over a specified temperature range. To avoid the error introduced by this approximation. which the form log P = B T ^ + log + is C. by G. so that aT.. for example of the form log? = it is ~ + B + CT + DT* +  . (27. Several other vapor pressuretemperature relationships of a more complicated character have been proposed from time to time.12). an expression for d In p/dT in terms the of use the ClausiusClapeyron equation. that if the experimental vapor preshere.
3 cai.05 K. 239." .1 respectively.206 X 10~*T + 1.68 X 1 " dlog p 1 dlnp ~~ _ dp^ ~dT~~ ~2303' dT it is 2. and dp/dT is 0..7.04398 X 0.303? df ' readily found that at the boiling point.05 68. of mercury.0 cm.0242 The RamsayYoung and (27. cc. Thus. multiply V 9 and V A#.1 .r<V.91635  1..04398 atm. if 1 deg.~ l and that of the liquid is (approximately) 0. Aff. can be represented log by the expression P  + 9.0242 cal.  (27 23)  A and TB. the two liquids have Suppose that at the temperatures T' the same vapor pressure p'\ hence. 239.206 X 10* + 2. respectively."" 0.~~ J at its boiling point. (of mercury) deg." 1 to convert this to cai. (27.. X X 0.34 X 10'7* The specific volume of chlorine gas at its boiling point is 269.atm. &H V = 271. ~ = 3. 268. that is to say.20) is neglected.1 cc.. since j. g. at 239. g. will by are 269. By and equation (27.05 K.10). .05 K. which is equal to unity. If the B log T term in equation if the heat of vaporization is taken as constant.~ l . Diihring Rules.. respectively.  < 27 24>  . Differentiation of the equation for log p with respect to temperature gives _ Further. Calculate the heat of vaporization of liquid chlorine in cal. g. be in cc. g. when p 1 is 76. the vapor pressure variation with temperature of two liquids represented by log If these A and B can be PA . i .""1 it is necessary to 0.^~ + CA and log PB  ^+ (7B . in 27! cm.7 cc.22) substances have the same vapor pressure TB. then p at the temperatures TA and so that.343 cm. g.4 239.1 . g.230 PHASE EQUILIBRIA Problem: The vapor pressure of liquid chlorine.7 cc. g.04398 atm.)^.1 and 0. .~ l atm.
and consequently by equa + tion (27. This Like the result is an expression of the rule discovered by U.062.Young equation (27. respectively. who found that C\ was small. in fact. This result was obtained empirically by W.. for Since the normal boiling points are 373. the ratio of these temperatures is 287.271 SYSTEMS OF ONE COMPONENT 231 Subtraction of equation (27. of mercury at 287. the ratio of these temperatures is 373. e. i. and B 714 K.27) is particularly applicable to pfcirs of similar liquids. TA is 1218 + 273 = 1491 K.g.e. the DUhring equation (27. is silver and sodium are both 1 mm.. DUhring (1878). ethanol. be equal to the ratio of the normal boiling points. T'JT'^ of the two liquids. in fact. although it has been found to hold with a . this constant should. if the substances are related chemically Ci is almost zero..23) then gives (27 ' 25) where C\ S.052. The same result can be stated in another way: the ratio of the boiling points of two similar liquids should have the same value at all pressures.) The boiling point of silver By rearrangement of equation (27. that for any two liquids which are related chemtemperatures at which they have the same vapor pressure should be constant. and ethanol has the same vapor pressure at 273. Ramsay.273 = 2139 C. to 760 mm. and T* 273 1155 K. is applicable may be illustrated by reference to water and ethanol. The vapor pressure of water is 12. 1.26) it is found that Ti or . in view of the extrapolation from 1 mm.2.5 1. i. Ramsay and (1885). is thus calculated to be 2412 .26). T'* is 882 sodium.26). these are the temperatures at which both have the same vapor pressure The two of 1 atm. estimate that of silver. (The is value 1950 C. of The normal boiling point of sodium Let 441 A + 273 = represent silver. ratios thus agree to within about one per cent..2 K for water and 351.24) from (27.2/351. the ratio of the K Problem: The vapor pressures of molten mercury at 1218 C and 441 C.e.2 mm. is a constant.5 K.2 K. The extent to which the RamsayYoung rule. experimental involved in this calculation. It is to ically.25) becomes Young A and B < 27  rp mf  r< 26 > be expected. 1491 = " = 714 T' A T' A 1155' 2412 K.TB TB T' B constant > < 27  27 ) the constant being independent of pressure. so that equation (27. the agreement is quite reasonable. is 882 C.26).5/273. therefore. represented by equation (27.5.
for the equations (27. pressure. is more nearly constant if it is measured at the same concentration of the vapor in each case. ibid. they have been mentioned because of their practical value in certain cases. . if the vapor pres. Ann.. Various attempts have been made to modify the Trouton rule. instead of at the same pressure of the vapor.26) and (27. Chem. i. Am. 1 Ramsay and Young. 51.. 37 (1887). 62. Chem.. Eng.~l mole"1 Thus..25) is zero. Ind. it is possible. Provided the vapor pressures of a reference liquid are known over a range of temperatures. provided they are not associated in the liquid state. deg. Diiliring. Trouton's Rule and Vapor Pressure Relationship. 25. 21. then . Perry and Lamb and Phil. This rule holds for many familiar compounds with molecular weights in the region of 100. to establish the complete vapor pressuretemperature variation of another substance from one datum for the latter. 806 (1940). 11.. provided both are associated. a statement of the generalization known as Trouton's rule (F. at 1 atm..)   + 4. Roper. Soc.27) can be exact only if the vapor pressures are represented by the linear equations (27. At the normal boiling point the vapor pressure of a liquid is equal to 1 atm. if A// v is the molar heat of vaporization at the normal boiling point !T&. Hildebrand (1915) the entropy of vaporization applicable. however..Young or Duhring rules. Alternatively. 195 (1933). Mag.232 PHASE EQUILIBRIA 27 j moderate degree of accuracy for substances of different types. or both are nonassociated. 1 27j.. Trouton. the molar heat of vaporization at the boiling point may be used for A//v an expression for the variation of the vapor pressure with temperature is thus obtained from the one datum. 21 cai. It has been found experimentally that for a number of substances the molar entropy of vaporization A3 V at the normal boiling point has approximately the same value of 21 cal. hence. and if the constant Ci in equation (27. hence. ibid. (27. Physik.59.g. Although these empirical rules. Leslie and Carr. hydroxylic compounds. It should be noted that the results obtained cannot be very precise. viz.15). 33 (1886). e. v /Tb may be taken as equal to 21 for many nonassociated substances. 163 (1880). 515 (1885).. 116 (1929). 810 (1925): Smith. for such substances C should have a constant value.. 20.1 . equation (27. as in Trouton's rule. 17. Carr and Murphy. /. H. AH The Trouton's law expression for the vapor pressure p.e. in atm. deg. lie outside the realm of thermodynamics. log l =~ + c ' As seen above.1 mole.16) can be written as which is 1884). 32. by means of the Ramsay.. so as to make it more widely According to J.28) As a first approximation. strictly speaking. 22. of any substance to which is applicable thus becomes log p(atm.
259 X 76.0 19. ibid. Davis.28) would lead directly to the RamsayIt is of interest to note that rule.3 Since T* is 80. it is Young equation. 1072 (1942). CA CB * n equation (27. respectively. This equation gives the variation of the vapor (sublimation) pressure of the solid. same form as 27k. 360 (1931). 33.14). By means of this equation. and hence an equation similar to (27. ibid. The Clausius modification in which V..) equation (27.25) would have to be zero. Problem: The normal boiling point pressure at 40 C. For vapor pressure charts. is the molar (or specific) heat of sublimation. At 40 C.1 = + 1 .0 + 273. 0. see Watson. ibid. 28. For estimation of heats of vaporization. see Gcrmann and Knight. Another possibility. f * 30. 26.10) is applicable to solidvapor equilibria.587. ibid. so that log p(atm. it supposes that the constant C has the same value for all liquids.1 cm. the value of T is 40. the various calculations referred to in connection with liquidvapor systems can be made. 477.* known and the result . p 0. or by the integrated form (27.2 7419 313. 401 (1941). Killefer. ibid.. ibid. 23. Cox. mole" 273. Chem. and Vv and V. Since the procedure is obvious it is not necessary to enter into details. . at the equilibrium temperature and pressure..16). of benzene is 80. which is equivalent to the use of Trouton's law. A// v is21 hence by equation (27. (The experimental value is 18. 33.. 565 (1938). but the calculation may be used to give an approximate indication of the vapor pressure when experimental data are lacking. is neglected and Vv is taken as equal to RT/p. 7419 cal. is permissible.2 K.3 K. is to choose the known vapor pressure as 1 atm. A// v may be evaluated from equation (27. as for an ideal gas. are the molar (or specific) volumes of vapor and solid. Hence. estimate its vapor 353.. The agreement is not too good.59.2 = 353.28) is essentially equivalent to the based on equation (27. 34. if this were the case. bthmer.27k sure is SYSTEMS OF ONE COMPONENT 233 at one temperature. log p(atm. and in the second place. Ind. An equation of exactly the (27.28) may then be assumed to apply at other temperatures. ~ dT T(V9  ' 7. 1226 (1934). + 4. 1440 (1941).) == = + = 4. SolidVapor (Sublimation) Equilibria..28). (27.) X = 7419 . 226 (1940). Meissner.28).1 C.6 cm.12) can be used for the vapor pressure of the solid. then by Trouton's law.) where AH.24) and hence Ci in equation (27. thus. Ramsay.259 atm. 32. Eng. at the boiling point in order to determine A// v this value can then be inserted in equation (27.59 = 0.Young In the first place. 613 (1936).
AH must be equal to &HV A/f/. the slope of the curve AO on the pressuretemperature diagram is greater than that of OB. Kirchhoff equation (12. one of which changes into the other as the temperature is raised.). at the same temperature. e. OB is for liquidvapor. as stated in 12j. Hence. A and B. the change of Aft with temperature and pressure can be represented by the general equation . For any process.. respectively. It will be observed that near the triple point. If a given substance can occur in two phases. Variation of Equilibrium Latent Heat with Temperature. near the point 0. the vapor pressures of solid and liquid.) thermodynamics. or whether it is the equilibrium value. For the solidvapor system. thus. is greater than A/f.234 PHASE EQUILIBRIA 271 It is well known that the vapor pressure curves of the solid and liquid phases of a given substance meet at the triple point.g.. in Fig. 271. then the value of the accompanying latent heat and its variation with temperature depend on whether the pressure is maintained conIn the former case the stant. the first law of respectively.. must be the same whether it is carried out directly or through the intermediate form of liquid. That this must be the case can be readily shown by means of the ClausiusClapeyron equation. are equal. of heat content in the transition solid > vapor. the change at a given temperature. the value of dp/dT is greater along AO than along OB. and so also are the Temperature Fio. at least. and By + OB. The three curves meet at the triple point where solid. 16. so that A#. 16 the curve AO represents solidvapor equilibria. 1 atm. ^ &H Pl V dT RT*' At the triple point p and pi. the slope dp t /dT of the curve AO is thus greater than dpi/dT of the curve of vaporization (A//. in the vicinity of the triple point. for the liquidvapor system. the relative values of the slopes dp 9 /dT and dpi/dT are thus determined by the heats of sublimation (Aff. in other words. 'RT*' whereas. liquid and vapor can coexist in equilibrium. Pressuretemperature equilibrium diagram temperatures T.7) will apply. this can be written in the form dp. _ dT dpi P Aff. and OC for solidliquid equilibria. but if equilibrium conditions are postulated allowance must be made for the change of pressure with temperature.
insertion of these results into equation (27. AH f L d(AV) ] 9T JP _R p A7 T ' and hence the quantity in the braces in equation follows. equation (27.30) then leads to dT with temperature. In connection with the variation of the equilibrium heat of fusion with tem However. If by some means. the vapor being assumed to behave as an ideal gas.27m and hence. . In this for the variation of the equilibrium latent heat (CP)A. f (27. ) + . is exerted on the two phases in equilibrium. inert gas in the free space above it.(CW.31) becomes ACp = (CW.e. small for the solidliquid phase change. i.33) 27m. For the liquidvapor change the value of d(AH v )/dT is not greatly different from ACp. the same pressure. In this event. SYSTEMS OP ONE COMPONENT 235 d(Aff) dT ~ r a(Aff) [ dT ] \P +L ra(Aff)] dP \T dp dT It can be seen from equation (20. the vapor pressure. When a liquid or a solid vaporizes into a vacuum and a state of equilibrium is reached. AV may be taken as equal to V v the volume of the liquid being neglected in comparison with that of the vapor. at constant pressure equal to the vapor pressure at the given temperature. where the constant pressure is the expression ACp is equal to (CP)B equilibrium pressure of the system at the temperature T. as may be seen from the following considerations.31) reduces to (Cp ) t _ (<7. temperature is not too near the critical point. the pressure on the liquid (or solid) is changed. that provided the It (27.4).20) that and according to the Clapeyron equation d(Aff) (27.g. e. . As shown in 27f. by introducing an insoluble. Dependence of Vapor Pressure on Total Pressure. (27. and so equation (27.32) where (Cp) and (Cp)i are the heat capacities of vapor and liquid. [d(A VJ/dT^p is usually perature. .. this simplification is not permissible.31) is equal to zero. therefore.. and this may be replaced by RT/p. respectively. and the foregoing approximations may be made with some justification. dP/dT = AH/T&V for a phase change.
hence. H. where VA and VB are the molar volumes of the phases A and B. so that VAdPA = VBdP B . Hence. let the accompanying change in the pressure on B. V. the molar free energies must be the same in each phase ( 27a) . where Ap is the increase of vapor pressure resulting from an appreciable increase in the total AP pressure exerted on the liquid. in the form Hence.' where P is the total pressure on the liquid and p is the vapor pressure. so that dp/dP may be replaced by Ap/AP. the Poynting equation is which is (1881). As seen above. at constant temperature. the pressures on the respective phases are then PA and PB* Since the phases are in equilibrium. is given by a generalized form of the equation first derived by J. In the special case in which A is a liquid and B a vapor.YsdPs. Consider any two phases A and B of a given substance in equilibrium at a specified temperature. dFA VA dPA and dF B . the criterion of equilibrium.86) . under the equilibrium conditions. the free energy increase dFA of one phase would be equal to the increase dFB of the other phase. The problem is treated below in a general manner. be dP B The molar free energy changes of the two phases are given by equation (25. equation (27.35) may be written (27. Poynting For equilibrium to be retained. Suppose the pressure on the phase A is altered by an arbitrary amount rfP^. if a small change were made in the system in such a manner that the equilibrium was not disturbed. so that The effect of external (total) pressure on the vapor pressure of a liquid is small. which is required to maintain equilibrium.236 PHASE EQUILIBRIA 27m the pressure of the vapor will be affected. Assuming the vapor to behave as an ideal gas. is equal to RT/p.24) as . dFA must be equal to dF B . without restriction as to the nature of the two phases or the method of applying the pressure. &l! dP V. respectively. the pressure changes on the two phases must evidently be inversely proportional to the respective molar (or specific) volumes.
in different more or contain two components may proportions. . .. deg.. Atcw. Thus.~ l mole" 1 The specific volume of water may be taken.36).  8 See. at constant temperature and pressure which are the same for all the phases.of equal molar Because each phase free energies in each phase requires some modification. M2(<o. Consider a closed system of P phases.018 27. can be readily Problem : The true vapor pressure of water is 23.. assuming ideal behavior. . it is necessary to introduce partial molar free energies.78 mm. When Ap 23.018 X 23. M2(P>. the whole closed system is in equilibrium. Glasstone. 2.g. so that V i is about 18 ml. further. total pressure.76 mm. the vapor pressure p is equal to the i.082 The vapor pressure is thus 23.018 0.082 literatm. as 1.28a from which the SYSTEMS OF MORE THAN ONE COMPONENT effect 237 the external pressure. In using equation (27. Hence. R will be 0. IX.76 + 0. . The chemical potentials.76 mm..e. 6. amounts dn moles of the components are transferred from one phase to another.0 X 298 0. in place of the molar free energies.76 A = A " . MKP). nevertheless. 8 28. or 0. the external pressure is increased 1 atm. 23. "Textbook of Physical Chemistry. indicated by the letters a. with sufficient accuracy. assuming the vapor pressure not to alter greatly.76 X 1. The effect of external pressure on the vapor pressure of a liquid is seen to be relatively small.0. pressure. then the equilibrium condition . the temperature and pressure remaining constant. . 1946. . SYSTEMS OP MORE THAN ONE COMPONENT If 28a. by equation (27. C.0. in equilibrium containing a total of C components. ^C(P). the water vaporizes into a vacuum. so approximately by that AP is 1.018 liter units. . and so according to equation (26. if Vi is expressed in liters and AP in atm.16) the sum of all . P. the units of R are determined by those of Vi and AP." 2nd ed. the subject has some significance in connection with the theory of osmotic pressure.. or partial molar free energies ( 26c). designated by 1. mole"" 1 . . of the various Akx) J components in the P phases may be represented by Mi(a>. it will be seen that Ap and p must be in the same the exact nature of which is immaterial. Calculate the vapor pressure when water vaporizes into a space already containing an insoluble gas at 1 atm. for example. 3. Suppose various small . . Conditions of Equilibrium. at 25 C.082 X 298 0. on the vapor pressure resulting from an increase ot e. Chap. Mi(fc>> M*<&).0. by introducing an inert gas.36). . a system of several phases consists of more than one component. at 25 C or 298 K. . . evaluated.
a tendency for each component. The Phua Rule. e. + Mi<6)dni<&> f f 4 0.2). therefore. etc. the partial molar free energy (or chemical potential) is equal to the molar free energy (see footnote. hence. it is essential that Ml(a) = Ml(6) = == ' ' = Ml(P) M2(P) (28. since the whole system is a closed one. until the values become identical in the two phases. that when a system consisting of a number of phases containing several components is in complete equilibrium. and the equations (28.2). at a definite temperature and pressure which are uniform throughout..238 the fjtdn PHASE EQUILIBRIA terms for all 28b It follows. 28b. all (28.3) It is seen. (28. If the phases of a system are not in equilibrium. There is thus seen to be an analogy between chemical potential and other forms of potential. for which such a difference exists.3) become identical with (27. subject only to the strictions represented by the equations (28. In other words. it is possible to derive the familiar phase rule which gives the relationship between the number of components and phases in equi . the chemical potential of each component is the same in all the phases.g.1) to remain zero for possible varre iations dn in the numbers of moles of the components. the total mass of each component will be constant. the chemical potentials There will then be of the components will not be the same in each phase. + If the expression in dnc(p> is = 0. matter tends to flow spontaneously from a region of higher to one of lower chemical potential. electrical potential. 26b). energy potential. to pass spontaneously from the phase in which its chemical potential is higher to that in which it is lower. therefore.1) At equilibrium. By means of the conclusion reached in the preceding section.2) equation (28. that the phases will be zero. It may be noted that in the special case of a single component.
Hence.4).1) = C . if such a system is to be univariant. which is maintained in equilibrium.e. and assuming that no other factors. system is thus P(C total 1). it follows that Total number of variables = P(C 1) + 2..4) is applicable to any univariant system. (28. for if the concentrations of all but one of the components are known. the degrees of freedom.3) : this is 1) independent equations which automatically equivalent to a set of C(P fix C(P The number of variables remaining 1) of the possible variables. this number of variables must be arbitrarily fixed.P 2. that the same result can be obtained if the univariant system consists of several components. the three phases would then be (i) the solid component 1. TJnivariant System of Several Components. equations (28. A simple example of such a system would be a saturated solution of a nonvolatile solid in equilibrium with vapor of the solvent.. Suppose a small"change is made in the system. form will then hold for the system even if The phase all rule in its the components are not present in every phase 27b 28c. the value of P will be 3. i.1) 2] order to define the system completely. such as surface or electrical effects. familiar degrees of freedom...e. therefore. The librium. (ii) a saturated solution of this substance in the liquid component 2.. and hence must be equal to the number of degrees of freedom (F). of the system. that of the last component must be equal to the remainder. which must be specified in order to define the system completely. for the compositions of P phases to be defined it is necessary to state P(C 1) number of concentration variables of the In addition to the composition. hence. i. However. by a more detailed procedure. i. at a given temperature to the in leads result the represented pressure.4) the phase rule derived by J. e. the number of composition variables is reduced correspondingly. and the number of variables.e. influence the equiconcentration terms..g. to avoid too great a complication of symbols. According to the phase rule.3). The fact of the closed system being in equilibrium. equaThe net effect will thus be to leave unchanged the number of tions (28. e. with C = 2. so that there must be three phases in equilibrium.P+ which It is 2. Gibbs (1875). etc. It is of interest to show. or variance. and undetermined . as given by equation (28.g. The 1 concencomposition of a phase containing C components is given by C tration terms. W. water. In is then [P(C . F = 1. the discussion will be restricted to a system of two components.C(P . and (iii) the vapor of the latter. It was indicated in that an equation of the form of (27. although its derivation was restricted to a system of one component. At the same time there will be a similar decrease in the number of independent equations determined by the equality of the chemical potentials. + + F = C . the uniform temperature and pressure of the system must be specified. may be noted that if a particular component is absent from any phase. . a salt.28C SYSTEMS OF MORE THAN ONE COMPONENT 239 librium in a system.
8) Since the system has remained in equilibrium. (28. In other words. is solid. and (28.e. equation (28.20) (25. as given by equations (28.6). (28. as described above...e.21). transformed into = .  VJ)dP + ( ^} dni  0. it is possible to eliminate the last term in each equation. the change of chemical potential in one phase must be equal to the accompanying change in the other phase.9) Suppose that when the dn\ moles of solid (solute) are transferred from the solid phase to the solution.n and (dfjLi/dP)T. must be identical.10) where SJ and V% refer to the molar entropy and volume of component 2 in the (pure) vapor phase. i. the chemical potential of the given component must be the same in both phases.e.&idT + FidP and + (*r 1 } dm.8). the number of moles of constituent 1 in the solution. The reason is that * Aa in f 26a.. (dm/dT)p. Bit By utilizing equations (26.7) and (28..9) is multiplied by n\. and the results added. found that  OS.vi =* P.7) Similarly. solid and solution. If equation (28. and (6F/dP)T V. hence. (28.S(dT + V{dP. (3F/dT) P  S. there is no term involving dn\ in equation (28. that  (S l  S'JdT + (7.  SS)dT + (f.26).6) can be. . by means of equations dp{ (25. equation (28. The accompanying change in the partial molar free energy (chemical potential) of the substance in the solution is of then given by whereas the corresponding change in the chemical potential of the pure which is equivalent to the change in its molar free energy. i. therefore.  VfidP + (j&) dm  0.240 PHASE EQUILIBRIA 28c involving changes of temperature dT and pressure dP and transfer of dn\ moles component 1 from the solid to the solution. it is necessary to transfer dn* moles of the component 2 (solvent) from the vapor to the solution in order to maintain the equilibrium.5) can be written as d/ii . i.9). dp > < 28 6 >  the primes being used to indicate the solid phase. (28. Since the molar free energy of the solid is independent of the amount. it follows. the number of moles of the substance 2.23) and (26.10) is multiplied by n>. the subscript N is used to represent constant composition. dpi and dn{. By proceeding in a manner precisely similar to that used in deriving it is equation (28. by subtraction.
15) this is zero. dP = AS dT AV and since ' AS may be replaced by &H/T.28d is SYSTEMS OF MORE THAN ONE COMPONENT 241 sure. this becomes which is identical in form with equation (27. This quantity may be represented by AS. As obtained above. will give the influence of pressure on the eutectic temperature at which two pure solids 1 and 2 are in equilibrium with saturated solution.11) parentheses. when inverted. 28d. It is thus seen that an equation analogous to that of Clapeyron has been derived for a univariant system of two components. for the formation of the equilibrium solution from the appropriate amounts of the two constituents in the solid state.12) gives the variation with temperature of the vapor pressure of a saturated solution.6)]. Of particular physicochemical interest are surface special circumstances. but in most instances their influence is so small as to be negligible. It is however. In this case AH and AF are the heat content and volume changes.&SdT + AVdP = 0. represented by PdV. and n 2S that of the n 2 moles of (niSi + nt$i) (niSi + + pure vapor 2. thermodynamic systems are invariably subject to gravitational and surface forces. n i^i is that of n i moles of the pure solid 1. A/? is the change of heat content accompanying the formation of the given solution from the solid solute and the vapor of the The same equation. it follows that 2 + . Electrical and magnetic forces may also be operative in work done possible.niSI + naS . and AF is the corresponding volume change.n^V^dP = { 2 0. therefore. For example. since n\S\ (26. In the thermodynamic treatment of systems in equilibrium it has been postulated. nyd^ for the solution at constant temperature and presequivalent to n\d^i and by the GibbsDuhem equation (26. respectively. .n&ftdT + The expression in the first (n l ? l . equation (28. is equal to the increase of entropy accompanying the formation of a saturated solution from n\ moles of solid 1 and n 2 moles of riaSa represents the entropy of the solution [cf. equation vapor 2. that other forces may have to be taken into consideration. The is then only work of expansion. the corresponding increase It follows.(n^ . that equation (28. (28.n^ + n P 2 . which may be rearranged to take the form ntS"). up to the present.11) may be written as of volume. Properties of the Surface Phase. . forces. Hence. and the quantity in the second parentheses may similarly be replaced by AV. solvent. the effect of which becomes apparent when the quantity of matter contained in the surface is relatively large in comparison with that of the system as a whole. that the only force acting upon the system is that due to the external pressure.4). and a similar result could be secured for any number of components.
the exact thickness of the region is immaterial.242 PHASE EQUILIBRIA 286 of Consider a heterogeneous system. not be specified. which may be positive or negathe system is then defined as the excess of that conof constituent of any tive. of on the the location postulated for the hypothetical ponents system depend surface.g. Equilibrium of Surface Phase. but the description is convenient. consisting two phases. in other words. The surface free energy F* may be expressed by a relationship similar to equation (28. In order to derive the thermodynamic properties of the surface phase. but as a region of more or less definite thickness. provided it contains all the parts of the system which are within the influence of the surface forces.13). Thus if n. c( and c? are the numbers of moles per unit volume. . consider a hypothetical state involving an exact geometrical surface placed between the two bulk phases. two liquids or a liquid and vapor. stituent in the actual surface phase over the amount there would have been if both bulk phases remained homogeneous right up to the geometrical surface. . geometrical surface. The transition from one phase to the other. in the interior of the two bulk phases. 28e. thus be regarded as the contribution to the system made by the "surface 11 excess amounts of the various constituents or. The surface excess.14) F is the total free energy of the system. then the number of moles n\ of surface excess of the constituent i is given by V n.13) for the surface excesses of the various com. It may be remarked that the socalled surface phase is not a true phase in the usual physical sense. For the general treatment which follows. F= where F' + F" + F..14). For the present purpose... Consider a small change in the system described above. Thus the two bulk phases. nj. but the surface chemical potential (partial molar free energy) M'/ and the surface entropy S' only will be employed here. its exact position need The actual values nj. the concentrations.e. so that the surface of separation is not to be regarded as sharp. . is probably a gradual one. of one or more components. c'iV + c?F" + nl (28. but subsequently this will be defined in a particularly convenient manner. viz. i. e. and and V" are the respective volumes of these phases right up to the imaginary geometrical surface. The free energy change dF is then equal to . (28. be may thought of as being separated by a surface phase. F' and F" are the free energies of the bulk phases calculated on the assumption that they both remain homogeneous The free energy F9 may right up to the hypothetical. A suitable position for this imaginary surface will be proposed later. Other thermodynamic properties of the surface phase are defined in a manner exactly analogous to equation (28. there will then be a surface of separation between the phases. consisting of the two bulk phases and the surface phase. of the surface phase. across the bounding surface.* is the total number of moles of the constituent i in the system.
+ + dF'  S'dT + + V'dP' + /iidni + M+ (28. The work required to increase the area of the surface by an infinitesimal amount ds.16) and (28. The latter is a measure of the reversible work which must be done for unit increase in the surface area under the given conditions. 9 (28. .SdT + V'dP' + V'dP" + yds + iVidn'i + I>?dnT where S is the total entropy of the system.e.18) dF Tt p. M  A MS (28. If there is no restriction concerning the passage of matter between the two bulk phases and the surface phase. When surface forces are significant.39) as dFr p = 0.15). in addition to constant temperature and pressure. which refer to the homogeneous bulk phases.13) as . (28. obtained by summing dF'. the quantity corresponding to VdP may be omitted. so that for equilibrium t + E^nJ.17). provided the sum for each component is equal to It follows. pressure and composition. stituents of the system. Since the surface work does not involve work of expansion against the external pressure. (28. however. = Upon applying 0.. it is seen that i + EMtdn? + M WnJ = (28. at constant temperature.20) therefore. dF" and dF . On the other hand..18)..19) this conclusion to equation (28.16) In evaluating dF for the surface phase. that dF9 = where  S'dT + yds + n[dn[ + ^ dn + 8 2 2 . M. since no matter passes in or out of the system as a whole.21) .S"dT 9 V'dP" + Adifi + n"M + . is equal to yds. S' For a system in which the only force acting is that due to the external pressure. It follows. since the surface contribution to the volume may be ignored. is dF  . the condition of equilibrium is given by equation (25. (28. it is necessary to take into account the free energy change accompanying a change in the surface area. dn? and dn\ are independent. where y is the quantity usually referred to as the surface tension. therefore. that for each constituent from equation (28. are given by equation (26. (28. the variations dnj. i.15) and dF' 1 = .286 SYSTEMS OF MORE THAN ONE COMPONENT 243 dF' dF" dF9 The first two terms. The expression for dF for a small change in the system should ( thus include the term yds. It is consequently seen from equations (28. zero. it is not difficult to show that this result must be modified by stipulating constant surface area. it may be identified with the net work and hence with the free energy change 9 25b).17) are the surface chemical potentials of the various conMI. + S" + S*. that dF.20) at equilibrium.
21). (28. and at constant temperature this becomes equation (26. 0. It is thus permissible to write equation (28.. a solution of a single solute.e. . and of a quantity depending upon the area of the surface. nl/s so on.dM + Tjd/iJ . depending only upon the thermodynamic state of the system.24) sdy + ZX4f! = thus providing a relationship between the change in surface tension and the corresponding changes in the surface chemical potentials. the result is dy or.15)] (28. . the surface chemical potential of any constituent of a system is thus equal to ite chemical potential in (he. equation (26.g.25) becomes . The surface free energy F* is the sum of the contributions of the various constituents. i. + <M + 25<*/*5 + s s by T 2 and . e. 28f.e.26) at constant temperature. (28.. (28. tion (28. 0. equation (28. and hence differentiation of equa where . the surface area.23) Upon comparison with equation S'dT + sdy + 2X44 = [cf.26) in the form dy + r. dF* is a complete differential. are the excess surface "concentrations" of the various constituents of the system. where s is the total surface area. + + F' = ys + nfoi + n M2 + .22) gives dF9 . replacing n\/s by TI. bulk phases at equilibrium. dy . are as defined by equation (28. pressure and surface area. i (2827) . [cf. Dividing through by s.6)]. + iWi + T2dM2 +  0. it is seen that (28. these "concentrations" are really the excess amounts per unit area of surface.25) where I\ Fa. i. For a system of two components..17). nj/ii n^nl .0.244 This result PHASE EQUILIBRIA 28f is an extension of equation (28. property of the surface.22) 9 Since F is a definite nf. nj. . the surface chemical potential of any constituent must always be equal to its chemical potential in the bulk phase.. The Gibbs Adsorption Equation. If the system is in equilibrium.yds  yds + sdy + n\dp\ + nM + + Adn\ + &dn\ + + sdy + nJ<M + Uridnl (28.. hence.13). the solution. The latter is equal to 75. =0.3) . at constant temperature. dy + Tid/ii + Tdri = 0. by equation (28.
2)] that the chemical potential ^2 of of a solution. at constant tern . Willard Gibbs (1878). In these circumstances equation (28.28). it relates the surface excess of the solute to the variation of the surface tension of the If an increase in the concensolution with the concentration (or activity). 28g. of radius r.. Another effect of surface forces relates to the change in certain physical properties. e. The free energy change dF for the transfer of dn moles of substance from the flat surface to the spheres is equivalent to the transfer of this quantity from pressure po to pressure p. this phenomand of the there solute deficiency negative enon is referred to as negative adsorption. Vapor Pressure and Solubility of Small Particles. is dy + F 2 dM 2 = be seen later [equation (31. i. the surface excess of constituent 1. study of dilute solutions make FI zero. on the one hand. is negative. is a in the surface. F 2 is of the solute occurs under these conditions. and a 2 is called the "activity idealized concentration for free energy changes. 0. tration of the solute causes the surface tension of the solution to decrease.28) becomes It will + RT . first derived by J.e. (dy/dc)T.29) and (28..g.. the activity being an ture. by equation (28. .30) are forms of the Gibbs adsorption equation. and hence FI and F 2 depend upon the arbiIn connection with the trary position chosen for the geometrical surface. the solute. may be represented by constituent any In a 2 where M is a constant for the substance at constant temperaM " of the solute. e. a spherical drop or particle of a pure substance. The equations (28. F2 will be positive. the vapor pressure Po differing from that of the small particles. the solvent. adsorption If (dy/dc) T is positive. r2 = \ RT\dlna T (28  M > For dilute so that solutions.g. (28. the concentration of the solute. Consider. Upon making the substitution for M2. in equilibrium with vapor at a pressure p. equation (28.28g SYSTEMS OP MORE THAN ONE COMPONENT 245 where MI and ^2 refer to the chemical potentials in the solution.27) becomes to zero. in other words. consider a flat surface of the same substance.1 may be replaced by c. so that there is an actual excess of solute in the surface. It will be recalled ( 28d) that n\ and nj. is made equal that it is convenient to choose the surface so as to to say.30). resulting from the difference in size of the particles of a solid or drops of a liquid. vapor pressure and solubility. On the other hand.
33) The surface area s of the drop is equal to ds 4irr2 .32). at 298. mole~l and r in cm.31) as dnRTln If ical yds. by combining equations (28.314 107 ergs deg. the correct form is obtained by using the "fugacity" in place of the vapor pressure.  24. hence it is possible to write equation (28. (28.303 X 298.31) The increase of free energy for the process under consideration is to be attributed to the fact that the addition of material to the small drops causes an appreciable increase in the surface area.34). Consequently. hence. it is seen that (28. If the PHASE EQUILIBRIA vapor behaves as an ideal gas. where y is the surface tension.35) would be in ergs mole"" .33) and (28.dnRTln^ (28. the spherical drops or particles is thus greater than that of the the proportion increasing as the radius of the particles decreases. the righthand side of 1 equation (28.2 log ^ p ~ 2 X TMX 18.25) 28g dF . mole""1 .0 dynes cm.1 . as will be evident from the next chapter." 1 and its molar volume is 18. Large drops or particles thus tend to grow at the expense of smaller ones.0 cc. The surface tension of water may be taken as 72. The higher vapor pressure of small drops or particles accounts for their tendency to disappear by "distillation" on to larger particles. and hence (28. The vapor pressure of Problem: The vapor pressure of a large (flat) body of water is 23. (28. and the spherdrop of radius r contains n moles. Calculate the vapor pressure of drops of 10~~ 5 cm.. then nV = and upon differentiation it is found that dn = ~ dr. in dynes cm. it is convenient to express as 8.35) Po r fiat surface. equation (28."" 1 mole" 1 . then by equation (25. (28.35) is not exact. whereas for the flat surface the accompanying decrease is negligible.246 perature. also in contact with its saturated solution.32) V is the molar volume of the substance under consideration. V in cc.314 X 10' X 2.0 mm.34) = Sirrdr. The increase of free energy for a change ds in the surface area is equal to yds.. If the vapor does not behave ideally. radius.01 For transfer particles in equilibrium with a saturated solution.2 K. at 25 C.76 mm. If y is R X 8. can be . Consequently. the free energy of from a flat surface.
respectively. Chapter XV). RT In . 4. 5. J. The specific volume of benzene vapor at its boiling point at 1 1 Calculate the heat of 1 atm. g.) 3. Chem.28g EXERCISES 247 expressed in terms of the concentrations of the solutions.9 55 C p 373.2 cc. is 356 cc. In this case 7 is the tension at the interface between the solid (or liquid) solute and the soluIt is evident that fine particles can have an appreciably larger solubility tion. 562 (1926)] from which the boiling point is found to be 80. The vapor pressures of mesitylene at various temperatures are as follows: t . The vapor pressures of carbon tetrachloride at several temperatures are as follows: t 25 113..36).0 mm. Use the equation for log p as a function of temperature in the preceding exercise to derive an expression for the variation of the heat of vaporization of benzene with temperature."" and this estimate the boiling point at of benzene at temperature vaporization 77. equation (28." 1 . Below its boiling point the variation of the vapor pressure of benzene with temperature is given by 1402. but this refinement may be ignored for the present.8 100 247. At its normal boiling point (77.25 120 381. large crystals.15 C) the orthobaric densities of ethyl acetate are 0."" and that of the liquid is 1.5 n** log p(mm.4 45 258.35) takes the form tions (cf. Show that if TA and TB are the temperatures at which two liquids have the same vapor pressure. cc. e.. Calculate the heat of vaporization by (i) the Clapeyron equation.1 C mm.20 C. (The actual value is 76. than large crystals of the same substance.46 51387.828 (liquid) and 0. EXERCISES 1.35 80 150. Strictly speaking.0 cm. [Mathews." . at least for dilute soluIn this case. 48. .g.16).8 35 174.Young rule. t p 60 67. Plot log p against l/T and from the slope evaluate the mean heat of vaporization of carbon tetrachloride in the given range. 2. pressure. Using the values of V and C just obtained estimate the normal boiling point of carbon tetrachloride.2621 .) 6. the plot of log TA against log TB should thus be linear. and see how close the result is to that expected from Trouton's law.) = 7.00323 (vapor) g. log TA = log TB + const. (The vapor may be supposed to behave ideally. (ii) the ClapeyronClausius equation. Soc.Co r . The rate of change of vapor pressure with temperature in the vicinity of the boiling point is 23.6mm.36) where c and c represent the concentrations of saturated solutions in contact with small particles and a flat surface. Am. AH 1 deg. (28. then by the Ramsay. g. From the results of the preceding exercise determine (approximately) the constant C in equation (27.8 C. the activity of the solute should be used instead of the concentration in equation (28.
Soc. dp/dT for water is 36.2 .~ l the ideal gas value.) 16. g. The variation of the vapor pressure of solid iodine is given by 68 cal. Chem. 14.~ . pressure? 17.248 PHASE EQUILIBRIA By means of these data and those given for carbon tetrachloride in Exercise 1. and then TA against log jTs. The mean heat capacity of water vapor in the range from 100 to 120 C 1 l is 0. ization of water in cal. determine how closely the Ramsay. pure water being the reference liquid. A It is required to distil the liquid at 100 C. At what temperature will the given solution boil at 1 atm.6 cal. and compare with 58.5 cc. and compare the result with that obtained in the preceding exercise."" plot log 7. What is the change of volume per gram accompanying the fusion of benzene? 10. g. The heat of vaporization of chlorobenzene at its boiling point (132.) At 110C. X . pressure. c should be approxi10~* if AP is in mm. where AT is the increase of boiling point for an increase AP in the external pressure. estimate the approximate pressure that would be used.~* at the normal boiling point.6 C. . 12. and for liquid water it is 1. (Craft's rule).Young rule.4 cal. Ramsay and Young (1886) found that in the vicinity of the boiling point the quantity T(dp/dT) is approximately constant for many liquids.7 C.0 mm.48 cal. 8. 11. Dtihring's rule has been found to apply to unsaturated solutions of a given An unsaturated solution of calcium solute.788 g.0 C) is 73. g." at 100 C. is Am. g. solution) has a vapor pressure of 240 mm.14 mm.374 of sublimation at 25 . determine the approximate value at 110C. g. log p(atm. g" 1 molar volume of the vapor at its equilibrium pressure at 25 C. deg. 13. A hydrocarbon (nheptane) is known to have a vapor pressure of 92 mm.479 cal. The heat C Estimate the and the specific volume of the solid is 0. 1 ." 1 Estimate the (approximate) pressure in cm. ."" 1 . liquid (mercury) normally boils at 357 C and its heat of vaporization is .0 C. taking V Vi as 277. chloride (30 g..5 C. The melting point of benzene is found to increase from 5."" 1 . g. cc." 1 the orthobaric specific Calculate the heat of vaporvolumes are 1209 (vapor) and 1. Estimate its vapor pressure at 30 C. Recalculate the result. 240 and 360 mm. and its 1 Determine the change of vapor pressure resulting from density is 0. and determine the temperatures at which the two liquids have the vapor pressures 120. g. [Giauque. for liquids obeying Trouton's rule." 1 at 110 C. and that it leads to the relationship AT cTAP.05 (liquid) cc.009 cal." Taking the heat of 1 vaporization of water as 539 cal. (Plot the vapor pressure as a function of temperature in each case.50 to 5. per 100 g. 9. Estimate its normal boiling point. Estimate mately constant and equal to 1.78 C when the external pressure is increased by 100 atm. (The experimental value is 185 mm. 53. 507 (1931)]. g. Show that this is a consequence of the Ramsay.. (The experimental value is 98.) = OC10 00 ^  2.) 15. . The heat of fusion of benzene is 30.Young rule is obeyed. The true vapor pressure of ethyl acetate at 35 C is 59. g. of mercury under which the liquid will boil at 130 C. The normal boiling point of nhexane is 69. at 75. pure water has this vapor pressure at 70. g. at 40 C.22 cc. /.^ the introduction of an inert gas at 2 atm.013 log T + 13.
0 cm. at the same temperature T.) p(mm. where p. Chapter T X to calculate the mean heat of fusion of ice in the range from 10 C. deg. (ii) the heat of vaporization.19) which is used when surface forces must be taken into consideration. and compare the result with that obtained in Exercise 4. (iv) the triple point temperature and pressure. iP .)  9. and pi are the vapor pressures of solid and supercooled liquid. Suggest a physical interpretation +B of this result.~ l between the vapor pressure curves of solid and liquid hydrogen cyanide at the triple point. Chem. AH/ is the (mean) molar heat of fusion and to m is the melting point of the solid. using the data in the preceding exercise. At appreciable concentrations. the variation of the surface tension y with concentration c of aqueous solutions of the lower fatty acids is given by 7 = A log c. 9 48. Soc..74460  1864. (i) the heat of sublimation. 23.06/!T (from 243. in mm. 20.EXERCISES 249 the boiling point of benzene at 77. Calculate the difference in slope. with pressure. 21.8/T 1453. 18. where A is a constant for each acid and B is approximately the same for all the acids. Show that if the vapor behaves ideally. Am.4 K). Show that the extent of adsorption of a fatty acid at the surface of its aqueous solution is then roughly independent of the concentration of the solution and of the nature of the acid. i. . (ft) liquid. 24.e. Prove the condition of equilibrium given by equation (28.) 19. /. 22. 299 (1926)]: (a) (6) log log p(mm. Use the data in Exercise 10. The vapor pressures of (a) solid. for a twocomponent system. Calculate temperature ranges. (v) the normal boiling (Note that the latent heats are approximately constant in the given point. (iii) the heat of fusion.10). . hydrogen cyanide are given by [Perry and Porter.7 to 258 K) (from 265 to 300. Give in full the derivation of an expression for the variation of a binary eutectic temperature.33902 7. respectively. Give the complete derivation of equation (28.
N.3) is always satisfied. Chap.2) will ^ .4) its F is the molar free energy of the gas and / is fugacity.. 37.5) 1 Lewis.. Actually. Chem. Acad. the relative fugacity. reversible stage of an isothermal change involving work of expansion only. XVII. be (partially) defined in such a manner that the relationship dF = RTdluf is (29. but the introductory treatment will be restricted to pure gases.3). not a but function /. 38. 1 lewis and M. mixtures. as distinct from the postulated behavior of ideal gases. FUGACITY OP A SINGLE GAS 29a. Definition of Fugacity. so that If (29.e. known as the fugacity. equation (29. viz. where (29. /i (29. in the study of chemical equilibria involving gases The fugacity is chiefly employed in connection with gas at high pressures. F2  Fx = RTlnfy. i. Randall.24). irrespective of whether the gas tion of (29. at a later stage ( 30b) it will be extended to systems consisting of more than one component. 1 According to equation (25. for an infinitesimal.RTd of the gas. may equation hold. U V may be replaced by RT/P. at a given temperature. Arts Sci. For a gas which does not behave ideally. In P.. 250 . It has been applied especially. Z.4) defines the ratio of the fugacities at two different pressures.3) at constant temperature gives ideal or not. "Thermodynamics and the Free Energy of Chemical Substances/ 1923. G. as will be seen in 32c. dF = VdP. G. phyf. Integra F = RTlnf+C.. 49 (1901). Am. By utilizing the free energy fu notion. Lewis (1901) introduced the concept of "fugacity. This may be seen by considering the definite integral of equation (29. 205 (1901). N." which has proved of great value for representing the actual behavior of real gases. Proc. (29. the system consists of 1 mole of an ideal gas. the integra tion constant C is dependent upon the temperature and the nature of the gas.2) dF a RT where P is the pressure (29.CHAPTER XII FUGACITY AND ACTIVITY 29.
25). thus. in general..5) shows that for an ideal gas the fugacity is proportional to the pressure. which may be written as F 2 /<\ = and comparison firing. it is necessary therefore to assign it a specific value in a particular reference pressures. it follows that at constant temperature gas equal RTdlnf = VdP or (29. and f/P is not constant. F2 For an ideal gas the difference of molar free energy in two states at the same temperature is given by equation (25. and the fugacity is always equal to the pressure. i. As the pressure of the gas is decreased. It is convenient to take the proportionality constant as unity. For an ideal gas the fugacity is equal to the pressure at all pressures. so that for an ideal gas//P = 1. To determine the fugacity of a gas at any pressure where it deviates from ideal behavior. lira P+0 L = " as 1 or ^ It will > 1 P 0. permits the evaluation of actual It may be mentioned that since gas presfugacities at various pressures.5) to give the In order to express the fugacity in any state. both of which apply to any gas. the behavior approaches that for an ideal gas.e. fugacities are recorded in the same units. difference F 2 FI (or AF). not proportional to one another. and for a real . For a real gas. the actual molar volume of the gas at the temperature T and For an ideal gas the volume of 1 mole is RT/P. however. 29b. and this is seen by equation (29. sures are usually expressed in atm. and /i and /* are the corresponding The experimentally determinable quantity is the free energy fugacities.6) V (dlof\ _ fdlnf\ ~~ \~tPj where RT ' (29 7) ' V is pressure P. but for a real gas this is only the case at very low pressures when it behaves ideally.. at the state. Determination of Fugacity: Graphical Method.29b where FI and FUGACITY OF A SINGLE GAS 251 are the molar free energies of the gas in two states.3). ratio of the fugacities f*/fi.1) and (29. the following procedure has been used. be seen shortly that this postulate. same temperature. which makes the fugacity of a real to its pressure at very low pressure. By combining equations (29. the fugacity and pressure are. of this result with equation (29. and so the gas at very low pressure is chosen as the reference state and it is postulated that the ratio f/P of the fugacity to the pressure then approaches unity.
and hence In (f/P) be800 Atm. 2. Phys.8) Hence from equation (29.252 FUGACITY AND ACTIVITY is 29b gas the quantity a. as postulated above. the area under the curve between the pressures of zero and P gives the value of the integral in equation (29.8). _ JL C P adP. Chem. therefore.JL adP. which may be defined by a function of the temperature and pressure. 2885 (1931).0365 400 1.7959 1.000 atm. against the pressure. has suggested that it would be preferable to * define the fugacity by means of equation (29.6).9) since.9846 100 0. it is necessary to plot a. Determination of fugacity of nitrogen gas To calculate the fugacity. (29.9) . virtually result is zero. 800 1. that JBT Since the 2 \ !T/P PV/RT values for various P's are given above.0641 can be readily seen from equation which defines a. Pressure (P) FIQ. derived from experimentally determined molar volumes of the gas at comes 2 zero. the In L . at constant temperature. it is possible to derive Tunell. /. the conditions f/P * 1 and/ * as then follow automatically.2557 (29. 35. or = in P . at zero pressure. various pressures. RTdlnf = RT:? din/ dl If this result is integrated p jf dp ' between a low. (29. f/P becomes equal to unity.9). P PV/RT It 50 0. 17. pressure and a given pressure P. P . Problem: Utilize the following data to calculate the fugacitiea of nitrogen gas at the various pressures at C.9846 200 1. a p V..
these may be plotted against P (Fig.20C FUGACITY OF A SINGLE GAS 253 the corresponding a/RT values..4 1191 1834 X 10~< atmr 1   0.11) it is possible to express as a function of V.000 3.834 f 48. at constant temperature. Jy* Since 7* Jy* = PV . and hence the integral in (29.39 . then integration of equation (29.64 a/RT Integral f/P 0. and/* is the value at a low pressure P*. 17). P 50 atm. thus. can be determined. it follows that In (///*) may be replaced by In (//P*). * The shape of the curve at low pressures has been adjusted to the fact that a then tends to an approximately constant value (cf. (29.9) this is equal to graphically.061 1. fugacity of a gas at pressure P. hence. 96. i. In P*.971 1.0596 0. 29d). that is.10.0288 0. it is seen that by RT.3980 0.979 0.6060 If / is the 29c.e. P .P*V*  where V* is the molar volume corresponding to the low pressure P*.2 424.0206 0. Determination of Fugacity from Equation of State. Utilizing the postulate that//P approaches unity at low pressure.489 1.967 0.9.82 .7) gives (29 10)  The grating variable of the integrand in equation (29.10) by parts. the gas then behaves almost ideally.08 1.10).54 1. /*/P* virtually unity.0320 0.* and hence the integral of a/RT between zero and any pressure P may be evaluated In (//P).7 194. by In/ is In/  In P* + ~ (PV RT  V C PdV\ . it is permissible to replace P*V* and upon substituting the result in equation (29.6. is now changed by inte /p I JP* VdP = PV\ J "iv  /v I PdV PdV. 100 200 400 800 1.6) or (29. the results are given below.11) can be evaluated analytically. and hence f/P and/ By equation (29.95 atm.95 . By means of an equation of state.
12) that RTb y . * The conventional values of a and 6 for oxygen. ^ .13) can be readily shown from the van der Waals equation (29. at the specified constant temperature.009 liter2 atm. 1. respectively (see and 3. that have been derived from experimental PV data at the given temperature. Since V* is very large. in any event they will not be identical with the tabulated a and b values. equation (29.5 y and combination of > this result with equations (29. thus. which is equal to RT/P*. a was 10~2 liter mole" 1 . for />___. Randall 8 using equation (29. I  __ .64 X * Lewis and Randall.14).13) gives (29 14) ' Consequently.11) and (29. derived from critical data.f v* \Jv1f */ "~~ ~ dv ' J?T* In _^_^_^__ xV J. 196. the fugacity of a van der Waals gas at any pressure can be calcuvolume at that pressure.12). for the latter are usually based on the critical data ( 5d). (29. p.111 _. By ^V and hence */ir# b c Pdv = c J^5 dv . these will differ from one temperature to another.32 10~*. lated from the C have been The fugacities of oxygen at a number of pressures at calculated by G. mole2 and b as 2. Because of the incomplete quantitative nature of the van der Waals equation (cf. Chapter II). /V* /" PdV + It (29. V* 6 may be replaced by 7*.254 FUGACITY AND ACTIVITY illustrated is 29C The procedure may be which the equation of state by reference to a von der Waals gas. . rcf. "TT ____ _^ . N. are 1. Lewis and M. and a/F* can be neglected. provided the van der Waals constants for the given gas are known.12) where a and b may be regarded as constants. It is only when other information is lacking that these may be used to obtain an approximate indication of the fugacity.* The taken as 1.12 X Table I). The values of a and 6 to be used here are those which have been derived from actual PF measurements at the required temperature. independent of the pressure.
__P RT ibid. Maron and Turnbull. It is an experimental fact. Chem. 4 Maron and Turnbull.29d results are recorded in FUGACITY OF A SINGLE GAS Table 255 XX. By using a more exact equation of state. Approximate Calculation of Fugacity. 33. Soc. 1536 (1941). the figures given under the heading PM.RT where AP. 33. that at not too high pressures the value of for any gas is a linear function of its pressure at constant temperature. equation (29. such as the BeattieBridgeman equation. Chapter II.961 0..960 0. but since this equation involves five empirical constants. 44 (1942).929 0. hence.8). 246 (1941). Ind.91 1. is given by <* 17 = RT V = p A.29 52. the treatment 4 is somewhat more complicated than that given above. A may it is equation be taken as constant at a given temperature. are the pressures which an ideal gas would exert if volume as the actual gas at the given temperature. the fugacitics obtained from equation (29. it occupied the same TABLE XX. PV PV . thus.0 174 338 540 108 220 381 465 Even though a and b are derived from actual PVT data. 69.87 0. 100 200 400 600 f 48. 29d. in addition to R.5 f/P 0. Table XX). equation (29..0 92. 64. C P 50 aim.. 0. defined by equation (29. and so it is possible to make use of the fact that In x is approximately equal 1 when x approaches unity. Chem. Utilizing this result. better values for the fugacities can be obtained.05 1. J. FUQACITT OF OXYGEN AT Pld.14) may not be too reliable over a range of pressures because of the approximate nature of the van der Waals equation. Am. . Exercise 7).85 0.925 0. From this seen that a. provided they are not too high. Brown.15) becomes to x P /_. see also. A so that a is (approximately) constant over a range of pressures.90 P/Pld.9) becomes or (29 l5)  At moderate pressures f/P is not very different from unity (cf. Eng. with which the van der Waals equation is in agreement (cf.
at ordinary temperatures. is the compressibility factor considered in earlier sections 20e). see 2245 (1931). even at (cf. and hence (29.5 200 225.1 25 25. It may be mentioned here that although the fugacities in Table are always less than the corresponding pressures. Rev. 1. and so equation (29..9).. so that RT n <***(!*). 108 (1939). (29. however. except at higher temperatures. The definition written in an alternative form. 638 (1931).256 PUOACITT AND ACTIVITY introducing the definition of a.16) that the fugacity will then be The results obtained for hydrogen at 25 C are greater than the pressure..000 atm... recorded in Table XXI. * also. Phys. 29e. that this relationship is approximately true can be seen from Table C up to pressures of about 100 atm. 848 (1932).. Generalized of Method (29.17). . The factor ( PV/RT 5i.16) oxygen at may be utilized to give reasonable values of the fugacity at moderate presFor gases which depart from ideal behavior to a greater extent than sures. ibid. problem in moderate pressures. Pressure FUGACITY OF HYDROGEN AT 25 C 100 106. and hence it is evident from equation (29. equation (29.16).4 50 51. does oxygen. I a = RT p 1 V = RT(. referred to above. 5 It XX for XX TABLE XXI. P fZidP. does not hold up to such high pressures. If this is inserted in equation (29. for example. it follows that f ln/lnP+ Jo 38. it is 296 Upon seen that (29 16)  P*V '!& so that the approximate fugacity of the gas can be determined directly from its pressure and molar volume. . this is not always the case 29b). this is equal to RT/V. This result may be put into another form of interest by introducing Pia. 40. 56.8 Fugacity 600 685 1. and hence. PV is greater than RT. 37.18) * Deming and Shupe. For hydrogen and helium. P \ PV RT K.8) for a given by equation may be T7 Determining Fugacities. viz.899 atm. idem.
4 1.0 y 10 1.6 L /ZZ 20 25 L 12 1.4 6 8 10 12 14 16 18 Reduced Pressure 00 5.0 /6.29e FUGACITY OP A SINGLE GAS 257 1. 18.8 es 71. Generalized fugacity curves .C/ 7 2.2 10 20 80 40 60 Reduced Pressure (*) FIG.
or of f/P itself. Chem. replacing the pressure T. ibid. . f/P. FUQACITY AND ACTIVITY 29f P terms in the integral by the corresponding.97 0. and rearranging. Lewis. ibid.. 24. and the integral in equation (29.17. 35. 100 200 400 * 1.258 or. Smith and Brown. Selheimer. 18. ibid. 100. 725 (1933). 5i that at a given reduced temperature and pressure the It was seen in * of all gases are approximately equal. 895 (1943). hence equafactors compressibility tion (29.) Fugacity with Temperature and Pressure.. F* . and the respective values of v are given below. equation (29. Eng. By utilizing these results.. 25.. 97 196 12 428 (The results are seen to be in very good agreement with those obtained by the accurate procedure based on PV data in the problem in 29b. Variation of states of Fwhere F* and /* ideally. C and Since T for nitrogen is 126 K. the ratio of the fugacity of the gas to its pressure.5 f/P 0. 302 (1935). is called the activity coefficient of the gas at the given pressure. i. P 50 atm. 4. In constructing the chart the values of K are derived from Fig.98 0.5) becomes 291. the following data for f/P are obtained from Fig. Newton.19) 6 An example of such a chart is given in Fig. ibid.5 atm.19) is a generalized expression which may be plotted graphically on a chart so as to give the value of In (//P). in which f/P is plotted as ordinate with the reduced pressure IT as the abscissa and the reduced temperature 6 as the parameter. and hence the fs can be calculated. Ind. for a nomograph applicable below the critical point. Lewis and Luke..20) by T. 257 (1936). ir .0 f 49 atm. Problem: Utilize Fig.07 3.. Souders. For reasons which will be understood later ( 30b).RT In L . (29. 18 is evaluated graphically. 18 to estimate the fugacity of nitrogen gas at pressures of 50. for any gas in terms of the reduced temperature and pressure. it follows that 6 is 273/126 = 2. Pc is 33.. see Thomson. 27. 515 (1932). 28.0 6. For two a gas in which the molar free energies are F and F*. 200 and 400 atm.19) being equal to P/PC where Pc is the critical pressure of the gas. reduced ^^ dT.e.98 1.20) Upon refer to a very low pressure when the gas behaves almost dividing through equation (29. (29. and the corresponding fugacities are / and /*. see also.
i. ture. However. 14 if the fugacity is known accurately at one temperaitself with temperature.5)]. Fig. 14 may be utilized to calculate the change in the fugacity of a gas with temperature. that a in A _n*H ' . of fugacity may be related to the JouleThomson Since (d///dP)r is equal to MJ. of the gas. * is the increase of heat content accompanying the pressure. the integral may be evaluated It is thus possible to determine the variation of the fugacity with graphically.e. Cp may be treated as independent of the pressure.21) with respect to temperature. expansion of the gas to zero pressure from the pressure P. In a sense. and combination of approximation. in conjunction with Fig. at constant pressure.CpdP. alternatively. L and so it is readily found by differentiation of equation (29. being this result with equation (29.23) the low pressure. is expressed as temperature. first if As a MJ. 14. the quantity discussed in 20e.T. at constant pressure. expression further.T.T. in Fig. and H* is the value at a very low. zero. p / dH\ } Xp (^ dP  rp J MJ. is The influence of pressure on the fugacity of a gas at constant temperature given by equation (29. so that the results perature.22) gives taken as zero.24). because of the variation of H* the direct use of equation (29.T. In this expression H the gas at the given pressure P. and a function of the pressure. .T. for which //* applies.CP [^equa tion (11. it is possible to carry out the integration in equation (29. hence.29f FUGACITY OF A SI. .VGLB GAS is 259 the result / F F* By equation (25. H H H The temperature dependence coefficient MJ. but more reliable values may be obtained from Fig. at constant temThis is. is not simple. (29>22) since /* is equal to the gas pressure at very low pressures and hence is indeis the molar heat content of pendent of temperature. in fact.28).22). 18 already includes the variation of fugacity with temperature.. MJ.7) which has been used in connection with the It is consequently unnecessary to discuss this determination of fugacities. (29.
for it is the heat absorbed. its fugacity will be equal to the vapor pressure.01 0.16). Every solid or liquid may be regarded as having a definite vapor pressure at a given temperature. at C. at constant temperature. H* is the molar heat content of the gas. = (3.3). therefore. since this is its significance in equation (29.e. If the pressure. the result obtained by combining them. the latter partially defining the fugacity.082X273 is OK ~3 5  The than fugacity of liquid chlorine its thus 3.16). vapor. liquid or gaseous substances. . the fugacity of liquid chlorine at C. the molar free energy of the liquid (or solid) must be the same as that of the vapor ( 27a). that V refers to the molar volume of the particular phase under consideration. 1 equal to 6.4). .66 atm. when a very small quantity of liquid or solid vaporizes into a vacuum. Since equations (29.260 FUGACITY AND ACTIVITY 29g 29g. The difference H* H has been called the ideal heat is it before.66 atm. per mole. The pressure of the H is now the molar heat content of the pure liquid or solid the pressure P. however.1). The variation of the fugacity of a solid or liquid with pressure or temperature is expressed by equations similar to those applicable to gases. As low pressure. although this vapor pressure may be extremely small for socalled nonvolatile substances. nevertheless. by equation (29. deg. and the molar volume of the vapor under these conditions is 6. will hold for solid. there is..7). i. although it is not exact.. an equation exactly analogous to (29.1) and (29. f . with / representing the fugacity of pure liquid or solid. Since the system is in equilibrium. It follows. from equation (29. the fugacity may be derived by means of equation (29. fugacity at constant temperature in each case.01 liters mole*" hence. approximately. at vapor where not the equilibrium value. by its vapor This rule is frequently employed. Problem: The vapor pressure of liquid chlorine is 3. but rather an extremely small pressure behaves as an ideal gas.59 atm. that the fugacity of the liquid (or solid) will be equal to that of the vapor with which it is in equilibrium provided. that the reference state is taken to be the same in each case. always a definite pressure at which a solid or liquid is in equilibrium with its vapor. of course. at C.22) is obtained for the variation of the fugacity with temperature at constant pressure. Fugacity of Solids and Liquids. hence the fugacity of a liquid (or solid) is measured. gives the effect of pressure on the It should be noted.0820 literatm. If the pressure of the vapor is not too high. The fugacity with 273 K V of the liquid is equal to that of the vapor at C and 3. with T equal to and R as 0.66) X 6. viz.~ l mole1 it follows that .. but at of vaporization.01 liters mole"1 Calculate . By following the procedure given in 29f. equation (29. vapor pressure is high enough for departure from ideal behavior to be considerable. which is somewhat less vapor pressure.
Insertion of NP for p> in equation (30. where the quantity MN now depends on both temperature and the total pressure.28).2). in place of the free energy.r N. the foregoing results are no longer applicable.3) then gives Mt = (M* + fir In P) H * DT* _ MN . in a given mixture of ideal gases at constant temperature. hence. but the introduction of the fugacity concept rectifies the situation.. By comparison of equation (29. Mixture of Ideal Gases.3) with (30.2) f^Cl Upon integration this gives ^ i I?1P In T Q\ is the integration constant. For a mixture of real gases. dju. when its partial pressure p* is unity.6) . at the given temperature.RTd \n P (30.5. /on K\ (oU.3) that M* is the chemical potential of the gas i. di4i RTdlnfi. Mixtures of Real Gases. of gases it is necessary to utilize the partial molar free energy. Since ni and n are constant.= d In P. The treatment may be considering. 30b. where N< is the mole fraction of the gas i in the mixture and P is the total pressure [equation (5. it is possible to write for a constituent i of a mixture of nonideal gases.1) it at constant temperature and composition.3). and if this is introduced into equation (30. the 30a. The partial pressure p< of an ideal gas is related to its concentration c in the mixture by p* = RTd ( 5b). and also on the temperature.8) ]. at constant temperature. chemical potential. According to equation (26. follows from equation (5. According to equation (30. Another possibility is to express p* as N<P. a system consisting of a mixture of ideal gases. = RTd In p^ * (30. the chemical potential of any constituent of a mixture of ideal gases is determined by its partial pressure in the mixture. (30. 261 MIXTURES OF GASES In the thermodynamic study of mixtures i. first. (30. i T~ Ki 1vk in . the value of which depends on the nature of the gas.3) the result is where M* Mi  (M* M* + RT In RT) + RT In a + firinc<.e.6) that d In p. It will be seen from equation (30. introduced by P can be expressed in the form dn = RT ^ .4) where M? for the given gas is also dependent on the temperature.30b MIXTURES OF GASES 30. the variation with total pressure of the chemical potential /it of any constituent i in a mixture of ideal gases.
 n* + RTlnf>. (30. at the is same temperature. equation (30. for the latter gives the chemical potential of the gas under consider . at all pressures. however. For certain purposes.7) and (30.7).. For a real gas. the proportionality constant is chosen as unity.8). On the basis of this postulate. as for a single gas ( 29a). as will be seen later.8) identical with /i* in /LI (30. the result. it is useful to employ a different procedure to express the chemical potential of a real gas in a mixture. the standard state is that of the gas behaving ideally at unit (I atm.7)]. ju is the chemical potential of the gas i when its activity a. but as the value of can be chosen arbitrarily. or as the chemical potential of the same gas if it behaved ideally at unit (1 atm.3) and (30.7) partially defines the fugacity in a mixture. it is evident from equations (30. the fugacity of an ideal gas in a mixture proportional to its partial pressure. the fugacity and partial pressure are taken to be identical. This conclusion is of general applicability.8) where a is called the activity of the given gas in the mixture.e.8) that the activity is proportional to the fugacity. the actual value depending on the arbitrary choice of the proportionality constant. The state of unit activity is called the standard state. This equation may be taken as partially defining the activity of any constituent of a mixture. as before. for an ideal gas.4) for a single gas. According to equation (30.7) shows that. the condition of unit activity is also arbitrary. In other words.. in practice there are certain states that are more convenient than others in this connection.) partial pressure [equation (30. the reference state is taken as the system at a very low total pressure. and in order to complete the definition it is necessary to specify the reference state. (30. is unity. This particular choice makes M in equation (30. For a gaseous system it is advantageous to choose the standard state of unit activity as that in which the fugacity of the gas is unity.262 FUGACITY AND ACTIVITY 30b where /* is the fugacity of the gas i in the given mixture.7) where the integration constant /x* depends on the nature of the gas and the temperature of the system. is modified so as to take the form jti  ju + RT]nai. and there is some freedom in its choice ( 37a) .e. the constant /** in equation (30. at the given temperature.3). Since M* and /A are both constants for a given substance at a specified temperature.7) becomes equivalent to that in (30.3)]. so that fi/pt is equal to unity. i.) pressure. the complete definition requiring specification of the condition which determines /i. M< Upon is integration. and it is postulated that ft/p* approaches unity as the total pressure of the mixture approaches zero. thus. analogous to equation (29. the gas at unit fugacity. and. and it may be regarded either as the chemical potential of a real gas when its fugacity in the mixture is unity [equation (30. i. Comparison of equations (30. and M is an arbitrary constant. The equation (30.3).
the constants are made equal by (30... which may be difficult to comprehend. however. ap a)/pi approaches unity as the total pressure becomes very It will be evident that this postulate makes the activity of a gas in small. is identical with that employed in connection with fugacity. e. an actual gas behaving ideally at 1 atm. Since the actual chemical potential MI must have a definite value. and is represented by the symbol y p script i to avoid the multiplicity of symbols. or the equivalent quantity /. ideal behavior.9) must be identical. is called the activity proaches Thus. since the latter is then identical with the fugacity. the ratio a p w/pi. by equation = N P. omitting the subcoefficient.10) where p is the partial pressure of the given constituent. irrespective of any choice of standard state.8). viz. i. ratio of the activity of any gas to its partial pressure becomes unity in the reference state.e. a mixture identical with its fugacity.9) of the where tf />(T) is the activity of the constituent i on the basis proposed standard state. and the chemical potential is expressed as t (30. equal to unity.7) and As already seen. just as does the standard state proposed above. where N is the mole fraction of the gas and P is the (5. as indicated in 5i.  is clearly understood. M = M * + RTlny p p..11) . which relates the activity to the The two quantities are then expressed in terms of fugacity. a p () should be equal to the partial pressure p. it follows that equations (30. i. may be written as . atm. In an ideal gas mixture...9). at very low total pressure. It makes the arbitrary proportionality constant. pressure.. may be taken as a measure of the approach to This dimensionless ratio. pi total pressure of the mixture./p. namely. that this coincidence of fugacity and activity a consequence of the particular standard state defined above. The standard state chosen in the foregoing is a hypothetical one. In some cases the standard state is chosen as the ideal gas at unit molar concentration. For the present purpose the partial pressure may be defined. Its use may be avoided. i. and so the activity a p u) of the given gas It should be in the mixture must be equal to its fugacity /t in that system. equation (30. the same units. however. (30.e.30b MIXTURES OF GASES 263 ation in the stale of unit fugacity. (30. by means of a reference The reference state chosen state which leads to exactly the same results.8) in the form /ii It is then possible to write equation = M* + RTlna p(i). which tends to unity as the gas apideality. the gas It is then postulated that the at very low total pressure of the mixture. (30.e.g. for any constituent of a mixture of gases. the particular standard state chosen.
9) shows that RT In U T + RT In o^o = and so. omitting the subscripts n i for simplicity. The expressions for the varia30c. although they will approach one another.12) Comparison of this result with equation (30. ~ and. Variation of Fugacity with Pressure. The activity coefficient ya in the present case is defined by a c /c. p J ' . = c . J gives ~ f \ (30.13) .e.11). ~"~ a* "P/TI """ ' . at constant temperature and composition of the gas mixture.^ With this choice of standard state. but it is not equal to y p By equation (30. This is equivalent to postulating that the ratio c(i)/c of the activity to the molar concentration becomes unity in the reference state of low total pressure.11) becomes M<  M* + RT In RT + RT In Oa o( (30.4) is identical with M of equation (30. and hence so that equation (30. the corresponding rcferenco state is that in which the defined activity coefficient is unity. /on 1^ ^oU. = ^ = ^. t (30.. differentiation (29. flZ In ap(0 7 = 72T In /<. and unity. the subscript N is used to imply constant composition.16) be observed that whereas the standard state is that in which the defined unity. tion with pressure and temperature of the fugacity of a gas in a mixture are similar to those previously obtained for a pure gas cf. at very lo\v total pressure. as seen above.14) 7.22)]. equations (29.7) with respect to the total pressure.15) but p for a nonideal gas is not equal to RTc and so the two activity coefficients will not be identical. i.lo. as the gas pressure is diminished.264 FUGACITY AND ACTIVITY 30c is the chemical potential the gas i would have if it behaved ideally at unit concentration. J As in 26a. It is seen that the proportionality constant which relates the activity to the fugacity of a given gas is now equal to l/RT.J (30.7) and Since M* of a gas depends only on the temperature. of equation (30. M? of equation * where M? (30. fit will is activity . this also approaches unity as the gas approximates to ideal behavior.
. therefore. . respectively. pressure. at constant temperature. by equation (26.15) is written in the logarithmic form. by equation (30. Upon differentiating with respect to P it is seen that. .30C MIXTURES OF GASES P<. To determine the dependence of the activity coefficient yp of a gas in a mixture on the pressure. For an ideal gas the activity coefficient yp is unity at all pressures..17). .26). . so that F is equal to F?.vr \ of (30.u = molar volume of the gas i in the given mixture. . . (dfjn/dP)r. . F<.18) that Upon introducing ~RT where P RT ' t ' Vf equal to RT/P. ra 2 .of a gas in a mixture of ideal gases is equal to its molar volume Ft in the pure state. F< with is now identical the actual molar volume F* of the gas. . i. The total volume F of a mixture of gases. As seen above. . at the same temperature and (total) pressure. . also equal to the sum of the volumes of the individual gases before mixing.mVi + n ? 2 + 2 + mVi + . hence. Fj. . . . and F? is always zero. are the molar volumes of the constituent gases . "p2. partial . It follows. The righthand side of this expression is.K the mole fraction N  t equation (30. equation (30. pressure and composition. so that F . ..e. it 265 Hence. F<. F* Further.19).. pressure P of the mixture is the molar volume of the pure gas i at the total on the supposition that it behaves ideally. J. the pure state. it follows being independent of the pressure. as explained above. incidentally.6) as F . if all the gases are ideal. is given by equation (26. the partial molar volume of each is equal to its molar volume at the same temperature and ni. tial molar volume "P. hi7 P = = ln/< In /< lnp< In P In N. this expression also gives the variation of the activity with the total pressure. where whose n it are the numbers of moles of the various gases molar volumes in the given mixture are "Pi. from (30. where P< is the partial follows that When the standard state is chosen so as to make the activity of a gas equal to its fugacity.. at constant temperature and composition. the defined partial pressure p* being replaced by the product of the mole fraction N< and the total pressure P.N \ or /T. that the parsince the latter is supposed to be ideal. .18) /T. . . . . in . where Fi.
however.7) is Making use of equation (26. hence Bf refers to the partial molar heat content under these condiIt will be shown below that for an ideal gas in a mixture the partial tions. also represents the variation with temperature of the activity coefficient of a gas in a mixture. /** is equivalent at the given temperature and pressure. It is unnecessary to specify the pressure because the molar heat content of an ideal gas is independent of the pressure ( 9e). p variation of the activity coefficient with temperature.21). at constant pressure and composition. Since equation (30. in the reference state.. As stated in 30b. 5k). Vi is.20). it is found upon differentiation with respect to temperature. and consequently Bi is equal to //* pressures. since a p is equal to the same equation represents the is the where y activity coefficient.21) This equation also gives the dependence of the activity a p on the temperaturCj since this activity is equal to the fugacity. like (30. it can be shown that the partial molar heat content Bi of any gas in a mixture of ideal gases is equal to its molar heat content Hi in the pure state at the same temperature. FUGACITY AND ACTIVITY 30d that there would be no volume change upon mixing a number of and volumes of the separate gases. and there is consequently no heat change upon mixing. it follows that for an ideal gas Bf fit is constant.25). not equal to Vt.20) is the partial molar heat content of the constituent i in the mixture.266 It is seen. For real gases. hence the equation for the variation of fugacity with temperature may be where B written / *\ i_ f \ rr* fr  (30.. that JEM dl /P. the result is equation (30. at all in . of ideal gases. and mixing change of volume (cf. divided through by T and rearranged. molar heat content is equal to the molar heat content of the pure gas at the same temperature.20) by ff*.. where the latter is the molar heat content of the pure gas i at very low pressures when it behaves ideally. Variation of Fugacity with Temperature. p being constant. therefore. it follows that the total heat content of a mixture of ideal gases is equal to the sum of the heat contents of the individual gases. It is consequently permissible to replace Bf in equation (30.e. hence the total volume of the mixture will usually differ from the sum 'will be accompanied by a If 30d.. By utilizing exactly similar arguments to those employed 30c when considering the volume of a mixture of ideal gases. Since Bi for an ideal gas is identical with #. RT 2 (30. to the chemical potential of the gas if it behaved ideally at a pressure of 1 atm. i. at constant temperature. in general. Further. 7 Pp.N *?*.
30e MIXTURES OP GASES 267 30e. Gillespie.24) can thus be evaluated graphically. and hence In (ff/p*) is zero. 1146 (1927). 28 (1926). Chem.. Tho RTdlnfi and a quantity a. it is possible to determine the partial molar volume t\ of any constituent (see Chapter XVIII).22) where P is the total pressure. If the low pressure P* may be taken as virtually zero. as In/. if is is a function of the temperature. 49. in equation (30. = In N< + In P =^= f * ai dP.23) The partial pressure p* of the gas is equal to N<P*. at constant temperature and composition. In this event. 47. 305. 3106 (1925). (30. 2172 (1027). the partial molar volume Vi of each gas in the mixture must be equal to its molar volume. principle involved in the determination of the fugacity of a gas in a mixture is analogous to that developed in 29b for a pure gas. . Rev. Am. Chem. equation (30. can be determined. According to equation (30.  In N. + In P + In 5  ^L C* a% dP. at constant temperature and composition.22). 18. Determination of Fugacity in Gas Mixtures: The LewisRandall Rule. ibid. ibid. (30. so that is then unity.17). i by (30. Lurie and Gillespic. 7 If special case in an interesting modification of equation (30. it is readily found that Upon of the integration. Soc. which composition of the mixture. at all pressures. and hence a* The integral at various total pressures may be calculated from equation (30. J. 48. 49. hence... where N< is the of the gas in the given mixture. Gillespie. it is seen that of t dP. ff/p* postulated in 30b.23) becomes mole fraction or In/.. between the limits very low total pressure P* and the appreciable pressure P. at the total pressure P. see also. There is 7 Gibson and Sosnick.24) PT7 data are available for the gas mixture. total pressure and defined for the gas Tom t on = . 359 (19&). and hence the fugacity / of the gas whose mole fraction is N< in the given mixture.24) possible in the which there is no volume change when the gases are mixed at constant temperature.
Since the chemical potential of a given substance must be the same in all phases at equilibrium. namely the vapor at very low pressures. see also. 2733 (1937). sents the change in heat content. 30d thus also give the variation with and of the temperature pressure fugacity of a constituent of a liquid (or solid) solution. therefore. This rule was proposed from general considerations by G. If the vapor pressures are not too high. this approximation is frequently employed. Am.21). when the constituent is vaporized from the solution into a vacuum (cf. 7. especially for vapor pressures of the order of 1 atm.. Lewis and M.17). on account of its simplicity. papers mentioned and Merz and Whittaker. tions of fugacities have shown that the Le>visRandall rule holds with a fair degree of accuracy at pressures up to about 100 atm. and so it is the "ideal" heat of vaporization of the constituent i from the given solution. to give an approximate indication of the fugacity of a gas in a mixture (cf.25) or N<f. 8 31. Randall. is used in each case. sometimes called an "ideal mixture. at the specified temperature and total pressure.9)]. that . just as was seen to be the case for a pure liquid or solid ( 29g). . 50. and so the fugacity of any constituent of a mixture is approximately equal to its partial vapor pressure in equilibrium with the mixture. now the partial molar volume and in (30.25) is frequently used. Actual determina32c). Vi is of the particular constituent in the solution y sponding partial molar heat content. pp. 59. 1. Krichevsky. Soc. 8 G. or less. it follows that the fugacities must be equal. It follows from the arguments presented above that it can apply only to a mixture of gases which is formed without a volume change. the rule represented by equation (30. Although the formation of gas mixtures is often a volume accompanied by change. 225227. Chem. Ri is the correThe numerator H* Hi thus repre in ref. provided the same reference state. The fugacity of a constituent of a liquid mixture may be expressed in terms of the fugacity of the vapor of that constituent in equilibrium with the mixture. /. Randall (1923). The equations derived in 30c.268 FUGACITY AND ACTIVITY last 3 la The /{ of two terms in equation (30." not necessarily consisting of ideal gases. ibid. 1522 (1928).24) are then equivalent to the fugacity the pure gas i at the total pressure P of the mixture [cf equation (29. ref. In equation (30. Fugacity in Liquid Mixtures. for a number of common gases.. N. LIQUID MIXTURES 3 la. at constant tem perature. It follows. Lewis and M. The fugacity of a gas in a mixture would then be equal to the product of its mole fraction in the mixture and its fugacity in the pure state at the total pressure of the mixture. 29g). N. the vapor may be regarded as behaving ideally. per mole. Infi hiNi /< + In/J (30.
31b LIQUID MIXTURES 269 31b. . which defines the activity coefficient 7# of i in the given solution. the value of M for a given liquid depends only on the temperature and is independent of the pressure.. and of the proportionality constant relating it to the fugacity. i. For dilute solutions the best choice of standard state for the solute is different from that adopted here (see 37b. The actual value of the activity. The standard state described above is equivalent to choosing the pure liquid form of any constituent at 1 atm. i. its . (31.1) as 1 atm. it follows from equation (30. this quantity may be stated in terms of the activity by means of the equation solution. liquids.e. standard state at the specified it is seen that (31. at . that the activity of the constituent i of the given solution is proportional to its fugacity in that where a is when the solution.. (31.2) activity of i is unity.7) that M< is = M* + #rin/< (31. M = M* + #Tln/?. pressure. If this result is inserted into equation (31. In general. so as to make the activity pressure. the standard state of unit activity is usually selected as that of the 'pure liquid at the same temperature and 1 atm. TNN. . i. M . the ratio a/N. varies with the composition and may differ from unity. the ratio of the activity a to the mole fraction N. unity. a t/N t tends to unity as the pure liquid state is approached. According to the postulated standard state.2) the activity in the given solution. pressure. in agreement with the statement made in 30b. depends upon the choice of the standard state of unit activity.. therefore.1) the general expression for the chemical potential of any constituent of a Alternatively.1) and (31.4) M<  M* + RT In/? + RT In a<. . as the reference state in which the activity is equal to its mole fraction. Except for an ideal solution (cf 34a) at atmospheric pressure. The chemical potential pressure.e. of any constituent of a mixture equal to unity for that substance in the pure liquid state at 1 atm. The activity scale is chosen. of a pure liquid at a given temperature and can be expressed by means of equation (31. Thus. the activity a< may be stated as the product of the activity coefficient and the mole fraction of the particular constituent. Activities and Activity Coefficients in Liquid Solutions.e. III)..2). at 1 atm. i. Since the chemical potential of any constituent of a liquid solution must be equal to that of the vapor in equilibrium with it. or almost completely miscible. and M is the chemical potential Comparison of equations (31. shows. but for the solvent in dilute solutions and for all constituents of solutions of completely miscible.e.3) where/? is the fugacity of the pure liquid in temperature.
written in place of /?? to which it is equivalent.17) and (31.25). pressure. it is found upon rearrangement that and hence. at constant temperature and composition. it follows that JL(^i\ RT\dP) T. and hence (d^/dP) T is zero. /* is independent of pressure. as indicated earlier. i. since N<.1) yields 31C and comparison with equation a<=j. It should activity coefficient r.N = Vi.H RT' /am* n ^ ' where P is the partial molar volume of the constituent i in the solution. If equation (31. pressure. upon differentiation with respect to temperature.270 FUGACITY AND ACTIVITY (31.5). be noted that equation (31. . is constant. is independent of the temperature. the mole fraction of the given constituent. In these circumstances. also 30d). Variation of Activity in Liquid Mixtures with Temperature and Pressure.6) also gives the variation of the YN with temperature. and utilizing equation (26. Upon differentiating equation (31.v .21) and (31.2) with respect to pressure. at the temperature of the mixture. since M is the chemical It will be seen later that potential of the pure liquid i at this pressure.5) which may be taken as an alternative definition of the activity.e. and //<. the activity at constant composition and pressure.. 31c.5). In accordance with the remarks made above.6). It should be noted that since a pressure of 1 atm. This result can also bo obtained from equations (30.2) is divided through by T. It is seen that the proportionality constant relating the activity to the fugacity of a constituent of a liquid mixture is I//?. This follows from the definition of TN as a</N. the variation of the activity coefficient with temperature vrill be exactly the same as that of the activity at constant composition and pressure. where /? is numerically equal to the fugacity of the pure liquid at 1 atm.6)* where Bi is the partial molar heat content of the constituent i in the given solution. is its molar heat content in the pure state at 1 atm. was specified in the definition of the standard state. the result is / ^ N V Ri RT* "" (31. at constant pressure and composition. (31. so that Si and Eft are identical. * The same t result can be obtained directly from equations (30. utilizing equation (26. for an ideal solution the partial molar heat content is equal to the molar heat content (cf.
C. (ii) oxygen at C and 200 atm. are functions of the temperature. (iii) carbon dioxide at 100 C and 250 atm. pressure.5. A is 1 . Soc.314 X 10~4 C is 4. 18) to determine the fugacity of (i) hydrogen at 25 C and 200 atm. Show that at moderate and low pressures (and moderate temperatures) f/P of a pure gas is approximately equal to its compressibility factor (K).. Exercise 6.A + BP + CP* + DP\ D an expression For nitrogen . t 52.9792 100 0.2482 800 1.31c EXERCISES coefficient 271 equation (31. at 25 C. fugacity. [Bartiett. Chem.292 X 10* C.~ l Calculate the free energy change for the transfer of 1 mole of water from liquid at 25 C to vapor at unit What error is involved in treating the vapor as an ideal gas (cf. which is the application of the concept of activity to the study of chemical equilibrium to be taken up in the next chapter. From these determine the fugacities at the various pressures and compare the results with those obtained in the preceding exercise. derive where A.276 X 10~ and is . B.400 cc. Am. Verify of 1. given in Exercise 1. given by the approximate rule applicable at low pressures. 2. 1374 (1932)].8). is usually not zero 9. Evaluate the fugacity of the gas at 300 atm.20 or more by means of Figs. Use the generalized fugacity diagram (Fig. has been given here for the present purpose. Chapter X)? form of the van der Waals equation applicable at low pressures. At 25 C.76 mm. show that the function a. Am.0196 equation (29.0819 Compare the results with those [Bartiett. 100. 400 and 1. g. The compressibility of a gas may be represented by PV/RT . 8. . 49.7) also gives the variation of the activity pressure. and 400 atm. at . /. up to 400 atm.9741 400 1. however. monoxide at Utilize the following data for 50. calculate the van der Waals a and b for carbon monoxide.000. 4 and 18. for the compression of nitrogen gas from 1 to 200 atm. by graphical integration based on 200 1. /. for the fugacity as a function of the pressure at a given temperature. EXERCISES 1. B is with P in atm. 687 (1927)]. Sac. 3. Calculate the free energy change in cal. By utilizing the at zero pressure. Chem..9) P PV/RT 25 0. 2. defined by equation (29. 7. Using the PV/RT values for 50 atm. Utilize the relationship between the free energy change and the fugacities in the final and initial states to show how the generalized fugacity diagram can be used to determine the free energy change for an isothermal expansion or compression of any gaa. 5.. YN with Further reference to activities and activity coefficients in connection with the properties of various solutions mil be made in later sections. this for * equal to 2 and values of 4.3. and the specific volume of the vapor under these conditions is 43.9890 60 0. hence. Sufficient. D . the vapor pressure of water is 23.000 : C to calculate the fugacity of carbon atm.8057 1000 atm.
920 3000 4.0 70. Show that in its standard state the chemical potential M of a gas is independent of the pressure. at which temperature and 1 specific volume of the vapor is 1675 cc. at 100 C to unit fugacity at the same temperature? Is the value significant in magnitude? 10. 18 to calculate the fugacities of carbon monoxide. (Note the high value of //P. which must remain the same in both phases.1 239. pressure.3 129. 50.6 116.8 90. where P is now the total pressure.5 72.327 2500 3. and compare the results with those obtained in Exercises 1 and 2. 11.4 241. Merz and Whittaker. The following values of PV/RT were obtained for nitrogen at high pressures at C: P PV/RT 1500 2. 13. 1522 (1928)]. J. of these gases at 400 C and a total pressure of 250 atm.11) with the Berthelot equation to derive an exCalculate the fugacities of carbon pression for the fugacity of a Berthelot gas.4 127.5 2 F! 466. Use the LewisRandall rule and Fig. 226.9 71.3 86.720 2000 3.7 120.1ml.Randall rule for the fugacity of a gas in a mixture [cf. 12. relative to the usual reference state of the gas at low pressure.8 441. . 1 atm. Am. Combine equation (29. C.1 91. for pure hydrogen and nitrogen.0 F 220.6) and (31.7). Extend the results of the problem in 29b and Fig.. 34 and 43 mole %. FUGACITY AND ACTIVITY Calculate the fugacity of liquid water at 100 C. Determine by the graphical method the fugacity of nitrogen in the mixture at the various total pressures. respectively.5 P2 447.5ml.) 16. test the Lewis. g. and compare the results with those obtained for the pure gases. Pi and F 2 are the partial molar volumes in a mixture containing 0. oxygen and carbon dioxide in a mixture containing 23. pressure the P 50 atm. The following data were obtained for the molar volumes V\ and Fi in ml. Give the alternative derivations of equations (31. derive a form of the Clapeyron equation (27. 14. 100 200 300 400 Vi 464.4 mole nitrogen. respectively.1 72. Chem.947 atm. What is the free energy change corresponding to the transfer of 1 mole of water vapor from 1 atm. 15. Soc. hence." .4 85. By considering the influence of temperature and pressure on the fugacities. 17 to determine the fugacity of nitrogen gas at 3000 atm.272 9. at various pressures P and On the other hand.6 mole hydrogen to 0.4) for the equilibrium between two phases of a single substance. monoxide at various pressures at C.
by the use of heat content and entropy data. and to show how they may vary with temperature and pressure. from left to right. Many chemical reactions. When. THE EQUILIBRIUM CONSTANT 32a. etc. However.p must be equal to zero [equation (25. Since the closed system is in equilibrium. a condition which may take a considerable time if the reactions are relatively slow. while dn\. etc. although to a very small extent. Chemical Equilibrium. It is possible. for example. .39)]. perfectly general reaction represented by aA + 6B + . to define the conditions of equilibrium. even in such cases it is probable that the reverse reaction takes place. (32. ^ ZL + mM + has been allowed to reach a state of equilibrium at a given temperature and external (total) pressure. on the other hand.CHAPTER XIII FREE ENERGY AND CHEMICAL REACTIONS 32. appear to proceed to virtual completion.p  G*iX*n L + MMdnM +)) (^dn/. By the use of the free energy concept. Further.2) . + /uBdnB + ). When a particular chemical reaction can proceed simultaneously in both directions. it is highly probable that the apparently stapressure. so that undetectable quantities of the reactants remain when the reaction is complete. are consumed. dn M moles of M.14)] dFr.1) where the M'S are the chemical potentials (partial molar free energies) of the indicated species. Suppose an infinitesimal change is made to occur in this system. the actual state of chemical equilibrium can be determined. a state of equilibrium will be reached when the system appears stationary at a given temperature and As is well known. (32. are formed. dn& moles of B. and a state of equilibrium is attained.. thermodynamics has been employed to throw light on the problems of chemical equilibrium. Consider a closed system in which the 32b. moles of L. equation (26. thus dn moles of A. the system still contains certain amounts of the reactants. as well as of the products. so that (MxdnA 273 + n*dn* +) 0. . The Equilibrium Constant. is one of dynamic equilibrium in which the reactions are prostate tionary ceeding in opposite directions at the same rate. The free energy change accompanying this process is given by [cf. this free energy change dF T.the state of equilibrium is attained..
6) using equation (26. the results are applicable. &F  (32. . (/ML + WMM +) (a/iA + bfjL B +. .8) and (31. . and hence AF.29).29) the lefthand side of (32. In the form given in equation (32.3) By equation (26. since RT is where the constant constant of the reaction.7) The commonly defined in terms of unit fugacity for gases aim.40)]. be written as . and a is its activity in the mixture under If the values of the chemical potential given by equation consideration. gaseous or be represented by an equation of the form [cf. . expression is sometimes known as the law of equilibrium. so that In (32. pressure for liquids. . . are introduced into (32..7) the law holds for any equilibrium irrespective of whether it involves one or more phases.e. &.3). and not to each phase separately. . . a. (32. . K. At constant temperature the righthand side of * is also constant. equations (30.a(A + RTln aA   ) ) ) b(A + RTln aB + )  = 0. Exercise 16).3) and (32. 32b various quantities dnA dn B dn L dM. The chemical liquid. (32. however.4) at equilibrium [cf. to the whole (closed) system.3) is equivalent to AF. for it provides a simple relationship between the activities of the reactants and products when equilibrium is attained in a chemical reaction at a given temperature.) 0. . K called the equilibrium i. The . (32. hence. the M values. . m. are independent of pressure (cf. . . and 1 * Since standard states are . . taking part in the chemical reaction indicated above must be in the respective proportions of so that equation (32. may potential /* of any constituent of a mixture. '*"?*'" = constant. . the equilibrium condition becomes (32.2) for the equilibrium condition may Z.2)] M = M + RT In a. . solids and solutions. equation (25.5) ju is l(A + RT In aL + m(& + RT In a M + . it follows that equation (32.4) represent the fundamental condition for chemical (and physical) equilibria of all types. 31b and Chapter XII.5) where the chemical potential of the given substance in the chosen standard state of unit activity. The equations (32. The special forms to be taken by the expression for the equilibrium constant in a number of reactions of different types will now be considered.6) is constant. the free energy change accompanying the complete reaction under equilibrium conditions.274 FREE ENERGY AND CHEMICAL REACTIONS .
Since the ratio of the fugacity /. TlXTiX..10)] and hence Kf cannot be exactly constant. ideal gas at 1 atm. hence equation (32.( 30b). 7L* a 7l X 7M* X X 7B X .25).e. X ' equation (32. in place of Kf. fi N. it is possible to replace If this substitution is made. It will be noted that the equilibrium constant is now represented by K/ 9 the subscript / being used to indicate that the activities are expressed by the fugacities. it will be homogeneous. pressure. i (32. /{/P. X pS X yl X 7M X PlXrtX".32C THE EQUILIBRIUM CONSTANT 275 If the reaction is 32c. the total pressure.to the partial pressure Pi of any gas in a mixture is equal to the activity coefficient 7. Equilibrium in Homogeneous Gaseous Systems.e. the activity of each reacting substance may then be replaced by its fugacity (cf 30b) in the equilibrium for the the so that constant becomes (32. According to the approximate rule referred to in 3Qe./!... taking place in a single phase. /ort > ' (32 8) Q\ where the fa are the respective fugacities. is the corresponding activity coefficient f y t of the particular gas in the pure state when its pressure is equal to P.8).8) becomes _ K " *' The data necessary able. the result. it is possible to write ' Nj X X N* X a /l X/ B X (32 ' ' ' n) the symbol K' f being used. Making this substitution in equation (32.11) may be written as = K' f f gL21 N MX Nj X <X . is given by equation (30.. If each of the /' terms is divided by P. viz.10) where /J is the fugacity of the pure gas at the total pressure of the mixture. id equal ) The first and third factors in equation so these (32. the change in the number of molecules to (I +m+ ) (a +6+ in the gas reaction. . in which its mole fraction is N. to show that the expression in equation (32.' fugacities) of the individual gases in and an for the evaluation of the activity coefficients (or a mixture ( 30e) are not usually availalternative treatment for allowing for departure from ideal behavior is frequently adopted.12) can be" obtained by experiment.. pA '  where An. i. one involving gases only..7) equilibrium equation system. PJ. If the standard state of unit activity is taken as the state of unit fugacity.11) is based on an approximation [equation (32. the fugacity / of any gas in a mixture. each fugacity factor by the product p 7. i. and may be combined to .
/V * of the activity coefficients defined by (32 1 15) ' A T  TL v A. At high pressures. and K/ and K c are identical.of each gas would be equal to N t P. so that ' K. When the departure of the reacting gases from ideal behavior is not large. so that the quantity defined by K' p would represent the true equilibrium constant.9) would be unity.18) For a gas reaction in which there is no change in the number of molecules.g. but a great improvement is possible by the introduction of the activity coefficient factor. .8). FREE ENERGY AND CHEMICAL REACTIONS 32c X NM X p *'N' A XN>X'K f NL ' Al . the nature of the variable being indicated by the subscript.13). however. ac is (oOi X x . or less. An is zero.x It may be noted that if the gases taking part in the reaction were ideal..16) is obtained by replacing each activity factor by the product of the concentration and the appropriate activity coefficient. = *?*"" is (BD"*" . this event. a very / can be obtained satisfactory approximation to the equilibrium constant from equation (32. when the total pressures are of the order of 1 atm. as will be seen below.7) may be written may . * The symbol / will be used for a function having the same form as the equilibrium constant. OOL X (qjft *"(. by equation (5. e. An alternative form of equation (32. equation (32..' (32 16) ' equal tof/RT. the values of K' p deviate considerably from constancy.14) where the function . TM V A. ..14). (32.)! X According to equation (30...13). . as defined by equac Kf  K X (RT)* n. is (32.17) The first tion (32. equation (32. mention be made of the form taken by the equilibrium constant when the activities ac are expressed on the basis of the standard state of unit activity as equal to that of an ideal gas at unit molar concentration ( 30b) thus. further. the equilibrium constant is then independent of the chosen standard state.276 give K'p\ thus.* ( 9 . term on the righthand side and hence obviously equal to K/. } and hence.8). the activity coefficient factor in equation (32. where /is the fugacity. the result would be identical with the expression in (32..K'XJy. Although it is not commonly used in the study of gaseous equilibria. the In partial pressure p. rfXy'JX'I m <v' /Qrt . as in equa K tion (32.13). (32.12) may K' f ho written in the form ..
hydrogen in the molar ratio of Njr. X 7n.)i X X X .. The Ammonia is Equilibrium. represented by K' c and the K This equation is K' X A. A which has been studied in some homogeneous gaseous equilibrium over a considerable range of pressure and temperature. it < and a proper application of this equation requires a knowledge of the fugacity of each gas in the particular equilibrium mixture./v% jNa <* /Ha available. Chem.20) The concentration function may be function by Jye so that . obtained in this manner by A. Jy e is and then the law exact.. (y. fractions NNH. 45. is not precisely constant. X CM X where K' e 32d.14). 1 i Larson and Dodge. . the reaction employed in the Haber process for the production of ammonia. Larson.. g/ = .12) or (32. 277 = c X 7. and NH.32d i.24) g. in the present case this takes the form . (32. . tW&. then K' ~ CL 4 X CM X X4X ' (7. Since the data are not is more convenient for practical purposes to employ the some what less exact equation (32. 2918 (1923). the proportion of ammonia in the From this the mole resulting mixture was then determined by analysis.. THE EQUILIBRIUM CONSTANT a. TN* . but for many approximate purposes of equilibrium is expressed in the form CL taken as unity.24). Dodge (192324) is given in Table XXII for a temperature of 450 C. ' (3SU9) activity coefficient .){.X< P A NNH In the investigation of the equilibrium. /. . 367 (1924). (T. Am. L. detail.)!.23) where the experimental quantity K' p is given by (32. and A selection of the results hence K' p could be evaluated by equation (32. 46. at equilibrium could be readily calculated. For the 32 22)  equilibrium.e.(32. mixtures containing nitrogen and 1 to 3 were allowed to come to equilibrium at various temperatures and pressures. Larson and R.. X (YJS. Soc. NN. T.
together with the correp sponding values of Kj. that is. as described in species may then be set equal to the product of its mole fraction and the appropriate activity coefficient in the equilibrium mixture.56 6. 2 For a reaction taking 32e.750 0.969 0. of K' JV. and the value of K' seen to increase rapidly with increasing pressure.278 TABLE Pressure TREE ENERGY AND CHEMICAL REACTIONS XXII. 18. Newton and Dodge.. represented by the second factor in equation (32. X seen that K' f is remarkably constant up to 300 atm. however. are recorded in Table XXII. * .55 6.51 6. up from constancy..25 8. X 30 50 100 300 600 1000 0.84 12.76 6. but this should be multiplied by the activity coefficient function J?N . there is appreciable deviation atm. By using the method described in 29e. Homogeneous Reactions in Liquid Solution.94 23. pp.905 0. i. 302 (1936).. ibid.42 10.. a = NTN.7) gives the expression for the equilibrium constant as It is _ N j. 13 et aeq. 577 (1935). "Equilibrium and Kinetics of Gas Reactions/' 1942. results. based on Fig. 18 which gives the activity coefficient f/P at any (reduced) pressure directly.. Pease. and this is undoubtedly due to the failure at high pressures of the fugacity rule for mixtures. The approximate constancy ob Newton. the standard state of unit activity for each substance is taken as the pure liquid at the temperature of the The activity of each 31b. Unfortunately.57 6.59 6.573 0. V X N* N B V X * (32. the function J^ has been calculated for various values of the total pressure. At higher gase* from ideal behavior at 450 C p is pressures. . 359 (1936).32 X 10~ An examination of the values of K' p shows that they are fairly constant 50 of below this pressure the deviations of the about to a atm. the deviations are considerable.o . place in a homogeneous liquid system.90 7. Chem. see also. and fairly constant At 1000 atm. Eng.988 0.26) 9O N is often employed. Chem.. R. so that equation (32. total 600 to pressure. reaction and 1 atm.25). XN X  (7y)L X (7y)S X .443 6.63 7. up pressure are evidently not very large.10). Ind. 27.953 0. N.e. to give the true equilibrium constant.25) to be verified completelyf but the equilibrium mole fraction function K' N has been determined for some esterification processes. 326 THE Nj f JH ^ NH EQUILIBRIUM AT 450 C Kf K' p 6. 27. The approximately constant equilibrium function jri N ~~ _ N L X NM X Ma N A ' ' . Gillespie. Rev..28 Jr 10~ 10 aim. pressure. no liquid phase reaction has been studied in sufficient detail to enable equation (32. The. as given by equation (32.
it is possible to derive a modification of equation (32.32f THE EQUILIBRIUM CONSTANT 279 tained in these cases is mainly due to the partial cancellation of the activity coefficients on both sides of the reaction. . (32. UM moles of M. TIL moles of L. 32f. and for these substances a special standard state is used ( 37b. . . the mole fraction of any constituent. if ML. Q is the molecular weight of the solvent. .29) and consequently. of the same constituent obtained by dividing n& by the volume of the solution in liters. A instance. MB. . the number of moles of solvent is greatly in excess of the total number of moles of the reacting substances.27) it is seen that a result which is of completely general applicability for the relationship between the mole fraction of a given constituent of a solution and its molarity. etc. its concentration in moles per liter. etc. so that JyN is not very different from unity.. in moles per liter. are the molecular weights of the substances takMA.. (32. .  = 2>M. However. If the solution is dilute. UB moles of B. IV). i.30) Vol. Volume of solution = f^^ 10(K)p liters. Homogeneous Reactions in Dilute Solution.28) in The ^olume grams by thus. and Thus.. If a solution contains n^ moles of A. so that n M and n n . the mass of the solution is given by is The concentration M . Most equilibrium reactions that have been studied in dilute solution involve electrolytes. . Af ass of Solution = noM + nM + n^M^ + + n L ML + n M MM + volume in ml. MM. is given by n B Hh n L + ra M < 32 27 )  (molarity) CA. . the concentration of A is given by (32.25) which is applicable to all reactions in sufficiently dilute solution. of solution If this expression is compared with equation (32. ing part in the reaction. of the solution in liters is p to obtain the then obtained upon dividing the mass and then by 1000 to convert into liters.e. the latter can be derived from the total mass of the constituents of the solution and its density p. dissolved in for no moles of an inert solvent..
32) that the concentration (molarity) of any solute in a dilute solution is approximately proportional to its mole fraction.129 mole liter* 1 0. to modify equation (32. and since this and its molecular weight are constant. and particularly if it contains no electrolytes. TABLE XXIII <~NiO4 C NO2 K'o literi 0. Cheni.778 1.04 X 1Q* last column shows that the solutions are be close to unity. sufficiently dilute for the activity coefficient factor to Cundall.07 1. if the solution is dilute.85 2. so that equation (32. 794 (1895). It is In possible.32) For a dilute solution. also. 1076 (1891).280 FREE ENERGY AND CHEMICAL REACTIONS (32.2 C.13 2. p is not greatly different from the density p of the pure solvent. are 3 The relative constancy of the values of K' c in the given in Table XXIII. therefore. and the concentration equilibrium function K' c is given by 4 The data over a range of concentrations. ) n /OOOON ' (32 33) +m+ it * (a + &+). the activity coefficient factor may be taken as unity.227 0.32).25) reduces to (32.31) reduces to 32t and hence equation (32.61 1. the first place. for a temperature of 8. Soc.84 X 10.324 0.mole 1.13 1. / M. Since the follows that g'. 67. The equilibrium is represented by NO 2 4 ^ 2NO N2 2.34) may be justified by means of the results obtained by J. If the mole fractions are replaced by the corresponding molarities.14 1. Cundall (1891) for the dissociation of nitrogen tetroxide in dilute chloroform solution. T.17 1. as before.. . utilizing equation (32. 59. it is found that M X where An. J. it follows from equation (32.05 1.26).405 0.25) in the following manner. is approximately constant at equilibrium. final factor in is equal to (I the expression is constant. provided the solution The use of equation (32.^vlf*'"* CA X* CQ x\ * * (3234) where K' c is dilute.
as a first approximation. but their values are not unity. At other pressures..37) then reduces to A. the mole fraction is ~ mA 1000 . equation (32. or liquid In all cases the general equation (32.35) o and consequently.. the number of moks of solute to 1000 grams of solvent. mon but the situation is considerably simplified by the universally adopted convention that the activity of every pure solid or pure liquid is to be taken as unity at atmospheric pressure.25) a molality equilibrium function. is chosen for substances present in the solid form. solutions and solids. viz.32g THE EQUILIBRIUM CONSTANT 281 is Another form of representation of the equilibrium in dilute solutions based on the expression of concentrations in terms of molality. in accord with the usual choice of the standard state of unit activity of a liquid as the pure liquid at the same temperature and 1 atm. in accordance with the defined standard states. Strictly speaking. This is. pressure. it may then be taken as equal to the mole fraction. hence the molality m\ is given by __ /00 OK v (32. its activity is no longer unity.7) is applicable. (32. pure solid at 1 atm. as seen above. It should be understood that if the solid or liquid involved in a heterogeneous system is not present in the pure state. this is only true if the total pressure on the system is 1 atm. K Km f ~~ mL X WM X' * /o 9 OQN (32. an analogous standard state. the activities of solid and liquid phases are constant.36) If this result is introduced into KT NA equation (32. The result of taking the activity of a pure solid or pure liquid as unity is that the corresponding factor may be omitted from the expression for the equilibrium constant. Chemical Equilibria in Heterogeneous Systems.. n may be taken as approximately equal to n If the solution is dilute. The most comheterogeneous chemical equilibria involve gases and solids. viz.38) so that the molality of any solute in a dilute solution is approximately proporIt is thus possible to derive from tional to its mole fraction in that solution. The mass of the solvent corresponding to n moles of solute A is n A/o. If the corresponding factors are then . that is. equation (32.39) 32g.27). (32. pressure. of course. but as solid or liquid solution.
y v = J /H S _ PH S i_ PH 2 O NH. although other methods are often preferable (see Chapter XIV). to be considered shortly.. and it should not be used in equations such as (33. other heterogeneous physical equilibria can be treated in the same manner... M.7)]. in which.. This quantity is not the true equilibrium constant. means of equation (26. 33. and the free energy of a mixture of moles of L. do not differ appreciably from the true equilibrium constants. and there is frequently a partial cancellation of terms for reactants and products.e. the partial molar free energies. the general reaction aA The free energy of + bB + of ^IL + raM + . In practice. in each case. A simple illustration of a heterogeneous reaction. as well as with temperature. . as a moles of A.6). etc. Consequently. is given i. however. the variation of the constant with pressure is frequently neglected. 6 moles of B. that vaporization (cf.. the result is a quantity which varies with pressure. These expressions are applicable to the systems of reactants and products at any 4 For review.. etc. 23 (1941). the constants obtained at pressures other than atmospheric. The Reaction Isotherm. the effect of pressure is likely to be small. the Fe and FeO total pressure of 1 atm. any mixture in terms of the chemical potentials. is at constant temperature. incidentally. /V. solubility. pressure and composition. Ind. Chern. strictly at a and with a good degree of approximation at all moderate pressures. 33.6). Consider. to determine standard Since the effect of pressure on the activity of a liquid free energy changes. equation (31.282 FREE ENERGY AND CHEMICAL REACTIONS 33a omitted from the expression for the equilibrium constant. and need not be considered 33g). once again. see Austin and Day. is + H 0(<7) 2 FeO(s) +H 2 (<7). therefore. and mention. and hence. on the assumption that the activities of pure solids and liquids are unity. Eng. _ /H 2 O NH 2 O Numerous instances of reactions of this type are to be found in the literature here. or solid is usually small [cf. freezing. by a/iA I F(reactants) = + &MB 4 . F (products) = ZML m moles of + WMM + . etc. 4 being present as pure solids. It is of interest to of physical chemistry. FREE ENERGY CHANGE IN CHEMICAL REACTIONS 33a.
5) are forms of the reaction isotherm first derived by J. J a is a function of the same form as the equilibrium constant involving. in this case. It gives the increase of free energy accompanying the transfer of any arbitrary concentrations (activities) to products at arbitrary As seen above.29) that (33.P would then be zero. M in of the standard state. and hence &F T p is then zero. from a comparison of equation (32.. is given by equation (33. chosen so as to correspond to the equilibrium state. it the value any substance.RT In K + RT In J a. The important equations (33. 33b. The standard free energy inreactants at . the symbol AFJ is sufficient. all in their standard states of unit activity.2). at constant temperature and pressure. the last term would be identical with RT In K.3) which. for the chemical Utilizing the general equation (32. * The relationship (33. for if the arbitrary were the equilibrium values. "" (33.2) * ^A X ^B X .RT In K.1) and (26. thus leading to the expression in equation (33. is thus given by &FT. P=RT\nK + RTln ^^^ ^ &A X &B X = . hence. M being potential + RT follows from equations (33. as indicated in the footnote in 32c. earlier. the two terms on the righthand side become identical. H. As stated AF* is independent of pleasure. result can be derived from equation (33.4) and (33.P = F (products) F (reactants) &MB + ' ) (33. are converted into the products. while &FT.e. not necessarily the equilibrium values. Standard Free Energy of Reaction.6) It gives the increase of free energy when the reactants. If this is substituted in (33. van't Hoff (1886). as will be seen shortly. AFS. . thus. in their standard states. in general. will be repeated here.5). ' " ' where the activities are It is evident any arbitrary values.3) AF T The same activities = RTlnK. it is found that. crease AFr. often referred to as the standard free energy.4) (33. because of its importance.6) is extremely useful.1) = M In a.2).5) where. of the reaction at a specified temperature T. energy increase AF accompanying the reaction depicted above. the arbitrary values of the activities of reactants and products. if the usual definitions of standard states are employed. if the arbitrary concentrations are concentrations (activities). (33. AFr.6) and (32. i.7) that (33.33b FREE ENERGY CHANGE IN CHEMICAL REACTIONS 283 The free arbitrary concentrations.3). =.
the subscripts T and P are omitted.9) AF? = . (33. so that equation (33. In connection with these expressions.RTlnK K For reactions where being given by equation (32. as defined above. or approximately ideally. The Direction of Chemical Change.10) form the reaction isotherm is sometimes employed for gas reactions. AF =.RTlnKf.14) AF = AF + RT In J K . the standard state of each substance is chosen so that the activity is equal to the mole fraction in the reference state. For gas reactions. (33. 33c. In general. for a spontaneous If the value of AF under a given set of reaction. Substitution of the value for AF^. the form of equation (33.284 FREE ENERGY AND CHEMICAL REACTIONS 33C for it provides a convenient method for tabulating the equilibrium constants of reactions.p = AFS* + RT In J.25). the standard state is usually that of unit fugacity. that is to say. ideal i.. . for the standard free energy changes. given by equation (33. It was seen in 25f that for a process.6). e (33. at constant pressure and temperature. the is corresponding equation AF . the fugacities may be replaced by the corresponding partial pressures.19). therefore. . consequently necessary to specify clearly the standard state employed in every case. the standard state is chosen as the ideal gas at unit concentration. gas at 1 atm.7) is then AF = AF? where + RT In J/.RTlnKN the equilibrium constant K$ being defined by equation (32.8) becomes AF in which If AF + RT In J p . If the gases behave ideally. pressure. (33.13) (33. this must also be the It is case.8) (33.7) and the reaction isotherm is frequently encountered in this form.p must be negative. to be spontaneous it must be accompanied by a decrease of free energy. the reaction isotherm may take the form (33. As seen earlier.e. into (33. the actual values of the activities and of the equilibrium constant depend on the choice of the standard state. it being understood that constant temperature and pressure are implied. &F T . From the chemical point of view the great significance of the reaction isotherm lies in the fact that it provides a means of determining whether a particular reaction is possible or not under a given set of conditions.11) (33.AF AF* + RT In J e.12) where the definition of =. especially for processes which appear to go to virtual completion.5). in solution. leads to AFr.
so that the free energy change is given by equation (33. von Ilelmholtz (1882). independent of the standard state. without altering the arbitrary activity function J a the latter may become less than K. for heterogeneous reactions. change. this takes the form . H. Incidentally. in this way.5) shows that the sign of AF depends on the relative values of the quanities and /a if the reaction is to be spontaneous.33C conditions is FREE ENERGY CHANGE IN CHEMICAL REACTIONS positive. ical Problem: It is 'required to pass carbon monoxide at 10 atm. so that AF is An K . This is equivalent to its omission from In J a since the logarithm of unity is zero. i. If AF is negative.O . the activity of each pure solid is taken as unity. it is sufficient to assume ideal behavior.. the equilibrium constant However. negative and the reaction is possible. and water vapor at 5 atm. AF = . although it was not stated explicitly. pressure into a reaction chamber at 700 C and to withdraw carbon Is this possible theoretidioxide and hydrogen at partial pressures of 1. if AF is positive. First. the reaction it 285 cannot possibly take place under those the conditions are altered. The equilibrium constant for the reaction is known to be 0. but there are two ways in which the situation can be changed. It can now be seen that thermodynamics provides a simple solution of the problem. Gibbs (1876) and of II. or both. On the other hand. pressures or concentrations. since the arbitrary concentrations (activities) of the reactants and products are stated in terms of pressures. the temperature may be changed in such a manner as to increase if. it may be mentioned that the same idea was undoubtedly in the minds of J.RT In Kp + RT In PcOt X Pn Pco * . The foregoing arguments are applicable to processes of all types. Second.5 atm. the latter must be less than the former. will be negative. for then AF If the conditions are such that J a is greater than K. . the reaction will not be possible under those conditions. X PH. van't Hoff (1883) indicated the importance of the free energy change. conditions. as mentioned earlier. the arbitrary activities. it will be assumed that the equilibrium constant is K/ or K p For the present purpose.71.e. the reaction with all the reactants and the products in their respective chosen standard states can take place spontaneously. of the substances concerned in the reaction may be changed so as to decrease the value of J a below that of K\ this means that the activities of the products must be decreased or those of the reactants increased. W.10). and is since there is no change in the number of molecules. An analogous significance to that just described can be given to the standard free energy AF of a reaction. which had puzzled investigators for many years until J. concerning the conditions determining the direction of chem. although may do so if examination of the general equation (33. the reaction cannot occur under those conditions. cally? The reaction is C0(g) +H 2 OG7) = C0 2 (0) +H 2 (0).
e.15) Differentiation with respect to the total pressure P.5 is the reaction X 1. 0. there is no connection between the magnitude of the decrease of free energy and the rate of the reaction.576 X X 973 log 0.""1 mole"1 the temperature T is 700 C or 973 K. i.71. in the form (33. the process theoretically possible. is of particular value in the study of chemical has also been used in connection with physical changes.045) 5. will not vary with the external pressure. but it esses. All that it is required * to know is the relative values of p and Jp 9 but it is instructive to calculate the actual free energy change. Although any reaction accompanied by a free energy decrease is theoretically possible. is AF is negative.=Since 4. to which it is equally applicable. *The latter is 1. For example.576 4. This is usually expressed in calories. of course. at ordinary temperature and pressure the free energy change for the combination of hydrogen and oxygen has a very large negative value. and since this is less than Kp .71 973 (log 0. and consequently the equilibrium constant K. deg.987 cal. The passage of an electric spark or the presence of a suitable catalyst. physical or chemical.340 cai. In a series of analogous reactions the rates at which the processes occur are often roughly in the order of the free energy decreases. however. at constant temperature. K AF . for different reactions. Hence. K .71 as given above. facilitates in this case the occurrence of a reaction which the free energy change shows to be theoretically possible.286 FREE ENERGY AND CHEMICAL REACTIONS 33d where the p's are the arbitrary values given in the problem. so that R is taken as 1.71 +  4.5/10 obviously possible. converting the logarithms. The extent to which the equilibrium constant of a reaction is affected by pressure can be determined by utilizing equation (33. 33<L Variation of Equilibrium Constant with Pressure. and p is 0. the standard free energy change AF. i. to all proc The reaction isotherm processes.6). but in general.e.. The general criterion of a decrease of free energy for a process to be spontaneous is applicable. yet the reaction is so slow that no detectable amount of water would be formed in years..045. gives lnK\ dP ) T 1 RTl dP Since standard states have been defined so as to be independent of the pressure of the system. 0. it is important to note that this is no indication that the process will occur with a measurable speed.576 X 1 ' 973 log 5X X 5 n 10 log 0. X 5. .
the constants obtained at other pressures vary with pressure in a manner dependent on the volume change of the solid and liquid phases involved in the reaction [cf. then the true equilibrium constant is obtained only if the total pressure of the system is 1 atm. is independent of the p for a homogeneous gas reacf and K' pressure. along lines which will be described in Chapter XIV in connection with physical equilibria. Such a change is necessary in order that the equilibrium constant may remain unaltered.19) to determine the effect of pressure on the activity coefficient factor. therefore. the equilibrium functions K' tion should vary with the pressure. This is. of course. Similar considerations apply to the influence of pressure on other equilibrium functions. operates to the advantage of the yield of amgases. 33e. and hence K/.. for example. + H.O ^ CO. Since a change of pressure is usually accompanied by a change in the composition of the system it is not possible to use equation (30. but the results have no direct practical application without introducing a number of approximations. The increase of K' p with pressure in the ammonia equilibrium. The subject is dealt with adequately in physical chemistry texts. Because of the effect of pressure on K' p . The calculation can be made by thermodynamic methods. Unless allowance is made for the effect of pressure on the activities. the actual position of equilibrium will be altered if the reaction is one involving a change in the number of molecules. at 600 C. equation (31. Although the true equilibrium constant of a gas reaction is not affected by the pressure. as is actually found to be the case (see Table XXII).33e FREE ENERGY CHANGE IN CHEMICAL REACTOINS 287 It should be noted that although K. Effect of Pressure on Position of Equilibrium. however. due to the dependence of the activity coefficients on the pressure at constant temperature. However. It is opportune to recall here the remarks made in 32g in connection with heterogeneous reactions. Problem: Estimate qualitatively the effect of a pressure of 500 atm. moderate pressures. the changes due to increase of pressure can be neglected at all . As is well known. In general. gaseous equilibrium . there is another aspect of this matter that merits attention here. monia in the Haber process. The effect of pressure on K' p due to departure from ideal behavior will alter the position of equilibrium even when there is no change in the number of molecules. in connection with the Le Chatelier principle of mobile equilibrium. increase of pressure will favor the reaction which is accompanied by a decrease in the number of molecules. as indicated in 32d. for reactions in solution. means that there is a larger proportion of ammonia present when equilibrium is attained at high pressures than would have been the case if the system had consisted of ideal This factor. such as K' N etc. on the CO + H. If the activities of pure solids and liquids taking part in the process are taken as unity.7)]. there will be an additional change in the equilibrium composition.
873 K. because of deviations from ideal behavior.8 atm. since there is no change in the number of molecules accompanying the homogeneous reaction..35\ 7H2 __ ~" n 77 U '"' The values of 7 given at the right are those based on the approximation that the activity coefficient of a gaseous constituent of a mixture is equal to the value In this case. 34.. i.2 K. PC H = 873/304 = 2.51\ _ 9q 7co "" LMm T = 500/34. pressure would have no effect on the position of equilibrium...77 Since J y has increased when the pressure is increased to 500 atm.. is is is Tc PC For CO: For T T c is is 134 K.29J 1. 218 atm.23 X X 1. At 1 atm. so that K d\nK = dT and hence. However.288 FREE ENERGY AND CHEMICAL REACTIONS 33f If the four gases behaved ideally. 12. 6 = w = 500/218  873/647  2.0/ d = 873/134 = 6. Variation of Equilibrium Constant with Temperature. a shift in the composition is possible when the pressure is changed.9 atm. it follows that where . in order to retain Kf constant.33). ent of the external pressure. C 33. and for this purpose the reduced temperature (6) and pressure (TT) of each gas are required.10 = " ' ' 0.8 + 8) = 24. __ Pco* Pco X T>H? X PH O S Tcos 7co X X desired to find the value of the activity coefficient factor J y at 600 C.2 f 8) = 21..09 1.2\ _ ~" 711 TT = 500/Q2. for the pure gas at the total pressure of the mixture.9 = 6.: 2 : T PC is 304 K. 18. the constant be on determined by differentiaequilibrium may temperature is independSince tion of equation (33. the constant pressure condition and the accompanying partial differential notation can be omitted.4/ 8 t TT 2 * ' ft 1<1U ' 1 2 0: c is is PC 647 K. causes the equilibrium to shift to the left. increase of pressure to 500 atm. The equi librium constant may be written as . The effect of 33f . Thus.e. pressure.6 atm. 72.6 14.87) _ " OQ Uy = 500/72. or pco X pn 2 o increase. 7 ^ ~~ 1.15) with respect to temperature. by equation __ 1 d(AJ R dT (25.85/ 7c = 873/(33. because of deviations from ideal behavior. and it is For For CO II. it follows that the product pco 2 X PH Z must decrease. and 500 atm. unity. the value may be taken as virtually At the higher pressure use may be made of the fugacity chart in Fig.
H. ding/ dT It follows. must also apply to AH . upon equation (33. and utilizing e and hence.33f FREE ENERGY CHANGE IN CHEMICAL REACTIONS 289 or.17) the heat of reaction adjusted to a low value of the total presgases behave ideally. therefore.e.. i.18) becomes Since is it A# + PAF + The variation of the functions K' f and K' p with temperature is not quite the same as that given above for f because of the change in the activity coefficient factor with temperature. It is to be understood.21) cannot be employed. .7). adjusted to ideal = AjB follows that Aff = A# behavior. the ordinary heat of reaction in the vicinity of atmospheric pressure. of course. Since the composition of the system does not remain constant when the temperature is changed.16). differentiation with respect to temperature. equation (30. taking logarithms.17) by A#.16) the rigorous form of a relationship originally derived by J. It was seen in 20e that at moderate sure. pressures the heat content of a real gas does not differ appreciably from the ideal gas value. it is consequently sometimes referred to as the van't Hoff equation. If the standard state is that of an ideal gas at unit molar concentration.. An(#!T). so that equation (33. For a homogeneous gas reaction the equilibrium constant is f and equation (33. but a method similar to that described in 34f. viz. as defined above.16) takes the form K ding/ = A# dT RT* (33. A# X>#(final is state)  >H(initial state). The equation (33. van't Hoff. In = Kc X CRT )* 7 71 . and for most purposes it is possible to replace A// in equation (33. in equation (32. 34i K . where A/f is when the K K Kf so that. in general.18). Kf = In K + An In R + An In T. that _dlng dT An _ Ag RT*' T ^ f==AH ^ n(fl2)  (33 18)  the heat of reaction at constant pressure. that the particular standard states chosen for the activities of the reactants and products in the expression for K. the equilibrium constant c is related to f by equation (32.
K A.16)] (33 21) ' where A/7 is the heat of reaction starting with pure liquid reactants and ending with pure liquid products. the standard state of each substance being the pure liquid at the equilibrium temperature and 1 atm.33) and (32.25). Provided the pressures are not too high. equation (33.34) that (33. and it is possible to write dlnK'c AH . the ordinary heat of reaction is substituted for AT. for a reaction in dilute solution. the constant pressure condition has been omitted from equation (33.21). Upon taking logequilibrium function K' arithms. since the equilibrium constant on the basis For many of the chosen standard states is independent of thfe pressure. the variation of the density Po of the solvent will not be large. should not be confused with equation (33. as before. It will be noted that. The variation of K' atm. However. giving the approximate result (33 22) ' For reactions in dilute solution. at the same time AT.34). (33 ' 24) It is important that this result.23) Provided the temperature range is not too great. and the last term in equation (33. which gives the variation of c for a and not A/7.17) in the approxi mate form dlnK' p dT where RT* ' (33. the results are of no practical value. purposes it is sufficiently accurate to replace KN by the equilibrium function KN involving mole fractions. it follows from equations (32. without introducing approximations. p with pressure is ignored. it is therefore the common practice to employ equation (33. The difference between d In K^/dT and d In K' e /dT may thus be neglected.290 FREE ENERGY AND CHEMICAL REACTIOH8 33f could be used. . homogeneous gaseous equilibrium. at 1 atm. Differentiation with respect to temperature then gives A# 1 [cf. the latter involves Q 9 .20) is taken as the ordinary heat of reaction at constant pressure. pressure.19). pressure and temperature T. it is convenient to use the concentration C) defined by equation (32. usually For a homogeneous reaction in a liquid system the equilibrium constant is conveniently expressed in the form of equation (32.23) may be taken as approximately independent of temperature.
e. between a pure solid and its vapor or a pure liquid and its vapor. Heterogeneous Reactions: Influence of Temperature. chemical or physical. where A// is now the ideal molar heat of vaporization of the liquid (or of sublimation of the solid) at the temperature T and a pressure of 1 atm. The dependence of the pressure p on temperature is thus usually expressed by the approximate equation (33. 2 . which is equivalent to K' rule no attempt is made to keep the total pressure at 1 atm. The various A# values refer to the complete reaction. with Aff equal to the heat of reaction adjusted to the value for the gas at low In studying these equilibria. Heterogeneous physical equilibria. the numerator on the righthand side equal to the ideal molar heat of vaporisation (or sublimation) at temperature .33g FREE ENERGY CHANGE IN CHEMICAL REACTIONS 291 In the foregoing discussion various forms of the van't Hoff equation. the corresponding factor may thus be omitted from the expression for the equilibrium constant. have been derived ous equilibria.. p and as a general quantity is the partial pressure p. the true equilibrium constant.5H 2 O(s) = CaO(s) + CO 2 (0) = JCuS0 4 .22).16). of equation (33. is equal to the fugacity of the gas in The varia32g). CaCOa(s) JCuSO 4 . equilibrium with the solid at a total pressure of 1 aim.3H 2 000 + H O(0). or even constant.. including the solid phases.g. the experimentally determined pressure. where Aff is the ordinary heat of reaction at the temperature T. but is maintained constant at some other value. 33g. thus. although the dissociation pressure should vary to some extent with the total pressure. K/. Because they present certain features of interest.g.. temperature is again given by equation (33. the activity is unity for every pure solid taking part in the reaction. dln/\ Atf? "FJp"^' is ( (33 ' 26) where. The variation of In/ with is here also equivalent to the equilibrium constant. according to the remarks in 29g.16).. since the solid or liquid is in the pure state. for example. brief reference will be made here to some heterogeneous equilibria. The equations derived above for homogeneous reactions apply equally to heterogene some exact and others approximate. e.. and others will be considered later. although. If the total pressure is not 1 atm. however.20) in the form . the fugacity of the vapor scribed. for equilibria of It is necessary to bear in mind. In reactions involving one or more solids and one gas. as mentioned in 32g. that in the form different types. 16) the relationship is applicable precisely to any equilibrium. can be treated in a manner similar to that just deIf the total pressure of the system is 1 atm. (cf tion of In/ with the temperature is then given by equation (33. the dependence of the fugacity on the temperature can be expressed by equation (29. as.
The standard change of heat content can be expressed as a function of temperature in accordance with equation (12. If the change of heat content A// were independent of temperature. Ay. Walde. 431 (1939). or against l/T should be a straight line of slope in with A.. deg. The results obtained in this manner are approximate only. Soc. or (33. Am. A/f/4. general integration of the van't Hoff equation would give [cf. equation (27.26) is the exact form of the ClausiusClapeyron equation (27.T* Id "4. that the volume of the liquid or solid is negligible. for heats of 5 reaction are known to vary with the temperature. /.15)] In K =  Kl .ff calories. Chem.. alternatively.~* mole""1 . A/9.r T. 97 (1936). so that the fugacity may be replaced by the vapor pressure. J. + constant. etc. A# .578V This equation. even when the heat content varies with temperature. * I0g 2 _ AiP/r. If this expression is 1 For a more exact significance of in equation (33. 57. gives so that the plot of log .16)..27).12). if Ajff is available. K K or. (33. this is exactly equivalent to the approximation used in deriving the ClausiusCiapeyron equation.29) where A. Chem. If the vapor is assumed to be leal. are derived from the heat capacities of the reactants and products and their variation with temperature. the equilibrium constant at any temperature can be determined provided it is known at one particular temperature. may be used to evaluate the heat of reaction if the equilibrium constant is known at two temperatures. 33h. so that Aff .AHg + AT + iA/ST 2 + \&yT* + .28).292 FREE ENERGY AND CHEMICAL REACTIONS 33h T and pressure P. In this simplification the assumption is made that the activity of the liquid or solid does not vary with pressure. as seen in 12j. and the total pressiuc is taken as equal to the equilibrium pressure. z R converting the logarithms and expressing R in cal. see Douglas and Crockford. It should be noted that equation (33. 45. the two equations become identical.576 Integration between the temperature limits of T\ and T 2 the corresponding values of the equilibrium constant being K\ and K*. 12k. Integration of the van't Hoflf Equation. Phys.
69 X 3 lO' 3 .47 X 10. derive a general expression for the variaDetermine the value of f tion of the equilibrium constant with temperature. the value of taking Kf is R as 0. A. K/ becomes 2.6 !T2 + 12. it follows that 12k. respecthe integration constant.r 9.~ l mole~ 1 the expression . etc.130 8 2 3 10~ 9 T 3 kcai.69 X 10~ T . JAy = it is 0. it is is possible to derive A#o by utilizing the procedure described in 12k. + fHk^ K According to the result obtained in the problem in to refer to the standard states. JT At 450 C.69 lO' X R X seen that T . JA/3 = 3. and the variation of In (or log K) with temperature can then be expressed in the form of equation (33. and utilizing these data it is 1.e. which is supposed A# = and hence. tively. If where K is either // or KN.7. 3. ' /' is 12. = 9. so that.00655.30). $re available from thermal measurements. the result dlnK and upon integration it is A#g "" A<* Aft "*" Ay "*" "*" " 2R 3ft "' found that for reactions in the gas or liquid phase. Aa =  7..130. and utilizing the heat of reaction and heat capacity data in 12k.130 7.69 X 10T .987 cal.64 log T 1.12 X 10. deg. 3 2 6 cat. it is possible to evaluate the Integration constant /'.47 2ft lO" 6 m T+/ .00655 at 450 C (Table XXII). 9.30).46 X 10~ T + 3.7.0. The accuracy of the resulting expression is limited largely by the thermal data. for these are often not known with great certainty. T.47 X . found that for m lnT + . if known at any one temperature.13 .07.07.46T + 3.X 0. AH and Aa. .46.46. the standard states chosen in 30b. 723 K. Actually.. ^ i.47 X 10~* cal insertion of these values into equation (33.303 log In Kf = Kf   8. and /' is K K Problem: Taking the equilibrium constant (//) for the JN 2 equilibrium to be 0..16).86 + lO'T  0. A#J = Upon 9.33h FREE ENERGY CHANGE IN CHEMICAL REACTIONS is 293 substituted into (33.0. Care should be taken to ensure that the standard states used in connection with the heat of reaction A// are ako those employed for the equilibrium constant. 31b correspond with those almost invariably employed in both equilibrium studies and heat of reaction measurements. . at 327 C.
viz. (33. so that by equation (33. . Problem: Utilize the following values of K/ for the ammonia equilibrium to an expression for A# as a function of the temperature.. Determine the standard heat of reaction... By writing equation (33. and hence Kf is 0. t 8.47 X 10~*T* = ~ . 6 Attention may be called to the fact that the procedure just described provides a useful method for determining heats of reaction from equilibrium constant data. A/?. 350 2.30) in the form K K K . the slope of which is 8. at 25 C. a simple graphical procedure is possible which permits the use of all the available data. It can be seen that if Aa. H. The standard heat of reaction can then be determined at any temperature in the range in which Aa. the integration straight line of slope equal to AjHoconstant /' can be readily evaluated. A.82 10~ 3 1. etc.55 500 10~3 3. it is possible to express A/? as a function of the temperature by means of equation (33.29). i. Eng. etc.294 FREE ENERGY AND CHEMICAL REACTIONS 33h At 327 C.. S.R In K + Ac* In T + it is ^T + %&yT* +   A 77 = = I'R.46T 8.810 J. are applicable.605 X 10~3 37. etc..810 cal. The values of the lefthand side (L.56 1. These results are plotted in Fig. In Kf is thus found to be (The experimental value is about 0.294  X .69 X 10~*T  X 0.486 10r3  X 36. If the has been determined at two or more temperatures.383 X 10~ 3  35.47 X 10~T* cai. + 3. and the corresponding 1/T's are then found to be as follows: L.31) seen that the plot of the lefthand side against l/T should yield a With A// known.69 X 10!P  0.. H.  7. the righthand side of equation (33. Aflo and /'.78 C 10~ 3 Kf X X X X Inserting the values for Aa. 19. are available. and Aa. tion (33. If the value of In is known at several temperatures.e.58 1. =et al. Ind.19.30) can be solved for the unknowns. 23. equa  4.62 400 10~2 1. equilibrium constant therefore.31) becomes A and AY given in the preceding problem. heat of formation of ammonia. are known. obtained from the equilibrium constants given above.46 In T + 3. 1002 (1931).53 1. This is consequently the value 3f A//JJ.27 450 10~ 2 6. i. equation (33. the points are seen to fall almost exactly on a straight line. Since Aflo has been derived above.e.. derive Temp.PR. and hence can be expressed as a function of the temperature.)  3. A0.041. S. 388 (1931).040. Chem. 600 K. Ed.29).38.30) still contains two unknowns.576 log K 7. Chem. l/T ..). A// Randall.
if the ammonia equilibrium is written as K *N 2 + f H* ^ NH 3 . This highly important equation equal to gives the variation of the standard free energy of a reaction with temperaAF is equal to RTln it is also.60 FIG. AF where the constant / is T + IT.33i FREE ENERGY CHANGE IN CHEMICAL REACTIONS i.32) I'R.6) this is equal to 33L Variation of Standard Free Energy with Temperature.30 1.(It will 8. and partly be noted that A/fJ obtained here temperature.223 + 328  12 = 10.0 02 W37.30) is multiplied (33. The value of AF given by equation (33.50 s l/T X 10 A#8 from equilibrium 1. an expression ture. by equation AF. 295 At 25 C. the standard free energy of the reaction under It follows. to uncertainties'in Aa. the result is RT In K. in effect.. which give the variation of heat capacities with It is also possible that the f values are not exact. If equation through by RT. from that adopted The discrepancy may be due partly to an error in the thermal A/7 value upon which AJ/jJ i n the previous problem is based. (33.810  2. Determination of constants (33..) K 38. etc. in the preceding problem.717 cal.0 1. that consideration.0 36. 298 K. Aj3.32) applies to the reaction as written for the determination of the equilibrium constant. differs by about 320 cal. and since for the equilibrium constant as a function of temperature. therefore.e. For example. 19.40 1. it is found that A# .
8) for the standard states. per mole of ammonia.987. 1 Problem: Derive an expression for the standard free energy of formation of mole of ammonia as a function of temperature.936 cal.130 + 12. may A# e.296 FREE ENERGY AND CHEMICAL REACTIONS 33j is as stated earlier. etc. etc. by comparing equation (33. on the equilibrium constants at two or more temperatures. it is readily seen that AF =  9.32) A# . consequently change of two moles of ammonia instead of one. so that Aa. This may be seen. In the "water gas" reaction (1) C0 + H 2 . and taking AFJM It  9.07fi!F. the latter being equal to I'R.e..46T In T 3.145 3. It will be assumed. of course.07.e. alternatively.130 cal.. In some systems there may be two or more equilibria which are established simultaneously. and evaluate AF at 25 C. seen shortly. as before. T as 25 C. AF values in another manner for calculating free energy changes. I' and hence / would be also changed.130 + 7. may be regarded as known. and /' equal to 12.30) this is based either on a single value of the equilibrium constant together with A// at any temperature or.32) with (25.69 X lO'I72 + 0. in a general manner. as will be Attention is (33. and the integration constant I. In order to utilize equation (33. This gives AF in cai. 8. i. a simple matter to derive the corresponding equation for . as derived in the second problem in 33h. it is found that Setting R equal to  1. and might be evaluated if AS were known.235 X 1Q~*T*  12.660  328 +6 7. for example. 33 j. it is more convenient to use entropy i. If the reaction were written .. it as should be for the formation be would doubled.CO + H 2 2 0.32) it is necessary to know A//S. with A7f J equal utilizing the results obtained in the first problem in 9.. is then similar to that described in 33h in connection with equation (33. with the result that AFJ 98 would not be greatly affected. = TAS However. may be drawn to the fact that the constant I in equation related to the entropy change AS accompanying the reaction. Simultaneous Equilibria: Addition of Free Energies.. The procedure for the derivation of AH 8 and /.//Ji t X /i f2 the standard free energy increase for the formation of 1 mole of ammonia. 298 K. the free energy Since AF is equal to of the preceding value. Aa. and AF the equilibrium constant f is /N n. that heat capacity data are available. A0. K N + 3II 2 2 ^ the equilibrium constant would be/N H3 //Nj X /H.810 cal. be noted that if a slightly different value of were employed.30) have previously been evaluated it is.g.. at high temperatures. there will be a partial dissociation of . which wouhd be the square RT In K. By to 33h. If the constants in equation (33.
or 6.6).2 K.790 cal.4.. hence. at 25 C. 297 carbon dioxide.33) It is thus possible to calculate any one of these equilibrium constants if the other two are known.2 log Kf 6. Kf = 1. expressed in calorie units.RTlnK 1 =.65 kcal. 54. 1 X flHjO oco. (2) and of water vapor.05 X Itr'at 25 C.4. immediately.CO + *0 H = H + K>2. will exist. it follows.. log Kf . is equal to AFjJ AFJ. 2 2 2 so that three simultaneous equilibria. taking logarithms of equation (33.33) and multiplying each side by it is seen that . and that for reaction (3) is 54. and consequently.RT In Kf it follows .33j FREE ENERGY CHANGE IN CHEMICAL REACTIONS viz.RT\nK + RTln K 2 z. . K* and 3 will be the same. An examination of the chemical equations for the three equilibria given above shows that..e. viz. Calculate f for the "water gas" reaction at this temperature.. . Problem: The standard free energy AF for reaction (2) is 61. with K.44 kcal. that K ffi  2  fAj (33... the constants are K = 2 Since these equilibria occur in the same system. K The standard free energy kcal. AF? . the equilibrium constant K\ is given by J v = R. for reactions (2) and (3). Consequently.e. like AF. they can be added and subtracted in an analogous manner. (3) C0 . i.790 .AF.. hence. if standard free energy equations are written out in a manner similar to that used for thermochemical (heat of reaction) equations in 12d. at least.AF2 . as written.. This fact has proved useful in the determination of equilibria which cannot be readily studied directly by experiment. 61.44 at 25 C. By RT. by equation (33.79 298. Since AFJ .98.65 6. i.576 X 298. the equilibrium activity of any substance involved in K\. reaction (1) is equivalent to reaction (2) minus reaction (3). X a Hl OCO 2 For reaction (1) 9 whereas. etc.
" 1932. 27..65 kcal. g) . by convention. "The Free Energies of Some Organic Compounds. Prosen. all the substances being in their respective standard states. Parks and H.. ibid. S. For example.298 FREE ENERGY AND CHEMICAL REACTIONS 33k 33k. are their respective pure stable forms at 1 atm.. the standard free energy of a compound is equal to its standard free energy of formation. "The Oxidation States of the Elements. 7 They can be utilized. i. Eng. pressure. U. par Data mainly from W. Because of their additivity their relationship to equilibrium constants. the standard free energy of 1 mole of water vapor becomes equal to the standard free energy of formation from its elements. Pitzer and Rossini. Ind. like heats of reaction. 384 7 (1936). Mines Butt. to the increase of free energy accompanying the formation of 1 mole of the compound from its elements. ibid. Standard Free Energies of Formation. 467 (1945). 34. ibid. 584 (1941). This is especially the case for reactions. so that the standard 54. to calculate the standard free energies of many reactions. 75 (1940). 33. and for other reasons.. Chem. .. Rev. = 54. for several of which the values could not be obtained in any other way. /. FoDrins and Miller. Wagman. 559 (1946). M. Res. 39 (1940). 36. ibid.. Pitzer and Rossini. ?)] = 54. the standard states being the gases at unit fugacity. etc.. Huffman. Stand. Kilpatrick.. the convention is adopted of taking the free energies of all elements in their standard states to be The standard states of solid and liquid elements zero at att temperatures. the methods available for the determination of free energy changes for chemical reactions will be reviewed in the next section.e. Thacker. and these are derived from the free energies of reactions in a manner similar to that used to obtain standard heats of formation from the heats of reaction in 12f.[F(H a. Pitzer. Kelley. 27. 255.65 kcal. If the standard free energies of the elements are set equal to zero. 407 (1937). There is no method known for the experimental determination of absolute free energies. 403 (1945).65 kcal. Pitzer and Rossini. hence. Wagman. at unit fugacity.. Latimer." 1938. but this is of no consequence. . Parks. Chem. Nat. free energy of formation of water vapor is This means that the free energy of 1 mole of water vapor in its standard state is less by 54. Kilpatrick. than the sum of the free energies of 1 mole of hydrogen gas and J mole of oxygen gas in their respective standard states at 25 C. 35. for the reaction between hydrogen and oxygen at 25 C. Prosen. 143 (1945). for gaseous elements the standard states are the ideal gases at 1 atm. Bur. like heats of formation (standard heat contents) in Chapter V. The standard free energies of formation of a number of compounds at 25 C are given in Table XXIV. 34.. S. On the basis of these conventions. The results are conveniently recorded in the form of standard free energies of formation of compounds. that is. M. Vol. mole"1 at 25 C. 406. Taylor Pitzer and Rossini. Bur. G. For the purpose of evaluating free energies of compounds. see also International Critical Tables. g) + Jf (O...65 kcal. it is useful to tabulate standard free energies. V. Kilpatrick. since the solution of and thermodynamic problems requires a knowledge of free energy changes..
that is.. incidentally. For example. viz. i. For this purpose.32. and /i is that corresponding to the vapor pressure. the free energy of formation of liquid water is recorded in Table XXIV. The vapor pressure which.0 137. the problem is simply to calculate the difference in. at unit fugacity. i. 2 O(Z) water is equal to the molar free energy of the vapor with which it is in equilibrium ( 27a).94. except near the critical point. but for certain purposes the standard free energy of water vapor. STANDARD FREE ENERGIES OF FORMATION AT 25 C IN KCAL. (33.74 NO(0) HjSfa) SO 2 (<7)  20..66 7.54 .34) where /2 is unit fugacity.70 CaCO.94 56. at*l atm. and in the standard state of unit fugacity.2 31. It is sometimes required to know the free energy of formation of a substance in one physical state when that in another is given. For most purposes. this is the standard state at ordinary temperatures. PER MOLE * Inorganic Compounds Substance AF Substance AF Substance HFfo) HBr(0) COfo) C0 2 (0) .14 Methyl alcohol(Z) 7. . use may be made of equation (29. and for which equilibrium constants could not be determined experimentally. ideal behavior is assumed (cf Chapter XII.33k FREE ENERGY CHANGE IN CHEMICAL REACTIONS 299 ticularly those involving organic compounds.86 5.34 50. at the given temperature.4 BaCO(s) Bi 2 3 (s) 271..5 29.87 71. ideal gas For this purpose.5). since TABLE XXIV. which proceed to virtual completion.12. it is necessary to determine the standard free energy change == Since the molar free energy of the liquid of the process 2 O(0).8 22.e.6 3.35) Pi 25d for the free energy is identical with the expression in change accompanying the expansion of an ideal gas.7 116. see Table 5 at end of book.61 16. Exercise 5) equation (33. free energy of 1 mole of water vapor at its equilibrium (vapor) pressure. .06 Benzene (I) For further data.81 .0 40.26 Substance 31.(a) Organic Compounds AF Substance Methane (g) Ethane (g) Propane (g) Ethylene(0) Acetylene(0) *  12.9 94.7 Sb 2 3 (a)  149.e. the ratio of the fugacities may be replaced by the ratio of the vapor pressures.6 270.7 Ethyl alcohol(Z) Acetaldehyde (I) Acetic acid(Z) 40.34) then becomes . is required. (33. H H 7 A/* = F2 FI = RT In  .
for the reaction ^ CO (^ + 2H*(0) (0) (33. i. i. the vapor pressure of the final state.70 2.76 mm. (x) AF =  5.084 cal. Writing the free energy of formation of each species below that for liquid methanol at 25.e. AFJ M is given by its formula.96.70 kcal.. and since equation (33.88  1. AJPV. Thus p 2 may be set equal to 760 mm. it is seen x x 331. the standard free energy change at 298. is equal to the maximum (reversible) work.0) = CHOH(Z).05. vapor at 1 atm.65 kcal.54.e. since pi. is based on the measurement of the E. for the initial state. which has been largely used for reactions involving ionized substances..""1 mole""1 . Calculate the standard free energy of formation of liquid methanol at 25 C. so that at 298. The first is based on the experimental determination of equilibrium conBy the prostants.. hence for water vapor.300 ffREE ENERGY AND CHEMICAL REACTIONS 331 of water at 25 is 23.. liquid.054 cal. It was seen in companying any process at constant temperature and pressure. 40. an expression can then be obtained for AF as a function of temperature. the vapor pressure being 122 mm.2 X 2. the units are immaterial..p.M. The second method.0 kcai.35) involves a ratio of pressures. C R AF  1. of the cell may be used to derive the accompanying free energy change.M. other than work of expansion. Determination of Standard Free Energies.. + free energy change for the reaction CQ(g) 2H 2 (#) 5. at that Problem: The standard is .'S of certain 25b that the decrease of free energy acgalvanic cells. and p\. i. Hence.0 + 0) = 6. have been used ..F. and the (maximum) E. at 25 C.P.2 K.. at 25 C.e. obtainable from that process.. AF is . Many processes can be carried out reversibly in a suitable galvanic cell.2 K.2 log 7oU PI = .576 X 298. cedure described in 33i. is 122 mm. If the particular reaction can be performed in such a manner that. and . with in cal.08 = 6.987 X 298. Three main procedures for the evaluation of standard free energies of reactions.56.96 kcal.e. so that the value at any particular temperature can be evaluated. For the process 8 OH(0) = 8 OH(Z).  = (33. is 760 mm.1.. i.RT In & = 4.CH 8OH(0)  + temperature. apart from work of expansion. and pi to 23.303 log 23.76 2. is given by CH CH AF . then the free energy change is equal in magnitude to the electrical work. and their combination in the manner indicated above. all the work is electrical in nature.88 kcal. assuming ideal behavior of the vapor. deg. The standard free energy of formation of liquid water is 56..76 mm.
F.M.M. applied from the potentiometer thus gives an accurate measure of the reversible (maximum) It may be mentioned that if large currents flow through E.F.F. if the external E. or reversible. of course. volts. The external E. increased by a small amount.F. at a given temperature and pressure.F. it is necessary that the cell should function reversibly. so that no current flows. and the process taking place within it is accompanied by the passage of faradays of electricity. and the E. the tests of reversibility are as follows. be stated. where (33. The number N of faradays required for the cell reaction can be readily obtained by inspection of the chemical equation. because of the slowness of diffusion. of such a cell. the chief interest is the evaluation of the standthat this ard free energy AF of a process.. involves the exact balancing of the E. coulombs.p this is usually understood. should take place. is passing.5)]. this number of faradays is equal to the number of equivalents of electricity.e.M.M. is measured. usually atmospheric. i. If the external E. etc.M.M.e. At the present moment. however..F. current will flow from the cell and a chemical change. that is. Fortunately.M.F. of the cell by an external E.M.M.F.F.M.. proportional in extent to the quantity of electricity On the other hand. E.. the cell when its E.500 int. E.F. charges.36) AF is the increase in the free energy accompanying the process taking in the cell. or int. that if the substances involved in the cell reaction are XIX . concentration gradients arise within the cell. so that the flow of current is zero or infinitesimal.. where F represents 96.M. may be employed for free energy calculations.F.M.F. voltcoulombs. It will be seen in Chapter can be calculated from AF and the activities of the substances present in the It can cell.e. of the cell.331 FREE ENERGY CHANGE IN CHEMICAL REACTIONS 301 subject will be considered more fully in Chapter XIX.'S.AF = NFE. observed is less than the reversible value.F. there should be no chemical change in the cell. of a voltaic cell is E int. of the cell. to a definite temperature place and pressure. the current should pass in the opposite direction and the cell reaction should be exactly reversed. as described above. is decreased by an infinitesimally small amount. it is necessary that the cell should be operated reversibly. In general. In order that the E. and E is its reversible. joules (cf. it will The N coulombs. To determine the maximum.F. transferred in the cell reaction (cf. it follows from the arguments presented earlier that NF . i.M.F.M. When the cell is connected to an external source of E. i. the potentiometer method. 3b). the work done by the cell is NFE int.. the current drawn should be infinitesimally small so that the system is always virtually in equilibrium. If the cell is a reversible one. which is adjusted so as exactly to balance the E. If the E. maximum. The value of AF refers. but for the be sufficient to accept the fact that cells can be devised in present which particular chemical and physical changes take place. of known value. almost universally employed for the accurate determination of E. by utilizing a form of the reaction isotherm [equation (33. and instead of writing AFr.M. or number of unit 45b).
20) takes possible. equation (25. the resulting E. This is true. hence.'S. for many reactions involving organic compounds.38). of reversible cells thus provides a simple. accurate. it is a relatively simple matter to obtain the heat of reaction Aff with reactants and products in their standard states. be evaluated if Aff and AJP are known.302 all FREE ENERGY AND CHEMICAL REACTIONS 33m present in their respective standard states. For gases. the entropies can frequently be derived from the respective partition functions. will be The standard free energy change is then given by the standard value the appropriate form of equation (33. The third method commonly employed for obtaining standard free energies depends on the use of entropy values. by means of equation (33. the entropies of solids. utilizing the third law of thermodynamics. for a process involving reactants and products in their respective standard . Standard Free Energies and Entropy Changes. of course. the problem of obtaining the standard free energy change would be solved. viz. Another procedure which has been found useful is to determine the entropy of an element or compound from a knowledge of the standard entropy change of the reaction and the entropies The entropy of all but one of the substances taking part in the reaction. as it provides a highly important practical application of the results obtained in the earlier study of entropy. from the general equation Atf that It is apparent . it is possible to evaluate the entropy change AS It was seen in Chapter IX that for the process at the same temperature. . If the entropies in their standard states are known for all the substances concerned in a reaction.38) In AF for any reaction could be calculated if Aff and AS were known.. the form the constant pressure condition being omitted as unnecessary. The measurement method (33. applications of this procedure will be given in later chapters. change for the whole reaction can. a direct method for the determination of the standard entropy change is For a substance in its standard state.F. for If the correinstance. sponding entropy change AS were known. liquids and gases can be obtained from heat capacity measurements. (33. and Various for evaluating standard free energy changes. many cases where direct determinations of free energy changes are not possible. this will be discussed in some detail in the following section. NFE.rAS.37) of E.M. and these can be converted into the values for the solid and liquid states by means of the entropies accompanying the phase changes as obtained from the corresponding latent heats. If the reaction can be made to take place in a reversible galvanic cell.F. 33m.36).M.
AS 1 = For the given reaction. 23. 3. bhe reaction. E. the entropy change for the reaction could be letermined.U.38 + iHg Ag(s)AgCl(s)KCl C! 2 (s) = + It may is be noted that in this particular ceil ail the substances taking part in the reaction are in their respective standard states.M.. at a certain emperature before attempting to carry it out experimentally.e.2.. respectively. deg. when the process is carried out reversibly. the cell process would require the passage of J.40) of the reaction can thus be determined the temperature coefficient of the E. the temperature coefficient of AgCl(s) X 10~4 volt degr 1 at 25 C. 1 1 express F as 23.070 cal.5) [10. divided by the absolute If the amount of heat liberated in a reversible cell when it temperature.U. equiv.1 . atom^ ). i.37) and (33. whose E. that E. Since X diver N . intropies for method does not With the standard and elements and compounds known (see Tables of for the available determination free is a means valuable QX).80 S(Hg 2 Cl 2 ) = = DS(Ag Cl) + S'(Hg)] (23. which is 3. is By definition.M.U. >perates could be measured.0 and 18. or not. +  . Because of experimental difficulties this ippear to have been used. the entropy change in a reaction equal to the heat change. by combining equations (33. x X X 7. from soln.33l) FREE ENERGY CHANGE IN CHEMICAL REACTIONS 303 States.o univalent. [n this case dE Q /dT is equal to dE/dT. and hence of equilibrium constants. deg.~ l mole""1 it is convenient is 1 equiv. it follows. Hg 2 Cl 2 (s)Hg(0. many XV .39) the reaction can take place in a reversible cell. AgCl(s) and Hg(2) are known from heat capacity measurements to be 1 l Calculate A5 for 10. for numerous reactions. p or many of the processes no direct experimental methods for obtaining hese quantities have yet been developed. thus simplifying the problem. o that .5 E. is 3.1 .F.. in which the Hg(J). Xf If SgL. Appendix). Application of Free Energy and Entropy Data.P.M.38 10~ 4 23. 33n.38 10~4 volt deg. AS = The standard entropy change Problem: For the cell 2 NF (33. reaction is Ag(s) the E. of the cell.80 cal. The entropies at this temperature of Ag().e. . mole.070 7.1 i.2 47.F. highly nergy changes.0 18. An important application of the lata is to decide whether a particular reaction is possible. mole~ (or g.0 E. Since the entropy is required in cal.39).^ (Table 1. is (33. volt"" g.CS(Ag) + + *<S(Hg 2 Cl 2)l iS(Hg 2 Cl2)3. and the standard molar entropy of Hg 2 Cl 2 (s) at 25 C. faraday.
17. Aff of formation of CHsOHfo) is . 32. so that for the reaction A is 1 .OHty)...84 1Q~*T  X 80.99 X 107 X (298.42 53.. 212.9 (2 X 0)] +  + = 57.75 cal.723 A#S .842 + 22. For the reaction as written above. At 25 kcal.26. together with A// at 298. Inserting these results.5 (2 X 49.09 cal.84. .00  51.1 .2 X 53. using heat capacity.5 17.  Atf .4 C.9 E.A#X .62 X + 2. into equation (33.9 49.  21.9  17. At 25 C. Hence.30 E. Aj8 X 10~$ ..1 kcal.48.304 FREE ENERGY AND CHEMICAL REACTIONS Problem: Determine the standard 33n + 20 8 (0) .342 + 24.7 195.837 X = 22.836 X 10~ 8 T X + 9.29).42 72.700 t + 298.700 = A#2  15. for CO.21 = 62. heat content and entropy data. at 25 + C.97 so that ACp = Hence. 147 (1940). or (. for the methanol reaction.2 K.63 for CH." and 47.0  16.[44.CO 2 (0) + 2H0(0 2 (0) free energy change of the reaction 4 (0) at 25 C.4 kcal. = 17.015 +  11. 2 X 31.700 cal.394 13.399 1.2 K.""1 mole"1 are as follows:  +   21.274 X  lO'T  68.0 + (!TAS .75)] 2 X 68.U.7 kcal.3 kcal. Chem. X C P (H Cp(CO)  2) 4.U. in the presence of a catalyst.3)] .1 21. determine the extent of conversion into methanol according to the reaction 2H 2 CO = CHOH(0).2)' + The standard entropies are 56. AT =  X 10~7 .A#  !FAS = 17. A# 2 is  The values of CP 48. Problem: A mixture of hydrogen and carbon monoxide in the molecular proportion of 2 to 1 is allowed to come to equilibrium. at 600 and 250 atm. X 10" 1 X (29S.06 + (2 X = [. AF Cf.26.2 1.4.2) 2  ." 1 mole.80 X 80.00)] 16. Hence. mole. Ewell.84 X 298. for 2H. = 298 X 57.[. deg.17. Ind.870 cal.3 212.894 6. that of CO is and that of hydrogen is zero by convention.94.7 kcal. AF . using the following standard entropies CH and heats of formation: CH 5 Aff 4 (<7) C0 a (0) H 0(0 2  44.09  5.4 0) = in cal. deg. Hence. deg. Disregarding side reactions.06 94.920 cal. Eng.TAS 21. 26.55 X 107 !P + 10r*T 0. 15.3 kcal.97 Aa =  15.1 68. .250 cal. at 298. Aff AS = [51. together with the generalized K + 8 fugacity chart.
when the omission will be rectified.42 13.27 At 600 K.65 2.lO)x .8(+8) CO 1.5 X 10~ X (600) X 10. It was stated in 23d that confirmation of the third law is to be found in the agreement with .2 134.84 X X 600 292  = .23 0.17.17 14.1 X 10~ atm.2. in this case.  5. then as a good J y X Kp hence.59 X 600 27. the numbers of moles at equilibrium are 2 z(CO) and z(CH 3 OH). for which An is . solution of the f and K' P being based on the fugacity equation by successive approximation There is consequently 67 per cent conversion of hydrogen into methanol under the given conditions.42 X 7 10~ 3 X (29S. are as follows: 600 t AF = at 600 K is equal to 8.02 7. (1 2z)./ 7 at at 250 atm.58 1.015 X In 298.820  + 4.950 with fugacities in atm. 33o.2 K.10 1. 1 are (2 z)/(3 2x) and x/(3 2z).42 If the system initially contains 2 moles of H 2 and 1 mole of CO.32). it follows that 7C/ 10~ 5 The data for the determination of the activity coefficient function . 2H 2 + CO K > fi .56 4. thus. ' K e P 34.870 = 17. Aa. A0 and A?. and so for the reaction 2z)/(3 CH 3OH(0).13 ' > (. and P 250 atm.920 + 15.13 If this may be taken as equal to the true activity function. 1.2) + 298.920 17. so that the data for the calculation of the free energies of ionic reactions are not yet available. Since 60.920 is + 36 + 13.111 +  1 1.84 X 298. Hence.1 X 10~4 approximation f p is 8. the subject will be taken up in Chapter XIX. it is possible to determine the integration constant / in equation (33. as standard gives x equal to 0. and x is the extent of conversion at equilibrium. + 15.5 X + 298.67.33O FREE ENERGY CHANGE IN CHEMICAL REACTIONS 305 Using this value of AF. the respective mole fractions 2x(H 2 ). ^ P p2 = x(3  2oQ 2 N H3 4 2 XNco is is 2.X (600) 3 2 7 3 46.2) 3 2 7 == + 26. the value of AF 600 given by In AF *  17.2 1.2(+8) 12. with T equal to 298.53 12.59. Confirmation of Third Law of Thermodynamics. and carbon monoxide Since K' p 1 of state.130 cal.2  11.920 + = 11. together with Af/J. However. K' 2. 10~ X (29S.920 46.6 " y c TT 7' CH OH H 3 2 513. 33. K Attention may be called to the omission of the entropies and heat contents of ions from the foregoing discussion.4 K 98./0.9 X T RT in K/ .9 X 10..7 atm.27.
this is found to be 2. 47 cal.1 The standard heat of formation of the oxide is known to be 7.. satisfactory agreement has been found in other instances of a similar type. that equation (33.30 . The third law entropies of silver oxide. and if the pressure of the gas is taken as 1 atm. 10. actions in particular.e.30 kcal.2. . deg. It was seen in 25g [equation (25. i. viz. but two simple cases will be considered here. + .41) energy and Q is the partition function of the given the molar energy content when all the molecules are in their lowest energy state.. Numerous examples of such agreement are to be found in the literature In the of thermodynamics.(298. may be regarded as confirmation of this (third law) postulate. can be derived from oxide. and so to determine the free energy change. mole" 1 and hence TAS should be the free energy of formation. A/S is 29. assuming the entropy to be zero at the absolute Very zero. mole"1 in complete agreement with the direct experimental value.41) may be written as species. i. or 0. .M.2 X 49. . silver and oxygen are 1 1 29. F is the molar free E Q is N fo so that _ #o ^ _ RT ln N <_ j' (83. The partition functions invariably refer to the ideal gaseous state.2 and 49.15.0158) = . at K. measurements and from the third law entropies of mercury. problem in 33m.0 cal. for the reaction 2Ag(s) the dissociation pressure (cf.1 (2 X 10. The standard free energy change for the formation of silver O 2 ({7) = Ag 2 O(s).e. silver and silver chloride.e.mole" respectively. at 25 C.59 kcal.RT In ^ .42)]. is the Avogadro number. the entropy of mercurous chloride was derived from E. Free Energy Functions. + .. therefore. that Fwhere Eo = . .. Analogous results have been obtained in many cases involving both inorganic and organic compounds.42) . deg. an alternative method of presenting what amounts essentially to entropy data is to utilize certain free energy functions based on the use of partition functions. the value of which is known from direct measurement. given by Aff 7. In connection with homogeneous gas re33p.0.306 FREE ENERGY AND CHEMICAL REACTIONS 33p experiment obtained by using thermal entropies in conjunction with other data..0158 kcal. the values apply to the usual standard state. i. Exercise 11). (33.8 cal. The fact that an almost identical result.59 kcal. . and hence for the reaction in which 1 mole of silver oxide is formed.1.2 X . 1 1 deg. Another procedure for testing the third law of thermodynamics is to combine heat content with entropy data for a given reaction.0). at 25 C..F. It follows."" mole" has been obtained by direct heat capacity measurements on solid mercurous chloride.
450 60. for temperatures up to 1500 K.711 53.876 49. giving T The quantity . since S is zero.12 contains values for the free energy function It will be observed that Table of graphite..508 48.477 45. the substance is in its follows.590 53.711 2. ref.238 43. this has not been obtained from equation (33.393 45.203 46.096 54.517 40.061 38.83 42. Kilpatrick. at a given temperature.05 62.21 59.5 52. is known as the free energy function of the substance.50 46. HQ = JBo. ref. el aL.31 800 31.98 1000 32.20 46.E + RT. 1 atm.688 51. have been determined in this manner and tabulated (Table XXV).49 54.91 48.697 47.884 58.597 50.1) Vy ~ /"' XXV becomes ( P fr .306 2.861 0.555 37.817 0. Wagman.453 46. the lefthand side ."1 MOLE"1 400 26...49 40.808 50.2 57. Rev.39 53.771 48.284 4.860 54. Chem. that at K.49 64.141 43.43).186 49.109 47.171 51.112 40.588 48. 7.21 57. Pitzer.42). ref. = E be written as H .148 39.828 39.314 49.138 47. It H 1 mole of an if # when RT is zero.174 36.28 54.181 51.033 66.(F (33.824 42.979 55. see references in Wilson. this may It is consequently possible to substitute HQ for EQ in equation (33.100 46.423 42.044 45.27 45. 17 (1940). pressure.86 48. therefore. Substance 298.43) is. 7. by the third law of thermodynamics. et cd.622 58. The method for the calculation of (F H$)/T for solids is based on the use of heat capacities.16 FREE ENERGY FUNCTIONS IN CAL.989 50. its value for any gaseous substance.422 44. + RT ideal gas.985 41.38 43.84 69.24 47.222 49.254 51. pressure.7 42.14 1500 K H N 2 2 2 Graphite CO CO.878 51.298 42.94 35.e.634 62.12 57.172 45.738 50.46 45. at 1 atm. 7.39 66. 8 24.951 37.06 52.06 50.350 43. equation (23. 9  E$)/T or  (F  Ho)/! that 7 TABLE XXV.771 45. For a pure solid.968 43. 27.53 38.25 44.306 55. which is applicable to gases only.65 61.380 53.95 51. of equation (33.4 49.43 53.33p FREE ENERGY CHANGE IN CHEMICAL REACTIONS 307 = E + PV.05 40. The data for a number of substances.81 600 29.8 46.734 42. DEG.42) or (33. Cl* HC1 NO HzS CH CH 2 4 clul NH SO. or standard state.461 50.43). and for By definition.826 57.895 45. i. For main sources of data. can be readily derived from the partition function for that temperature. also.614 44.01 37. .688 1.
if CP of the solid is known as a function of the temperature. Several methods are available for arriving at the proper values of A7/o. so that placed by E first The of free . it follows (33. hence. The change in the free energy function accompanying a particular reaction is A(F Ho)/T. (33. However. represents the standard state. the results may be obtained indirectly from partition functions The energy content of an ideal gas is independent of the pres16c). Calculation of Standard Free Energies. From this fact it will be evident that the foregoing method of obtaining AFJ5 is really equivalent to the use of the entropy change. (cf.47) . of heats of reaction. and E$ and H$ are identical. instead of using experimental heat capacity data to derive A//2 from A# values. and this may be written as T so that T ' _ (ipo rjro \ J + Affg. at a given temperature. (33. that is. pressure. nt 1 atm.46) and that since # = E + RT for 1 mole. it follows upon integration that X . As seen earlier ( 12k).45) term on the righthand side can be derived directly from the table energy functions.308 FREE ENERGY AND CHEMICAL REACTIONS 33q the symbol S being employed since the pure solid. E EQ. (33. +RT. including heat capacities at several temperatures. since Cp is equal to (dH/dT)p. A//8 for a reaction may be evaluated from thermal measurements. and hence for the determination of the standard free energy change AF it is necessary to know A#o for the given reaction. but these all require a knowledge of heat content changes. for Hence. CpdT. it follows immediately that F = // TS. can be obtained by analytical or graphical integration. can be utilized to calculate equilibrium constants or the standard free energy changes of gas reactions in the following manner.44) Upon combining these two expressions with the relationship the standard state.8) may be resure. Further. (F 7/J)/ T The free energy functions 33q. E in equation (16.
A third method for obtaining A# has been employed in certain instances by utilizing heats of dissociation derived from spectroscopic measurements. the value of Atf at XXV and XXVI to determine the standard 2 2 free energy change of the reaction.29 The entropy relative heat content any temperature may be derived from the free energy function and the by utilizing the relationship S = .386 2.2992 3.123 10.172 1.   A[(F  //X)/f] A(//  //) .322 4.385 4. . calculated from partition functions by means of equation (33. PER MOLE 400 2. Substance II 2 H RELATIVE HEAT CONTENTS IN KCAL.53 4. From Tables i.203 3.834 6.865 2.11 2. These results refer to the substances in their lowest energy state.584 9. Utilize Tables + JO (0) = H O(0).e. it is then a simple matter to obtain Al/jj by means of the relationship A//  (33.072 0.876 HC1 NO HS 2 CH CH 2 2 4 6 2.5720 8.873 800 5.37 11.16 2.33q FREE ENERGY CHANGE IN CHEMICAL REACTIONS 309 Values of 7/8.257 10.666 1000 6.075 7. i.27 4.460 17.365 2.701 14.78 7.0. 9.073 2.H8)/!F] + [(# . XXV and XXVI the following data are obtained at 25 C.deg.035 2. and can be calculated if necessary.082 5.8.2 K: 24.497 7.47).HI "Seeref.238 2.130 34.70 14.694 kcal.004 13.195 3. are usually small.966 7.e.397 2.03 5.560 18.198 4.031 37.854 5.198 1.17 10. TABLE XXVI.80 kcal.222 8.407 2..365 2.549 8.41 600 4.44).070 2.77 at 3.700 7.537 5.323 4.Hg)/!T].694 11.792 2.359 17.024 2.254 5..79 21.282 oal.782 0. for a number of gases at various temperatures.669 2.279 4.129 4.923 3.689 6.814 11.99 5.78 10.[(F .210 5.503 2. have been recorded (Table XXVI). 10 For pure solids.190 * 298..53 2.56 C 2H C H2 NH SO 2 * 3 2. Problem: For the reaction 25 C is  H 2 (0) 57.206 2.423 21. If A/f for the reaction is known at any temperature (Chapter V).48) the last term being evaluated from Table XXVI.92 8.10 5.731 2.580 1500 K N. and hence correspond to AffoJ the corrections required to convert the results to Affjj. 298. Graphite CO C0 2 C1 2 10. H Q HQ at any temperature may be derived from heat capacity measurements by means of equation (33.321 12.776 11.2656 5.22 3.024 ~ (F* HD/T # .00 2. known as the relative heat content.22 7.784 3.63 17.* = .75 7. to the standard states.252 2.01 11.59 2.
0.11 kcal.11) . partition function of the atomic species consists of the electronic and translational contributions only. 57.45).16) as where the subscripts The A t (3352) . Equilibrium Constant and Partition Functions. For many purposes it is not necessary to know the actual partition functions.RT In /Qo/Ar + using a notation similar to that in RT In f in this case. it equal to K .69)  By 33r.80 . = X COV^ft X (QVAOl X (Q /^V)B X WWL A ^o fiT 7 ' and hence. Since. 2 for which T? f / (Q/AQl . by equation (33.43). translational and rotational factors.49) becomes In IT 7 + 6B In H = IL + mM +. the equilibrium Constants can be readily calculated.50) thus also requires a knowledge of A#J. for they may be derived with sufficient accuracy by means of the equations given in Chapter VI.64 kcal. " .57.. respectively. is fundamentally the same as that described above. although formulated somewhat differently.2 X 8.. seen that Since AF is (33. which can be obtained by the methods described in 33q. There is another approach to the problem of evaluating free energy changes of gas reactions from partition functions which.AtfJ/ftr ' ~(CVA r /OQ ' K1\ (33 51) )2 1 and 2 refer to the atoms and molecules. AF . A ^2A.282 X AHJ is  57.54.(. 276).. AF  kcal. but for the diatomic molecule 2 the partition function involves the electronic. The method of calculating K/ based on equation (33.80 Since Aff is equation (33.310 FREE ENERGY AND CHEMICAL REACTIONS 33f 57. it follows that for any homogeneous gas reaction. viz.. p. .49) JLlfJL For the general reaction aA equation (33. If this and the partition functions of the reactants and products of the process are known. The calculations may be illustrated by reference to the simple case of the dissociation of a gaseous molecule into two atoms. The translational partition function is given by equation (16. is 32c (see footnote.298. and also the contribution of one vibrationai mode.(10~) + (.
pressure.. equation (33. . For molecular iodine. and all the atoms may be regarded as being in the state for which the resultant quantum number j is The value of A#J is known from spectroscopic measurements to be 35. and so the equilibrium constant can be calculated without any chemical or thermal 2. Q. hence.e. the result will be the translational contribution to the partition function of the gas in the standard state. by replacing V by RT/P. (33. Inserting these values in the equation given above.53) is set equal to 1 atm. are the respective electronic factors. respectively. Qt = ^ RT.. the partition functions are based on the postulate of ideal behavior of gases. the other information respectively.. the atom The rotational and vibrational factors in the partition function of the diatomic molecule A* are given by equations (16. The moment of inertia of molecular iodine is 743 X 10~ 40 g. dissociation of hydrogen. For atomic iodine. e. i. required for the evaluation of the equilibrium constant Kf can be obtained from spectroscopic data.. and N measurements. together with + N . These are independent of the pressure (or volume) and require no adjustment or correction to the standard state.e. convenient to write Qt in a slightly different form. nitrogen and the halogens. and representing the masses of the atoms and with R m A molecules by m\ and m 2. hence if P in equation (33. is the AvoIf i. ." described.e. In order to obtain K/ t the standard state is that of the ideal gas at 1 atm. In some cases. R. where P is the pressure of the gas. mi is 254/7V.atm. Problem: Calculate the equilibrium constant Kf for the dissociation of molecuatoms at 1000 C. m\ is 127/AT. where gadro number. i. h. 2.51) becomes RT h* N * vh* U _ e T ' where Q e and Q \ ez the vibration fre1 In addition to A#J. cm. This result is applicable to both atoms and of each unit particle. / is its is the co is moment of inertia symmetry number. which is derived in the manner already quency in cm.2 and the vibration frequency is 214 cm. and the symmetry number is 2.52) becomes n Qt (ZirmkTy'* jr*  RT ~p(33. equation (33. respectively. therefore. of the molecule A .33r where FREE ENERGY CHANGE IN CHEMICAL REACTIONS 311 V is the molar volume. The electronic state of the molecules may be taken as a singlet. i.24) and (16. For the present purpose the partition function is required for each substance in its standard state.30). 4..e. Q*\ is 2. oxygen.g. deg. using the appropriate value of the mass or the molecule A2. respectively. the value of A//J can also be derived from spectroscopic studies.54) in cc. the masses m\ and m 2 obtained from the atomic and molecular weights.53) As seen in 16b. k. molecules.~~l mole"1 ."1 lar iodine into .a is 1. It is.480 cal. and the universal constants TT. and c. Utilizing the foregoing facts.00.
Q 2 Q* and QA are used to represent the partition functions.. units and R in the brackets in cc. respectively.55) becomes where b is also a constant.312 FREE ENERGY AND CHEMICAL REACTIONS 1 33S mole" 1 . Z. i. CD. 1234 (QVAQ.. ft. and so they may be omitted. For such a reaction. The expression for the translational partition function [equation (33. / the molecule. 693 (1942).:itm. AC where definite temperature. For the diatomic molecules the electronic factors may be taken as unity. the complete contribution is virtually unity. a very simple. 425.55) will lead to a value not very different from unity. . or double decomposition. i. cleg. of the gas reaction The example given above provides and vibration frequencies to AB + CD = AC + BD. the equation for the rotational partition function for a diatomic molecule may be written as I .30) for each vibrational mode.54)3 may be simplified in form.g. equation (33. and BD.e. and a is the same for all gases at independent of the nature of the substance. X x X/Rr _ &210J e HllRT ' (33 55) ' where. 885 (1034). Equilibrium Constants of Metathetic Reactions. and there would be an 11 appropriate term of the form of (16. so that it is possible to write equation (33. 33s. 476. see Zeise. 39.50) as . 40. if somewhat approximate. c and k in c. thus." it is found Kf of inertia (for 12  21)  O. of the diatomic molecules AB. for simplicity. . In a similar manner. The j. 48. be extended to reactions involving more complex substances. a simple illustration of the use of moments calculate equilibrium constants.. expression can be derived for the equilibrium constant.JS4. For polyatomic. at a given temperature. particularly if diatomic molecules only take part in the process. as in the case. 662. the symbols Q\. 11 For extensive reviews. for example. in which there is no change in the number of molecules. because of cancellation of terms. the molecular weight of the gas. 1273 K. (1 verv gfccw/fcrji^ are no different from unity. and.e. the equilibrium constant is independent of the standard state ( 32c). 758. nonlinear molecules the rotational contributions to the partition functions would be given by equation (16. 8ir*IkT 6 0r is M ""rtT" ?' is the moment of inertia of four vibrational factors. in any event. the cancellation of the terms in equation (33. Making the appropriate substitutions. in their standard states. The method can. that at 1000 C.s. 895 (1933).34). if they are not individually unity. Elk. When a reaction involves a metathesis. of course.
at 298 K. 48 (1934). answer the following questions: (i) Will a mixture consisting of equimolecular proportions of water vapor and hydrogen at 1 atm.22. Soc. via. ideal K' v for the methanol equiwas found to be 2.459 X X (8. see tables in text or .55)* K1. 2 2 Utilizing the free energy concept.. Bleakney and Md. is X D H X found to be 83 1Q. and hence calculate K/ at 250 C. Chem.1 X 10~2 Apply the behavior.40 ).OV/O/l/Z T m + I log Mm x ^ M f + log 7 'Hi ^ i J* * jjj 1K jjj 2 DI 83. 128 for HI and 4 for D 2 so that by equation . 101 (1943). The following equilibrium constants K/ with fugacities in atm.55 cal. The molecular weights are 2 for H 2 129 for DI.0876.. 57.35 1. /. consequently the symmetry numbers cancel. the Fe. Phys. 11. J. thus be derived from A/f for the reacof inertia. total pressure be capable of re Urey. A#J the moments of inertia are as follows: 2 (0. The symmetry numbers for H 2 and D 2 are each 2.. .40 ). and free energy data. . H + 2DI = 2 2HI +D 2 at 25 C. after converting the logarithms. Libby. J. and disregarding departure from ideal behavior. i.459 2 40 10. = Fe 2 2. entropy at end of book. cm. heat capacity.576 X 298 "*" 2 g2 X g (4.920 X 10~ HI(4.56) is zero. "Cf. 321 (1935).33s or EXERCISES 313 + The value of the equilibrium constant l + lJJ (33. and its logarithm in equation (33.31) 2 (129)* 0.55. ). 0...56).e. * For heat content. Chem. and the symmetry numbers Equations of the type of (33. FeO and C being present as solids: Fe + H O(?) . of the substances taking part.FeO + H + CO = FeO + CO C + H 0(?) = CO + H 2 2 K. and the molecular weights. espe12 cially if the temperatures are not too high. Urey and Rittenberg. EXERCISES * At 250 C and 170 atm. were obtained at 700 C. t 2.. so that the corresponding factor is unity.52 1. where the error of the vibrational partition functions is very small. isotopic exchange reaction Problem: Determine the equilibrium constant of the homogeneous gaseous between hydrogen and deuterium iodide.0 3 (128) X 4 "*" 4.56) have been em may moments due to the cancellation ployed particularly in the study of isotopic exchange reactions.31 g. 2H 2 librium. log K ""' Zi.. Urey and Greiff. and for HI and DI they are both 1. 2. Rittenberg. and X lO" 40 ). corrections for deviation CO + = CH from pressure the value of 3 OH(fir). t Phys. From spectroscopic measurements.56) tion. (33. 137 (1933). DI(8. 2 (0. 1. Am. Chem. 1.
g.. hence.314 ducing FREE ENERGY AND CHEMICAL REACTIONS at 700 C? What is likely to be the effect of increasing the total Will a gas mixture consisting of 12 mole carbon monoxide.) equilibrium constant at 500 C. let x be the mole fraction of 8 formed at equilibrium. allowing for deviations from ideal behavior. Ind. . Also check the value for A Off H ).AHJ. 1. . together with heat capacity data. is allowed to come to equilibrium at 450 C at (i) 1 atm. the maximum (equilibrium) conversion of nitrogen and hydrogen into ammonia. (ii) 200 atm.. etc. K NH NH H + +H t 600 0. ref. 4.02 300 10~8 3. 3.78 X 10~* at 800 K.. accompanying the reaction of steam at 100 atm.30 Use a graphical method. for maximum conversion to 3 .) 10. Check the results derived for 25 C in the preceding exercise by using tabulated free energy and entropy data.) 5. 29c) . Use AF values at 25 C. Eng. i. i. at any definite temperature and pressure. Chem. in the molecular proportion of 2 to 1.64 800 0. What are the standard free energy and entropy changes for the reaction at 25 C? 6. Ns and Hi molecules in the ratio of 1 to r.]..e. ref. Austin and Day. to derive an expression for the variation with temperature of the equilibrium constant of the reaction SO S JO . estimate the composition of the final mixture in each case. together with the generalized fugacity diagram. and find the condition which makes dx/dr equal to zero. (ii) allowing What is the standard free energy change of for departure from ideal behavior. Utilizing . based on heat capacities. to derive A#J for this and hence develop expressions for AF and A# as functions of the temperature. determine the true (ii) by means of the van der Waals constants (cf (Cf. tend to deposit carbon at 700 C? Above or below what pressure is this likely to occur? [Cf . the reaction at 800 K? 8. (i) assuming ideal behavior of the gases. Pease.95 900 C K reaction. obtained. 23 (1941). 9 of an inert gas (e. The following values were obtained for the equilibrium constant of the C0 2 = CO 2 O: homogeneous gas reaction 2 .S0 8 (0). Show that in the reaction 2 8 assuming ideal behavior of $H 2 == the gases. set up an expression for p in terms of mole fractions and total pressure..98 600 atm. What would be the value of f at 450 C? 9. Hence. Calculate the free energy change in cal. is obtained when the reacting (Suppose the equilibrium system consists of gases are in the proportion of 1 to 3.. A# 7.88 50 100 108 4. make a therinodynamic study of the reaction exercise. 1) to be as follows: FeO pressure? (ii) % % % K P K' p 3. nitrogen) at a total carbon dioxide and 79 mole mole pressure of 1 atni. (Use the value of K/ obtained in the preceding + K heat content. with carbon to form carbon monoxide and hydrogen each at 50 atm. heat capacity and entropy data. 33. The values of p for the ammonia equilibrium at 500 C and various pressures were found (Larson and Dodge. total pressure. 10" s 6. For the reaction C() + H 2 0(0) = CO + H 2 the equilibrium constant Kf is 2. N + NH .39 700 0. A mixture of sulfur dioxide and oxygen.e.51 X X X X 10~' Calculate the fugacity correction (i) by using the generalized fugacity diagram. 2.
calculate the free energy functions and relative heat contents..2O(J) Hg(l). 514 (1942)]. Agis PbCl 2 (s) of two faradays is Pb 2AgCl(s) 2Ag. [cf. Eng. The j value for atomic hydrogen in the ground state is i and no higher electronic states need be considered. Ind.5 X lOT. Using heat content data. which may be taken as the mean values over the pressure range. Calculate the free energy change of the reaction.2* C 605 717mm.] 18.1 188. 61.) N 2 + $H 2 = NH* reaction except 17. [See Stephenson and McMahon.M.43) and (33. By making use of the expression for the variation of Cp for graphite with temperature. 7. of the cell 2 (0) aq HgO(s).0 X 10~*!T. 54.EXERCISES 315 Determine the extent of conversion of an 2 O(0) = C 2 H 8 OH(0).21). Determine the standard entropy change for the reaction at 25 C. and for O 2 by 6. The reaction Ag(s) JHg 2 Cl 2 () = AgCl() Hg(l) takes place in a reversible cell whose E. molecular 2H is hydrogen exists in a singlet state. /. is 0. at 1000 K.M. Determine Atf. (The fugacity of the hydrogen gas may be taken as 1 atm. Suppose nothing were known of the the heat of reaction at 25 C. Am. in which the reaction for the passage of two faradays is 2 (g) HgO() . is 0. (ii) the E. 19. Chem. by equations (33. 5. Hg.55.87 and AS for the reaction Ag 2 O = 2Ag JO 2 at 25 C. AgCl. of the cell PbPbClj 1.F. hence calculate AF for the reaction at 25 C.M. The E.1 .F. 11. Chem.8 kcai. equimolar mixture of ethylene and water vapor into ethanol at 450 C and 200 atm. may be used: Ag. 1 2. determine A# at 25 C for the reaction considered in the preceding exercise. cc. estimate (i) the free energy change of the cell reaction. 2186 (1932)] to be as follows: 1 +H p 173 422 178 509 183.50 1.) 15.9264 volt at 25 C.50. Am. relative to the value at K.. Utilize the free energy function K H . Calculate the equilibrium degree of dissociation of molecular hydrogen into atoms at 3000 and 1 atm. pressure. and 25 C. Aston. (The following densities.0455 volt at 25 C and 1 atm. 1. and state whether the results tend to confirm the third law of thermodynamics. Soc. for Ag*0 by In this temperature range Cp for Ag is given by 5. Hg(J). Exercise 3).F.86 X 10~4 volt deg." 1 . The value of A#J for the reaction 2 known from spectroscopic measurements to be 102.9 X 103 !T.56.. of the cell at this temperature? What is the * (The experimental value is 0. 14. 13.47). and utilize them to determine the equilibrium constant of the reaction at 500 C (cf. The dissociation pressures of silver oxide at several temperatures were found by Benton and Drake [/. Using the moments of inertia and vibration frequencies of the molecules given in Chapter VI.F. 10.F. Soc. Chem. 34. E.) 16.M.AgCl(s). pressure.60 8.) 13. By using equation (25. calculate its free energy function and heat content. the cell reaction for the passage sat. Calculate AS by using the third law entropies in Table XV. 437 (1939).. of the ceil. at 1000 atm. soln. HgCl* + H  KOH H + + + \ + H + + + + + and relative heat content tables to determine the standard free energy change of the reaction CH4 + CO a = 2CO + 2H* at 1000 K.15 g.4900 volt. (Use heat content data from Table V to obtain Aff at 25 C. The temperature coefficient of the standard E.M. AF 13. Use this result together with the known free energy of formation of mercuric oxide to calculate the standard free energy of formation of liquid water at 25 C.
In the reaction Fe() 2 (0).) vapor into hydrogen atoms calculating the equilibrium constant of the reaction HiO OH.) 22. 33k. REACTIONS Determine the equilibrium constant of the isotopio exchange reaction C. and take A#J as equal to the bond energy of the O bond which is broken in the reaction.316 20. The and 4 for electronic statistical weights in the normal state are 1 for HsO. (The experimental value Hi + Dt .FeO(a) iron is greater than that of the oxide. (Cf problem in gas.) . higher energy states may be neglected. is 3. at 25 C. given that AHJ is 157 cal. at 2000 K.2HD at 25 H+ radicals. energy change for the process CHOH(0) .28.O vary 21. Estimate the extent of dissociation of water and hydroxyl by H H + +H with pressure? 23. Determine the standard free CHsOH(Z) at 25 C on the assumption that the vapor behaves as a Berthelot The vapor pressure of liquid CHjOH is 122 mm. How does the constant /HI//H. (Utilize the vibration frequencies and moments of inertia in Chapter VI. the density of the HjOfo) . where the vapor is treated as an ideal gas. FREE ENERGY AND CHEMICAL. using the method of partition functions. 2 for OH.
To avoid the possibility of confusion the symbol / is used here for the pure liquid.e." 2nd ed.1) where fi is the fugacity of the constituent . 1 The use of the foregoing definition of an ideal solution implies certain The variation of the fugacity /? of a pure properties of such a solution. this is misleading. that if equation (34. Hildebrand. 317 . either in the vapor or in the solution in equilibrium with it. see J.e. the partial vapor pressure Pi of any constituent of a liquid solution is equal to the product of its mole fraction N and its vapor pressure p? in the pure state. i. viz. is given by equation (29. i. at least for a solution of two components.. An ideal liquid solution is defined as one which obeys an idealized form of Raoulfs law over the whole range of composition at all temperatures and pressures. Chapter II.. the proportionality constant is equal to the fugacity of that component in the pure state at the temperature and pressure of the system. and/? is the fugacity of the pure liquid at the same temperature and pressure. so that H? is the H 1 t It is the common practice to represent the fugacity of a pure liquid by the symbol/ . since they are identical ( 3 la). whereas / is not. but in general the quantity / is dependent on the pressure. at low pressure. pure liquid at 1 aim. H. pressure. and * that of the ideal vapor. liquid i with temperature.. that in an ideal solution the fugacity of each component is proportional to the mole fraction in the given solution at all concentrations. dT where P RT* ' H* is ff? is the molar heat content of the pure liquid at pressure P. "Solubility of Nonelectrolytes.22).e. According to the original form of this law.. t For thermodynamic purposes. however. form it is preferable to use the idealized (34. 1036. i. 1 For a review of the properties of ideal solutions.! It will be seen below. and / is retained for the standard state. at constant pressure and composition. At this pressure / and /* become identical.1) applies to one constituent over the whole range of composition it must also apply to the other. Properties of Ideal Solutions. therefore.CHAPTER XIV THE PROPERTIES OF SOLUTIONS .. Pi = N p?. It follows.34. since the fugacity in the standard state is thus implied. IDEAL SOLUTIONS 34*.
15) in the form ideal liquid solution resembles n\dn\ H n^fjtjt = " 0. >.2) from (34. the result is 'In hold for any solution. therefore. the partial molar heat content of any constituent of an ideal solution (Si) is equal to the molar heat content of that substance in the pure liquid state (H?).1). thus. The DuhemMargules Equation. i. at constant temperature and pressure . Consequently. it can be readily shown that 1 _ ~ dP Jr.. at the same temperature and It follows then that there is no change of volume when the liquid pressure.6) . by equation (34. which for heat contents takes the form This expression will solution. components of an ideal solution are mixed. it follows that for an ideal solution H? ffi must be zero. there is no heat change upon mixing the components of an ideal solution.7) and (30.N . (34. when present dT where Ri is 7r. ( (34>5) As before. the condition fOIL an infinitesimal change of composition is given by the GibbsDuhem equation (26. equation (26. an ideal liquid solution resembles an ideal gas mixture ( 30d).318 THE PROPERTIES OF SOLUTIONS 34b For the same substance ideal heat of vaporization ( 29g). equation (30. 31 a). 34b. In this respect.v? RT . As a result. H? and St are identical. For a system consisting of a liquid solution of two components in equilibrium with their vapors. is independent of the temperature.e.17). and adopting a procedure similar to that given above. hence. utilizing equations (29. but in the special case of an ideal equal to N*. subtracting equation (34. so that the partial molar volume Vi of each constituent must always be equal to the molar volume V? of the substance in the pure liquid state. an an ideal gas mixture ( 30c). /t//? is H becomes H H = niH? + n //? + 2 The total heat content of the mixture is thus equal to the sum of individual heat contents of the pure liquid constituents. and ln/P with respect to pressure. at constant temperature and composition. for a mixture of definite composition. Since the mole fraction.21) is applicable (cf.6). the mole fraction of that constituent. in solution.. ///? is constant for an ideal solution.3).N RT* Upon here the partial molar heat content of i in the liquid solution. so that in this respect. also. By differentiating In/.
0.e. (34. the chemical poIt is then possible.6)]. tential is determined by the composition only. however. + dNi = dN 2 .6) is divided by n\ n*.11) equation (30. if the temperature and pressure are maintained constant.10) giving a useful form of the GibbsDuhem equation. it is seen that RTdlnfr [cf. (34. + N* = 1. so that equation (34. respec and energies or chemical potentials. (total) pressure and composition of the solution. and 2. (34.9) Since the sum of the two mole fractions seen that or dN 2 = dNi is equal to unity. i. /** is a constant for the substance at constant temperature.9) can be written =0. The chemical potential of any constituent of a solution depends on the temperature.1)..10) gives 2) . and upon substitution in equation (34. and insertion of this result into (34. C7Ni Jr. to write. Upon differentiation at constant temperature. MI and + the result is 7 HI +n z ni + + N^MS * dfJLl = A 0. therefore. (34.P \ON2/7W' L.34b IDEAL SOLUTIONS of moles of the constituents 1 319 where ni and n* are the numbers tively. P T.8) \ NI lnN 2 /7'. for an infinitesimal change of composition. it is (34. According to equation (31.7) where NI and N 2 are the mole fractions of the respective components.7) it follows that </ N2 = . present in the solution. M2 are their partial molar free If equation (34. the chemical potential of any constituent of a liquid mixture is represented by where /* represents the fugacity of the given constituent in the liquid or in the vapor phase with which it is in equilibrium.
irrespective of whether the solution (or vapor) is In the derivation of this equation no assumption or postulate ideal or not. derived independently. Margules (1895).12) is applicable to any liquid solution of two constituents. it follows that mind that f% be /2 . so that equation (34. is compared with equation (34. d In NI \  1. it can be shown that if the Raoult equation (34. A. it is found that d or / ^ i In /i /. so that /I  Nl/P. but it involves the supposition that the vapor in equilibrium with it behaves ideally. Qibbs (1876). The form given in equation (34. It is important to note that equation (34.14) since result.320 THE PROPERTIES OF SOLUTIONS 34C This is the precise form of what is known as the DuhemMargules equation. by J. W. If this which is applicable at all concentrations. Lehfeldt (1895). and R. the fugacity of each component in the vapor may be replaced by its respective partial (vapor) pressure. and in various ways.15) Upon is comes equal to /? when N2 integration. It is frequently encountered and employed in a less exact form which is based on the approximation that the vapor behaves as an ideal gas.P also at all concentrations. of these constituents. 34c. Upon taking logarithms and differentiating with respect to NI.1) is applicable to one constituent of an ideal binary solution. (34. it is seen that /ain/. By means of the DuhemMargules equation. and hence they are of completely general applicability.12) becomes In pi \ d\npz\ (34 13) ' where p\ and 3)2 are the partial vapor pressures of the two constituents in equilibrium with the liquid containing the mole fractions NI and N 2 . at constant temperature and pressure. 1. over the whole range of composition. (34. Suppose the law holds for the constituent 1. Application of Raoult's Law to Both Constituents of an Ideal Solution. was made concerning the properties of the solution.13) is also independent of the ideality or otherwise of the solution. M. the results are based only on thermodynamic considerations. Duhem (1886). P. In this event.12). bearing in unity.\ \dlnN2/T. it must also apply to the other constituent. /? is constant for a given temperature and external pressure. respectively.
at a given temperature. Am. P = pi p 2 . If equation (34..34d IDEAL SOLUTIONS 321 It is clear. although for strict 2 accuracy it should be understood. The plot of the Mole Fraction Nj0 partial pressure of each constituent N a 0 N. Farad. 20. that if Raoultfs law is applicable to one of the constituents of a liquid mixture. as shown by the thin lines in Fig. Provided the pressure is not too high. at all compositions. Chem. and Kaaamoweky. it must be equally applicable to the other constituent. it must hold for the other. The total vapor pressure P is the sum of the two partial pressures. Trans. This has been implied in the foregoing treatment. Vapor pressure curves phase.i against its mole fraction in the liquid FIG.17) so that the total vapor pressure also varies in a linear component in the liquid phase. + Pfraction of either NipP Nip? + + (1 Ni)pf  P? + Ni(pP  p?). the restriction of constant total pressure is not emphasized. however. 705 (1940). in many of the practical applications of Raoult's law given below.e. therefore..16) as given at the commencement of this chapter. should remain constant as the composition is changed. Bury. for ideal solution should be a straight line passing through the origin. 34d. Cf. i. (34. since N 2 is equal to 1 NI. the vapor will not de ment always it is part greatly from ideal behavior. the fugacity (or vapor pressure) is virtually independent of the external pressure ( 27m). it is the vapor pressure which is the corresponding property of practical interest. so that ' pi  and for all mixtures of the two constituents 1 and 2. Vapor Pressure Curves. hence. 36. (34. Although precise thermodynamic treatrequires the use of the fugacity in the equations given above. At moderate pressures. . J. 20. Krichevsky manner with the mole 2168 (1036).. under which the system is in equilibrium. Soc. Attention may be called here to the restriction in connection with Raoult's law that the total (external) pressure.16) is applicable over the whole range of concentrations for one constituent. at constant temperature. hence. 57. and permissible to use Raoult's law in its original ( form Pi = N#?. Soc.
at 30 C. of\ benzene in vapor _ 64.. "l " (w/Mi) M* w/Mi ~ + (w/Mj Mi + A/ 2 benzene (Mi) 92. and of toluene (M 2) it is 92. (For alternative method of obtaining the weight composition. the proportions by weight are then obtained by multiplying by the respective molecular weights. and N 2 by 1 with equation (34.0. Let are w be the weight of each constituent in the mixture.19) that the total vapor pressure is not a linear function of the mole fraction composition of the vapor. should contain 3.) By replacing N by then combining it 1 NI in equation (34.18) ' provided Raoult's law is applicable. then of the v (34.0 mm.18).2 .2 mm.322 THE PROPERTIES OF SOLUTIONS 34e 34e. Composition of Liquid and Vapor in Equilibrium. it follows that From it is P?) this result possible to calculate the total vapor pressure P for It is fraction of the constituent 1 in the vapor. in the case of an ideal solu . and p 2 0.23 parts by weight of the former to 1 part of the latter. viz. at 30 C. are then pi wt. although it is such a function of the composition of the liquid phase.541 X 118.8.8 wt. the mole fractions NI and N 2 are . Determine the partial pressures and weight composition of the vapor in equilibrium with a liquid mixture consisting of equal weights of the two constituents. assuming the vapor to behave as an ideal gas.0 The partial vapor pressures.0 + 92.64. The composition vapor phase in equilibrium with any liquid solution is readily derived from the fact that the number of moles (or the mole fraction) of each constituent in the vapor must be proportional to its partial pressure. if the molecular weights Mi and M 2 respectively. see Exercise 23.0.8 mm. and that of pure toluene is 36.459 X 36.0 16. assuming Raoult's law and ideal behavior of the vapors. although the liquid contains equal weights of benzene and toluene.7 = 16.7 mm. Problem: Mixtures of benzene and toluene behave almost ideally. the vapor. value the mole any Ni. = 0. If Nj and N represent the mole fractions of the two components in the vapor. the vapor pressure of pure benzene is 118. of toluene in vapor X X 78 92 Consequently.0/16. The ratio of the numbers of moles (or mole fractions) of the two constituents in the vapor is thus 64.0 = ' and *" u "2 ~ ~ MX Mi +M 2 The molecular weight of Nl is 78.17) so as to eliminate NI. evident from equation (34. sathat * 78. and NI..
dfi or d In/* Since the composition of each phase changes at the same time. the vapor will always be relatively richer than the liquid in the more volatile constituent.34f tion. The change in //. When the temperature of a liquid solution is changed the composition of the vapor in equilibrium with it will be The relation between the mole fraction of a given affected accordingly.e.18) that for an ideal liquid system. (34. as in Fig. i.e. 21. must tilen be equal to the change in /. and FIG. at constant pressure. At any value of the total respectively. Influence of Temperature. for the liquid phase. and hence Ni/N2 will exceed Ni/N2.20) becomes T. respectively.. 21..21). in which the upper (linear) of the vapor. so that equation (34. the one with the higher vapor pressure. 34f . This fact is fundamental to the separation of The limitations arising in connection liquids by fractional distillation. 21.17) or (34. and suppose the temperature is increased by dT.e. with temperature is given by equation (30. for the vapor phase. 31a). constituent in the liquid and vapor phases can be readily determined by making use of the fact the fugacity must be the same in each phase if the system is to remain in equilibrium. For example. It can be seen from equation (34.P RT* 'dr.P The variation of ln/i. and lower (nonlinear) curves represent the total vapor pressure as a function of the mole fraction composition of the liquid (NI) and of the vapor (N'I). p? will be greater than Mole Fraction p!?. IDEAL SOLUTIONS 323 By utilizing either equation (34. the component N t Nj0 N{ 1 is the more volatile.20) T.21) . pressure P. if. dfi or d In //.19) it is possible to plot the variation of the total pressure with the mole fraction of either constituent The result is shown in Fig. Let // and /t represent the fugacities of the constituent i in the vapor and liquid phases. by an equation of the same form (cf. and that of ln/<. the system remaining in equilibrium.. 35c. the point A consequently gives the composition of the liquid which is in equilibrium with a vapor of composition represented by the point B. with nonideal systems will be considered in 35b. i. it follows that P. Composition of liquid the vapor will contain relatively more of the and vapor for ideal solution component 1 than does the liquid with which it is in equilibrium. i.N< (34.
34a) it is then seen that These . it follows from equation / V (34. the fugacity /<.23) A/A . Since constituent 1 is the more volatile. for the pure substances. For practical purposes. The result just obtained is applicable to any liquidvapor equilibrium. T. and the righthand side of equation (34. According to Trouton's law ( 27j). the quantity NjN2/NiN^. A#i is less than A/?*.P N Similarly. or partial pressure. If the ratio of the mole fraction in the vapor phase to that in the liquid. if. equation (34. and at the same time the partial molar heat content terms Fli and ff' t may be replaced by the corresponding molar heat contents // and H't. is that in the liquid phase. the lower the boiling point Tb that is to say. Ni/Nt. in other words. The value of ki/kt will thus increase with decreasing temperature. the heat of vaporization. should be large. this is 34e that if component 1 is the more volatile.e. hence. is represented by fc. irrespective of the behavior of the gas phase or the solution.24) will usually be negative.21) can be greatly simplified. therefore. dT P the numerator on the righthand side being equal to AjfiTv the molar heat of vaporization of the constituent i at the temperature T and pressure P. respectively. which equivalent to ki/k*. _H' t H< _ AHV . By equation (34. however. these are assumed to be ideal.1) that for the liquid solution results can be inserted into equation (34.324 THE PROPERTIES OP SOLUTIONS 34f where B( is the partial molar heat content of the constituent i in the vapor phase and #. the smaller the value of A#.. . since ideal behavior has been postulated for both phases (cf. &Hv /Tb is approximately constant for all substances. the ratio N/N For purposes of fractional distillation it is deskable to make difference as large as possible.. the more volatile the liquid. For an ideal gas mixture. it follows that for any constituent of an ideal system ' It will was seen in exceed N^/NJ. i. at constant temperature and total pressure ( 5b) it can be readily seen. 30d. and hence better fractionation can be Achieved by distilling at a low temperature. of any constituent is proportional to its mole fraction N<. that . this means .21).A// 2 ' (34 24) * and hence it is of interest to find the conditions which will tend to increase the value of Ai/fo.
ideal solubility of ethane at 25 atm.84 atm. It is thus possible to calculate the solubility of an ideal gas in an ideal solution at any temperature below the critical point. 1. of ideal gas at pressure on the vapor pressure (cf . 30. tit. appreciable departure from ideal behavior would probably occur.7 atm. ref. 100 C and Problem: The vapor pressure of liquid methane is 25. provided the vapor pressure of the liquid form at the same temperature is known. op.024 mole fraction... it is necessary to estimate a hypothetical vapor pressure by suitable extrapolation. In order to extend the method of calculating ideal solubilities of gases to temperatures above the critical point.. p? is 42 atm. the hypothetical value at a temperature above the critical point may be evaluated on the assumption that the heat of vaporization remains constant. and if it behaves ideally Raoult's law will be applicable. liquid may be treated from the thermodynamic standpoint as a liquid mixthe gas ture. so that P2 = 1 Nspi . The Solubility of Gases.25) interpreted as giving the saturation solubility. N2 = The be 0. where /2 is the fugacity in the 3 solution. i. pressure. way the solution of a gaseous substance in a 34g. If the gas is assumed to be A K ideal. . ^ = 0. at 120 C. In this connection. pressure in any solvent should The solubilities of ethane in hexane and heptane are not very different from the ideal value calculated from equation (34. hence. If the vapor pressures at any two temperatures are known.25).024 mole C and 1 fraction. This is best done with the aid of the integrated form of the ClausiusClapeyron equation. at at 25 C and 1 atm. Calculate the ideal solubility of ethane in a liquid solvent at the same temperature at a pressure of 1 atm. i 27m) is neglected. assuming the gas to behave ideally. 3 Problem: The vapor pressure of liquid ethane at 25 C is 42 atm. when the liquid cannot exist and direct determination of the vapor pressure p is not possible. and /J is the fugacity of the pure substance in the liquid state at the same temperature and external pressure..34g liquid can be IDEAL SOLUTIONS 325 that distillation should be carried out under reduced pressure. then/2 = N2/JP. Estimate the ideal solubility of methane in any solvent 11. the fugacities may be replaced by the respective pressures. and p 2 is specified as 1 atm. is designated as constituent 2.. and the solubilities would differ from the ideal value calculated above. (34. however. * Hildebrand.e.25). Utilizing equation (34. N 2 mole a partial pressure p* and a specified temperature. In solvents which are not chemically similar to the solute. the is then vapor pressure of the liquefied gas at the same temperature p? and total pressure. p. the very small effect of the total external which may be an fraction. for in this made to boil at a lower temperature than normal.
00325. and hence its mole fraction N. / 173 4. .7 atm.e.7 g " Aff.  25..25) hence. which is assumed to remain constant. p is 25. 173 K.576 \ 153 2. in principle.84 X 153 \ 173 / ' A#.84 atm... and at . i. i. that the smaller this vapor pressure the greater will be the Gases which are difficult to solubility of the gas at a given temperature.120 C.e. Utilizing this value of the heat of vaporization. the easily liquefiable gases would be the more soluble in a given solvent at a particular temperature.. AHV may also be identified with the heat of It should be noted that solution of the gas. Even though most solutions of gases are not ideal. 153 K. This gives p? to be used in equation (34.25).22) in the form . p 11. such gases will consequently have low solubilities.0031 and in xylene it is 0. by liquefying * This condition would be approximated at total constant pressure if the vapor pressure of the solvent were negligible in comparison with the pressure of the gas. the ideal solubility of methane at 25 C and 1 atm. if the gas pressure p* is 1 atm. f (34 26) ' provided both gas and liquid solutions are ideal. mole fraction. .) According to equation (34..0026. the ideal solubility of an ideal gas under a pressure of 1 atm.14).e. lows. 34h.* equation (34.576 \ 173 173 \ X 298 / ' p = 308 atm... those having low boiling points.. . is derived from the analogous expression g p 25.037 11. in any solvent. will have high vapor It is thus to pressures. this general conclusion is in agreement with experimental observation. (The observed solubility in hexane is 0. Influence of Temperature on Gas Solubility. where p? is the vapor pressure It folof the liquefied gas at the experimental temperature and pressure. 0. The latter can be determined.  cal. i. should be equal to l/p . The influence of temperature on the solubility of a ^as is given by equation (34. hence by the integrated ClausiusClapeyron equation (27.037/298 4. the hypothetical vapor pressure p at 25 C. remains constant. liquefy. mole" 1 . therefore.326 THE PROPERTIES OF SOLUTIONS 34h is At 100 C. In the special case in which the partial pressure of the gas. is N 2 = 1/308. 298 K.e.26) becomes where A# v is the molar heat of vaporization of the liquefied gas at ^he given temperature T and total pressure P.7 = 2. i. be concluded that if solutions of gases in liquids behaved ideally. that is to say.
there are many instances in which the solid phase is a solid solution containing both constituents of the system. SolidLiquid Equilibria. the latter point of view is usually adopted. the constituent present in excess. However. and this is equal in magnitude. the ideal solubility of a gas. be first treated in a general manner and the results will later be applied to special cases. If the two components of the system are such that it is not desirable to distinguish between solvent and solute.e. The relatively few cases in which this rule fails. the temperature is said to be the freezing point of the solution at the particular composition and pressure. and the simplifications which are possible when the solid &H consists of a single substance will be introduced later. it is more A/7V as the heat of solution convenient for practical purposes to regard If as of be taken this mole independent of temperature. Since it is unlikely that the latent heat of vaporization of the liquefied tions. equamay per gas. i. the composition of the solution may be regarded as giving the saturation solubility of that constituent at the temperature and pressure of the system. therefore. if the of the solubility of the gas with temperature. separates as a solid. If the solution is ideal.g.. On the other hand. are to be attributed to marked deviations from ideal behavior (cf.e. solubilities at two or more temperatures are known. it has been tacitly assumed that a pure solid separates from the liquid solution in each case. the heat of solution can be calculated. if the solvent. certain aqueous solutions of hydrogen halides. It may be noted that since the heat of vaporization V is always positive. In the preceding paragraph. but opposite in sign. and adding the resulting liquid to the liquid solvent so as to make the saturated solution. the compositions of both phases will be altered if the system is to remain in equilibrium. However.341 IDEAL SOLUTIONS 327 the gas. to the heat of vaporization of the liquid constituent 2 under the specified condiA further consequence of the foregoing argument is that the heat of solution of a given (ideal) gas forming an ideal solution is independent of the nature of the solvent. at the experimental temperature and pressure. at a given pressure. If the solid phase is that of the solute. When one of the components of a binary solution separates as a solid phase. the constituent present in smaller proportion. gas can be determined at normal temperatures and pressures. the fugacity of a given constituent must .. The most general case will be examined first. The subject will. should decrease with increasing temperature.27) can be integrated so as to yield an expression for the variation On the other hand. i. as far as thermodynamics is concerned the two types of system are fundamentally the same. the system may be considered from two points of view.. hence the heat of solution is equal to the heat change in the first stage. there is no change of heat content in the second stage of this process ( 34a) . in spite of the change in composition and temperature. 34i. e. 35a). When the temperature of a system consisting of a binary liquid solution in equilibrium with a solid solution is changed. Although this is frequently true. tion (34. since each involves an equilibrium between a binary liquid solution and a solid phase of one of the constituents.
e. By following a procedure 34f it similar to that used in connection with the analogous problem in .P Ni (34.. in the form / \ 1_ __ \ A TT (34.29) then becomes solution This equation gives the variation of the mole fraction solubility with temperature or of the freezing point with composition. i. and the latter will be deferred to a later section. which . Hi and B( become equal to the molar heat contents of respectively. the fugacity of any constituent in each phase is proportional to its mole fraction in that phase.21)] . and.31) gives the variation with temperature of the concentration of a saturated f is the molar solution. T.Hi B'i i at the molar heat of fusion of the given temperature and pressure.n dT JP where AfiT/ is _ ~_ ~ A/7 . heat of fusion of the pure solid solute at the given temperature and pressure. 8ln(Ni/N.P ** \ N< T. Influence of Temperature on Solubility.30).328 THE PROPERTIES OF SOLUTIONS 34j always have the same value in both phases. and T.* As before.. hence. In the special case in which the solid which separates from the liquid is a pure substance.28) reduces to pure liquid and solid i. equation (34. If component 2 is taken 34j. at the same time. at constant pressure. AH is * In the present chapter. equation (34. this result can be simplified by postulating ideal behavior for both liquid and solid solutions.P Ni 1.P where Bi is the partial molar heat content of the constituent i in the liquid phase and #'< is that in the solid phase. The former aspect of this equation will be considered below.28) T. is found that [cf. to be the solute. that is to say. equation (34. it is supposed that at constant temperature and pressure. In these circumstances. in accordance with the usual convention. a prime is used to designate the phase (vapor or solid) in equilibrium with the liquid solution. equation (34. respectively. the variation of solubility with temperature. N' { is unity at all temperatures and pressures. according as i is the solute or solvent.
2 C. i.. 29. . the slope of this line should be equal to A/7//4.576. Andrews. /. Chapter X. Chem.. It is only in a few cases.33) to hold exactly. Soc. (1925). Assuming A#/ to remain constant at 4. 882 et seq. 2402 (1935). should be a straight line terminating at the melting point.. op. phys.. Chem.353 K. J. and solubilities in fair agreement with experiment can be calculated from equation (34. ref. the pure solid is in equilibrium with liquid of the same composition. 191 (1915).540 be employed with cal.. Proc.32) or (34. When the solid and solute are similar in nature the solutions behave ideally. Problem: The melting point of naphthalene is 80. Ind. Z.32). Chem. Hildebrand. 1 atm. Nat. 57. Chem. that the slope has the theoretical value. equation (34. Acad. expressed in mole fractions. this is not surprising. (34.. If the heat of fusion is independent of temperature. et al. 1. Eng. ...e. 1. Ward. 449 (1893).. . According to equation (34.33) the plot of the logarithm of the solubility of a solid. 36. Phys. utilizing 4 only the melting point and heat of fusion of the Solid solute. Washburn and Read. linear over a considerable temperature range. and its molar heat of Determine its ideal solubility fusion at this temperature is 4.. Sci. 39. + *Schroeder. and second. Am.34j IDEAL SOLUTIONS 329 It will be recalled that this result is based on two assumptions: first. Germann and Germann. ideally of C in equation (34. i.31) can be integrated at constant pressure.540 cal.33) may 273 . Experimental observations have shown that in many cases the plot of log N 2 against I/ T is. and Tm as 80 equation (34. that the solution behaves ideally. 1/!T. mole*"1. that the solute which separates from the solution is always pure solute and not a solid solution. Johnston. it follows from equation (34. in fact. .e.. when the mole fraction N2 of the solute in the liquid phase is unity. moie~ l . to yield C.33). II. see also.32) that C is equal to AHf/RTm . ibid. Upon inserting this result. This expression gives the solubility N 2 If the solution behaves in mole fractions. however. the temperature is then the melting point Tm Since In N 2 is now zero.g. for the saturated solutions would have to be ideal for equation (34.32) where C is an integration constant. as a function of the temperature. it is seen that or where A/?/ is the molar heat of fusion in calories. at 20 C. Morris and Cook. T equal to 20 + 273 293 K. 2402 (1935). 93 (1944).. eft. e. log N 2 against the reciprocal of the absolute temperature. it is the whole over possible to derive the value composition range. Thus.
and hence the force acting upon it. It is to be anticipated. ethyl bromide and iodide. which is a measure of its tendency to escape from the solution. if the heats of fusion of two substances are not very different. which form nonideal solutions. solution of gases. nhexane and ftheptane. so that the actual parIf the constituents of a ideal behavior are to . deviations be expected and are. and hence the quantity in the parentheses is always negative. THE PROPERTIES OF SOLUTIONS 4.018 in methanol and 0. Such is actually the case. and which might be expected to form approximately ideal solutions. therefore. benzene and toluene. the experimental values in solvents which are chemically similar to the solute.224 mole fraction. for the relatively few liquid systems which are known to behave ideally. .. cules must be similar. that under these conditions the partial vapor pressure (or f ugacity) of each constituent. for example. observed. consist of similar molecules. the one with the larger value of Tm i. are 0. if two solids have similar melting points.e.266. will be directly that if proportional to the number of molecules of the constituent in the liquid phase..266 mole fraction. NONIDEAL SOLUTIONS Theoretical considerations 35a.0456 in acetic acid. the one with the lower heat of fusion should be more soluble than the other. in fact. the values are quite different.330 hence. from mixture differ appreciably in nature. 35. Second. In hydroxylic solvents. should have the smaller mole fraction solubility in any solvent. this is because the melting point Tm must be greater than the experimental temperature T. or to approximate to ideal behavior. e. These deviations are most frequently "positive" in nature. with the higher melting point. ethylene bromide and propylene bromide. That this should be the case can be readily shown by means of a procedure exactly analogous to that employed in 34h in connection with the heat of Two general from equation (34. deductions concerning the solubility of solids may be made First. viz. 0.g.540/293 35*  353 \ N2  0.. nbutyl chloride and bromide. The ideal solubility of naphthalene in any liquid solvent at 20 C should thus be 0. the two types of moleThe environment of any molecule in the solution. This is equivalent to stating that a mixture of two liquids consisting of similar molecules would be expected to obey Raoult's law. and consequently for a given solute the former should be independent of the nature of the solvent. Deviations from Ideal Behavior. and benzene and toluene.33). is then not appreciably different from that existing in the pure liquid.241 and 0. respectively. show a mixture of tw6 liquids is to behave ideally. For an ideal solution the heat of solution is equal to the heat of fusion of the solid at the given temperature and pressure.
which holds for solution of all types. The general conclusion to be drawn. thus ff t is greater than H?. is equal to niBi n 2fl?. op. indicating positive deviations for constituent 1.1)]. Negative deviations from ideal behavior are only observed in systems in which the different molecules have a very strong attraction for one another. Vapor Pressure Curves for Nonideal Systems. the slopes of the two partial vapor pressure curves are related by the DuhemMargules equation. implying positive deviations from ideal behavior for constituent 2. if the A * For a review of the behavior of nonideal III. By using arguments analogous to those presented above it is a simple matter to show that the formation of a solution exhibiting negative deviations from RaouWs law is accompanied by an evolution so that /2 #  H H + + . if its partial pressure (or fugacity) is less than that required by Raoult's law. in this particular case. heat must be abbefore mixing. instead of being equal to. therefore. 22. the same must be true for the other component. it follows from the argument in 34c that /ain/2 \ \d In N 2 /r. Incidentally. these results refer to a constant depicted in Fig. consequently H? /?< for each constituent is positive. respectively. 1. For a nonideal solution exhibiting positive deviations /<//? for each component is greater than its mole fraction N. if f\ is greater than. equation (34. that is to say. njt 2 sisting of ni moles of constituent 1 and n 2 moles of 2. solutions. At any given composition. therefore. The general nature of the vapor pressure curves showing positive and negative deviations are and B. cit. the ratio ///? usually decreases with increasing temperature. According to equation (34. see Hildebrand. This means that for a system of given composition for which the deviations from Raoult's law are positive. t ref. while the sum of the heat contents of the separate sub3tances is niff? it is evident that Since z is greater than i is greater than H? and the heat content of the solution must be larger than that of the constituents In other words. is that upon mixing two liquids which yield a system exhibiting positive deviations from RaouWs law there is an absorption of heat.4). 35b. H. sorbed when the pure liquids are mixed. it will be evident that if the deviation from Raoult's law is "negative" for one component. Thus. contive. the numerator H? t must be negaThe total heat content of the solution. temperature. Chapter . For a system which manifests negative deviations from ideal behavior the ratio ///? increases as the temperature is raised.35b tial NONIDEAL SOLUTIONS 331 vapor pressure (or fugacity) of each constituent is greater than it should be if Raoult's law were obeyed.\ It is an experimental fact that as the temperature is increased most liquid solutions tend toward ideal behavior. 6 of heat. NJ/? [cf. the other constituent must do likewise. Thus./> must be greater than N^/?. It can be readily seen from the DuhemMargules equation that if one constituent of a mixture exhibits positive deviations from ideal behavior.
. 581 (1942). Z. 1278 (1938). Chem. where N! and Ng refer to the respective mole fractions in the vapor phase. corresponding to any composition of the solution.. and B the uppermost curve gives the total vapor pressure as a function of the composition of the liquid. so that the vapor contains more of the constituent the addition of which causes an increase in the total vapor pressure. 35. Scatchard and Raymond. Carlson and Coibum. Am./p f and dpi/dtfi for each constituent. 905 (1934). /. Eng. however. A . Zawidski. B For any given solution the value Nonideal solutions: (A) positive deviations. i. 22. 35d). Soc.e.. 60. (B) negative deviations two constituents have been determined. This is frequently used as a test of the reliability of experimental Where it appears necespartial vapor pressure data for nonideal mixtures. The corresponding curve as a function of the vapor composition will lie below it in each case. Chem. that N{/N is equal to pi/p* ( 34e).. x sary. 129 (1900).d^ (3gl)  constant temperature and pressure being understood.. Ind. The quantities N. 504. Beatty and Calingaert. ibid. 26. allowance should from ideal behavior. which is possible even if the solution not ideal. the DuhemMargules equation (34. 34. can be readily derived if the partial vapor pressure curves of the Mole Fraction Mole Fraction A FIG. . of the product of N t/p and dpi/dNi should then be the same for both constituents. If an expression for the partial vapor pressure in terms of the molefraction composition of the liquid is available (of. phys. 6 be made for the deviation of the vapor In both Figs. 22.332 THE PROPERTIES OF SOLUTIONS 35b is yapors are supposed to behave ideally. an analogous expression for the vapor composition can be derived by utilizing the relationship based on the postulated ideal behavior of the vapor.13) may be written in the form Ni. Chem.rffil^Nl.
A liquid mixture having the composition represented by a maximum or a minimum will distil without change of composition. for the proportions of the two constituents are then the same in the liquid and vapor phases. the total vapor pressure is to increase as the mole fraction of constituent 1 in the system is increased. since the partial of any component never decreases as its mole fraction in the liquid pressure is increased. NI Pi C?NI is ^1 + Nj. Liquid and Vapor Compositions. In any event. Such maxima and minima are the cause of the formation of the familiar constant boiling mixtures or azeotropic mixtures. be associated with a minimum in the curve.2) vapor pressure respect to NI gives The total P equal to p\ + pz.1) may be written as . or If the 2J>2!. pi/p* (34. P* N2 vapors behave as ideal gases. a negative deviation will. may be derived from the DuhemMargules equation. then any appreciable positive deviation from Raoult's law will lead to a maximum in the total vapor pressure curve. The factor dpt/dtfi. and hence it is necessary that is equal to N'I/N^. Consequently.4) is positive. by equation (35. the condition for dP/d**i to be positive. dNi is equal to (35. and thus. Since the increase in the mole fraction of one component of a binary mixture must be equal to the decrease for the dN 2 as seen in 34b. equal to dp 2 /dN 2 must always be negative. by equation 2j>2!N N 2 (35. using the form of (35. respectively.5) . even if the vapor pressures of the pure constituents are appreciably different. in the same circumstances. I dp* . it is necessary to determine under what circumstances the righthand side of equation (35.18). the relative compositions of liquid and vapor in equilibrium. hence equation other component. that is to say. p dNi 2 (35. phase is that . j and differentiation with dP _ dp . marked positive or negative deviations can lead to a maximum or a minimum.35C NONIDEAL SOLUTIONS 333 If the vapor pressures of the two pure constituents are close together.^o.2). (354) Nip 2 / Suppose it is required to find the condition that makes dP/dxi positive.1). similarly. which are applicable to systems of all types. in the total vapor pressure curve. That this must be the case will be shown in the next section. Some general rules concerning 35c.
positive or negative.e.8) where /? and /? are. An equation. (35.. and the vapor will have the same composition as the . and in 21 and 22).6) * N S which is an expression of general applicability to each constituent of any mixture. For a maximum or minimum in the total vapor pressure curve. that all terms beyond the first in the exponents of equation (35.6).8) can be . however. /3a. The constants j8i. i. By combining equation (31.2) for the activity of any component of a liquid solution in terms of its chemical poRTlna*. 7i and y*. For nonideal solutions. since it would mean that the partial vapor pressure would remain constant in spite of a change of composition.8) would then become identical with (34.5) which defines the activity tential. ideal or nonideal.7) and /i .334 THE PROPERTIES OF SOLUTIONS 35d In other words. dP/dxi must be zero. which are not independent. The of this conclusion has in been 34e for seen already general applicability 35b for those exhibiting marked nonideality (Figs. or N 2pi must equal Nip 2 The former condition is unlikely. as usual. as stated above.N^etf N ^ Nl i+"'.. ideal solutions. it will be supposed.7) and (35. either dp*/d$\ must be zero. 71. the result is + and hence /. a = ///?. the fugacities of the pure liquids. and so for a maximum or minimum in the total vapor pressure curve N2pi = Nip* or Ni/N2 = Pi/p* If the gases behave ideally. as is frequently the case. Pi/Pa is equal to NI/N^. In order to describe the procedure for evaluating the constants without making the treatment too complicated. by equation (35. AU /ij as the relative fugacity..e. General Equations for Liquid Mixtures. etc. the vapor must be relatively richer in the constituent 1 than is the liquid with which it is in equilibrium. and equation (31. For an ideal solution. if dP/dNi is to be positive. and extent of departure from ideal behavior. The vapor thus contains relatively more of the substance the addition of which to the liquid mixture results in an increase of the total vapor pressure.7) and (35. this can be written as (35. liquid in equilibrium with it. this equation may be written as (35. hence. replacing the vapor pressure by the fugacity. 35d. they were proposed because they appeared to represent the experimental data in a satisfactory manner.. Margules (1895) to express the variation bf vapor pressure with composition of liquid mixtures in general.. Utilizing the fact that x is equal to e1 " *. i. was suggested by M. depend on the nature. It should be understood that these equations have no real theoretical basis. can be derived from the slopes of the fugacity actually partial vapor pressure curves at N< = or N< = 1.1). the sign and magnitude of 0i.4). somewhat similar to (35. etc. these constants would all be zero. viz. so that equations (35.
Of.7). respect to In NI and In N 2 . when the vapor pressures are not too high. J.9) where conditions.8). and /. to the The equations approximation that 71. Zawidski.12) these results must be identical. since p? or pip may be regarded as In most cases. at either end.3). &\ is equal to 2 for the variation of fugacity with the mole fraction thus become . It is thus possible to derive /3 directly from the slope. = N^e^iAi+*i>. 6.7) and (35.10) The relationships between the constants ai. and hence. Soc.35d NONIDEAL SOLUTIONS 335 Upon taking logarithms of these expressions and differentiating with neglected. and differentiating each with respect to NI. Farad. thus. in accordance with equation (35. Chem. are negligible. 336 (1920). Chem. it is seen that and According to equation (34. of the plot of the total vapor pressure against the mole fraction. It is then found that aij3* 7 a2 and atjSi = ai. at constant temperature and external pressure. it is possible to determine ft from equation (35. 16. Soc.. same Under most ordinary By inserting the value of pi or p 2 for a solution of known composition. thus.. J. /i 3 is . (35. . van Laar (1910).9) by the respective partial pressures. .N 2/e*K. addition of the results gives dP/dNi. Replacing the fugacities available. Levy. and aNi = p? p?e* ff . 7 2 etc. variation of the vapor pressure with composition. Ind. Am..9). see also. which is said to be more convenient for certain purposes. Porter.8) and (35. was proposed by J. NI = an^d NI = 1.9) then give the partial vapor pressures. Eng. Trans. they are frequently used in the in both cases. in the equations (35. 33. 7 this form. the fugacities may be replaced by the respective The equations (35. Lewis Murphree. an alternative method is used. can be derived by means of the DuhemMargules equation in a manner similar to that described above. via. when NI 1 and 0. Another form of the general empirical equations for the variation of the fu gacity with composition. the results are ~ P?t when NI = = and N2 = N2 = 1.. respectively. (35. 1 (1924). and . which are different from those in the Margules equations (35.NrfeW5 and /.. 46. 928 (1941). Two special cases ** ~j may now P?e*0 be considered. . 0i and <* 2 2 . ref. (35.
by lowering the temperature or by changing the components. negative. in which. with vapor pressures in place of fugacities.e. of course. a consequence of the DuhemMargules equation. by means of the equations (35. when the vapor pressure (fugacity)composition curve of one component of a binary mixture is known. this quantity. partial miscibility. is increased. 35e. Partially Miscible Liquids. so that the exponent is positive in the latter case. Both the Margules and van Laar formulae are capable of representing positive and negative deviations from ideal behavior. be seen. positive deviations. it can be readily shown that the variation of fugacity (or See Carlson and Colburn. . the relationships among the constants a. however.. are useful for the analytical expression of experimental data. particuIt is of interest to note that larly for extrapolation and interpolation purposes. Mole Fraction Partially miscible liquids Nl has a positive value. the exponential factor is greater than unity. automatically determine the nature of the curve for the other component. In the former case. 8 The Margules and van Laar equations.. a separation into two This can layers. i. 23. which is a constant for a given pair of liquids at a definite temperature..e. This is. In the event of large positive deviations from ideal behavior. for a system N~0 FIG. e. ref. this factor is less than unity. becomes possible. 0. As exhibiting positive deviations from Raoult's law.9). negative deviations. the values of which can be obtained from vapor pressure curves..336 THE PROPERTIES OF SOLUTIONS 35e so that there are only two independent constants. The systems considered so far have consisted of completely miscible liquids forming a single layer. i. for example.g. the exponent being . etc. 6. that is to say.
6 and c. which is the same in both layers (points a and c). 1. having different compositions. Porter. irrespective of the overall composition of the system. of course. be reached by means of the phase rule. ref. the partial vapor pressure of a given constituent will have a constant value. DILUTE SOLUTIONS It has been found experimentally that as the mole a constituent of a solution approaches unity.* In Fig. 6 and c. quite similar curves will be obtained for the other. Actually. the situation is similar to that arising in connection with the van der Waals 5d) the point b cannot be realized. 23. be identical. It is evident from Fig.. et al.36a NONIDEAL SOLUTIONS 337 partial vapor pressure) with the composition of each substance may be repreIn order to make sented by curves of the types I. for a given temperature. as obtained experimentally. The same 10 conclusion can. for example. op. and the fugacity. ref. Butler. 674 (1033). 36. cit. will occur at the same compositions on the curves for the two constituents of the system. 10 See. 23 that when two layers are present. when the conditions are such that two liquid layers are formed. is flat between a and c. In between the compositions represented by the points a and c the two liquids are partially miscible at the given temperature.0 (curve II) the curve exhibits a horizontal inflection. . the points a. is plotted against the mole fraction of the corresponding constituent in each case. as seen in curve III. a. The points of horizontal inflection C will. such systems exhibit a lower consolute temperature. within a parpairs of liquids ticular temperature range. at a given temperature. of course. is When and if /3 exceeds . equal to the sum of the separate partial pressures. will likewise be constant. . curve. Chem. Large positive deviations from ideal behavior can thus lead to incomplete solubility of one liquid in another.. Similarly.. this value the fugacity curve has a sigmoid character.1)3. p. 52. II and III in Fig. at a parThe ticular temperature. The point of horizontal inflection C on curve II corresponds to the critical solution (or consolute) temperature for the given system. "Textbook of Physical Chemistry". total vapor pressure. Hemy's Law. below this temperature the liquids are not completely miscible in all proportions. as regards temperature and composition of the liquid. having the same fugacity. This curve implies that there are three different solutions. 1946. which are in equilibrium with each other. the relative fugacity f/f t rather than /. 23 there are shown the relative fugacity (or partial vapor pressure) curves for one constituent of the system. equal to 4. There are then two liquid layers. 2nd ed. provided the two layers are present. 36a.. J. see also. S. Glasstone. above which the liquids are not completely miscible. 7. * For certain decreases as the temperature is lowered. or equation (cf partial vapor pressure. the results comparable. Soc. which should be capable of coexisting in equilibrium at the given temperature and external pressure. 9 Hildebrand. Chapter X. the fugacity of given fraction of that constituent approximates to the value for an ideal system [equation (34.
equation Raoult's law. in accordance with the usual convention. in which the solvent obeys Raoult's law and the solute satisfies Henry's law. (36. it is necessary to treat the product* of dissociation as distinct molecules when evaluating the mole fractions of solvent and solute. From the remarks in 34g it can be seen that equation (36. Raoult's law. equal to/?A/. A and B. Further. 22. for the solute. the solute does not do so unless the system as a whole. the observation referred to above may be stated in the form: In a dilute solution the behavior of the solvent approaches that required by Raovlt's law. i.. this constant becomes identical with r f$ when k is unity. although the solute in the dilute solution does not necessarily obey Raoult's law. pression of Henry's law. Employing the terms solvent and solute to indicate the constituents present in greater and smaller amounts. 22. respectively.3) where k. that is. two methods of approach to the problem are of interest.338 THE PROPERTIES OF SOLUTIONS 41 36a even though the behavior at lower mole fractions departs markedly from This fact is indicated in Fig. which may be written as by ft /2 = N2& as NI > 1 and N2 > 0. It is obvious that in dilute solution the solute cannot obey Raoult's law unless k' is unity. i. when the system is ideal over the whole range The result given in equation (36. viz.. as stated above. It is necessary now to consider the behavior of the solute. A and B. exhibits little or no departure from ideal behavior. . even though it may depart markedly from ideal behavior in more concentrated solutions. as NI approaches unity and N 2 approaches zero. the empirical equations (35. (36. it follows that the molar concentration of the *For a solution containing a solute which dissociates. it does conform to the simple expression /2 = N*f?k'. unless ft is very small In other words. the constituent present in small amount. the fugacity of a solute in dilute solution is proA dilute solution may thus be defined as one portional to its mole fraction. ideally. However..9) /i /a become as = NI/? N*/?e** NI as NI 1 > and 1 N2 (36. pressure or fugacity curve becoming asymptotic with the corresponding ideal curve as the mole fraction approaches unity.1).e.1) and N2 0. This conclusion is in harmony with the results depicted in Fig. that is. in any solution. and the solution is dilute.3) may be interpreted as implying that for a saturated solution of a gas the fugacity of the If the gas behaves solute is proportional to its mole fraction in the solution. over the whole range of composition. nevertheless.2) According to (36.2). it is seen that in the dilute solution. by the actual partial the ideal. the behavior of the solvent tends toward that required is constant. is equivalent to /2 and hence is also constant. although the solvent in a dilute solution satisfies or zero. since = Na/ffc'.3) is an idealized exof concentrations. Taking component 1 as the solvent and 2 as the solute.e. is a constant. in the dilute solution. where k' is equal to e* (36.
24. . then for the solute. the influence of the total pressure 34c). component 2. Raoult's law and Henry's law For a system exhibiting positive deviations. curve II * may be taken as typical.3) is equal to /?.4) can be carried only over the same limited range. 24. but the statement of the law given above is a generalized form of wider applicability. applicable over the whole range of composition. i. It follows. Curve I is for an ideal system obeying Raoult's law over the whole concentration range.e. the solubility. it can be readily shown that the reverse must also be true. like Raoult's law. that in any solution for which RaouWs law is applicable to the solvent. then the solvent must obey RaouWs law over the same range of composition.e. (36. > ' /2 which = N2 fc as NI 1 and N2 > 0. this gives ln/2 or = In N2 + constant. By general by equation integration. and Henry's law and Raoult's law are identical . Henry's law must hold for the solute. This is equivalent to the original form of Henry's law (W. if Henry's law is applicable to the solute. is identical with equation (36. is proportional to the pressure of the gas. the integration of equation (36.3)] is possible by the use of the DuhemMargules equation. It is readily seen that if fi = NJ/?.4) In 34c this result.* These are characteristic properties of a dilute solution. 1803). in the dilute range. which shows the partial vapor pressure (or fugacity) curves of three types. i.3). over the same con centration range. just as to restriction of constant external pressure should apply At moderate pressures.36a DILUTE SOLUTIONS 339 saturated solution. The Raoult's law to Henry's law. therefore.15). at constant temperature. ( may be neglected. as and N 2 > 0. but if the solvent behaves ideally only when its mole fraction approaches unity.. Mole Fraction FIG. The foregoing conclusions are depicted graphically in Fig. Incidentally. A derivation of Henry's law [equation (36. was taken as (34. which dealt only with gas solubility. as is the case for the solvent in a dilute solution. however.. Henry. for such solutions k in equation (36.
hence it is seen from equation (36. that equation (36. the fugacity (or vapor pressure) curve of the other constituent. the solvent. 36b.6) that the integration constant If this result is inserted into equation (36. It is seen. so that TT T. would approach that for an ideal system obeying Raoult's law. it follows that equation (34. In NI is negative.30). which is that of the solvent.5) gives lnNl=  + c ' (36 6) ' where C is the integration constant.6) it is equal to A Hff R TV becomes the freezing point of the solution containing NI mole fraction of Since NI must be less than unity. therefore.3)]. in the form . integration of equation (36... which are applicable to such solutions. T must be less than TO. an approximation which can reasonably be made for dilute solutions. In this expression NI is mole fraction of the solvent in the solution which is in equilibrium with solid solvent at the temperature T and pressure P. The Freezing Points of Dilute Solutions. irrespective of whether If the it behaves ideally or not at higher concentrations. which is not shown in the figure.5) should apply at the freezing point of a dilute solution in equilibrium with pure solid solvent. but the curve has an approximately linear slope. as postulated above. dT P RT*' ' ^ (36. the freezing point of the solution is always less than that of the pure solvent. and since A/// is positive. the solute.e. indicating that it satisfies Henry's law [equation (36. heat of fusion is taken to be independent of temperature. THE PROPERTIES OP SOLUTIONS 36b at the lefthand side of the diagram. called the lowering of the freezing may be replaced by TO. in other words. When the liquid phase consists of pure solvent. The same is true for curve III which represents the fugacity of a substance exhibiting negative deviations from Raoult's law. it is clear from equation (36. Since in any dilute solution the solvent behaves ideally. NI is unity and the freezing point is then To. i. in the respect that it obeys Raoult's law. A#/ is the heat of fusion of the solid solvent under the same conditions. i. In the region in which Henry's law is obeyed by one constituent of a solution.7) that the freezing point must decrease at the same time.7) may be expected to apply to any dilute solution. further simplifications. provided the solid phase is the pure solvent and not a solid solution. can be made. Since equation (36. Since NI decreases with increasing concentration of the solution.e..5) gives the variation with composition of the freezing point of a dilute solution. there is marked departure from Raoult's law.340 i. .e. For a dilute solution the difference between T and T is small. and if T where T is solvent.
since 1 equal to N 2 the mole fraction of the solute.9).36C point of the solution. it is hence equal to the molality of the solution.9) In a dilute solution. i. since the solution is dilute n 2 may be neglected in comparison with ni. as indicated in equation (36. giving N2 = or r m2 2. NI is only slightly different frcm unity.11) equal to JZToJf i/lOOOAff/.e. Since the solution must be dilute for this equation to be applicable. respectively. dissolved in 1000 g. tJie depression of the freezing point is proportional to the mole fraction of the solute. then + M Upon substituting this result into equation (36. where ni tion is possible. to determine the molecular weight of the solute. equation (36. 0.8) may be replaced by N2 . therefore. 1. (36. it is possible to use the freezing point lowering of a solution. Determination of Molecular Weights. and hence N2 may be taken as equal to n*/n\. It will be apparent that if this equation were applicable at such a concentra where X.9).8) If the solution is sufficiently dilute. Because of the relationship between the mole fraction and the molecular weight of the solute. of solvent.11). it follows that In NI in equation . is DILUTE SOLUTIONS represented In 341 by NX . and i and Af 2 are their molecular weights. in conjunction with equation (36. If w\ and w* are the respective weights of the solvent and solute in the solution. The factor m . (36. The mole fraction N 2 is equal to n 2 /(ni and n are the numbers of moles of solvent and solute. ^0. in the solution. is a constant for the given lOOOwt/wiM* is seen to be equivalent to the number of moles of solute. 36c. it is found that This equation may be written in the form RTlM Xm. m.7) becomes (36. a further simplifican2).. which is solvent. l ' 1000AU/ (36. so that In NI is approximately equal to NI NI is Further.
1263 below that of the pure solvent. third. where A/f/ weight is M is i.054 must 0.e.054 g.054/0. g.6)* X 30. of solute to 1000 g. at appreciable concentrations the approximations made in its derivation are no longer justifiable.987 1000 X (278. the molality of the solution is equal to 0/X. where Af * is the molecular weight of the solute. M*  6."1 .8).11) to be applicable. of solvent.342 tion. It is obviously strictly applicable only to very dilute solutions. It will be observed that equation (36.0247. of benzene has a freezing point which is 0. provided the solvent still obeys Raoult's law. it is necessary to make use of equation (34.0247M 2. Since the solution contains 6. may be replaced by The two latter approximations are avoided in equation (36. that N 2 may be set equal to n 2 /ni. either from the known freezing point To and the heat of fusion or by determining B/m at various molalities. from actual freezingpoint measurements.11.. thus. instead of pure solvent. whose formula into pure liquid at its freezing point T The value of X for any solvent can thus be determined in two ways.11) in solutions of moderate concentration. is 5.054 g. Separation of Solid Solutions. Calculate the molecular weight of the solute. the heat of fusion per mole of the solid solvent. that TQ T is equal to TO.1 1) = 5. Assuming the solutions to be dilute enough for the . 1. These are as follows: first. THE PROPERTIES OF SOLUTIONS 36d X would be the lowering of the freezing point for a molal solution.11) is used as the basis of the familiar procedure for the determination of molecular weights by the freezing point method. that In NJ N 2 and fourth. and this gives somewhat better results than does (36.2 cai. hence X is referred to as the molal freezing point depression constant.11 = 0.2 By equation (36. hence.1263/5. i. the molal depression constant X for benzene is given by R ^ 1000A#. so that m mrepresent 0.29). If upon cooling a liquid solution the solid phase consists of a solid solution.0247  245. that AT/ is independent of temperature. and extrapolating the results to infinite dilution. A Since both and A/f/ can be expressed in terms of calories. Actually a molal solution would be too concentrated for equation (36.4 C and its latent heat of fusion solution containing 6. of triphenylmethane in 1000 g. Problem: The freezing point of benzene is 30. 36d. . 1 . 6. and so X may be defined as equal to 9/m as the when m solution approaches infinite dilution. . noting that A#//Af i is equal to the heat of fusion per gram. second.
The equation (36. The Boiling Points of Solutions.22). it is found that (36. In NI by N 2 InNj by . solutions.13) yields T For dilute liquid and solid and TT Q by T\\ TQ 6 To /* . for which N. the mole fraction of solute in the solid phase.14) then reduces to = RT* (N2 ~ Ni) ' (36 16) ' which may be compared with equation (36. the constituent present in excess. when the solid phase is a solid solution of known composition (N). nay be treated by means of equations already derived. Z. It should be noted that if N is less than N 2 the value of is positive.36e DILUTE SOLUTIONS 343 fugacity of the solvent. and the solution has a lower freezing point than the pure solvent.. i. that of the pure solvent. and the freezing point of the solution is above that of the pure solvent.9). is zero. at the same pressure.Xm(l so that it is possible to k). . Chem. NJ. equation (34.15) gives the change in freezing point with composition (NJ) of the dilute solution. However. negative. . 322 (1890). In this event. so it has a higher boiling point. replaced is equal to and equation (36. to be proportional to its mole fraction in both solid and liquid phases. at constant pressure. integration of equation (36.e.. Just as a solution has a lower than the pure solvent. Another form of equation (36.. the freezing point of the solution. the vapor consists entirely of solvent molecules! md hence NI is unity. and TO. as postulated above. provided the solution is dilute enough for the solvent to behave ideally. this equation becomes RT where A#/ is the molar heat of fusion of the solvent. T may be 0. there is a larger proporIn these circumstances 6 is tion of solute in the solid phase than in the liquid. provided the solute is nonvolatile and hence is not present in the vapor phase. the result is . By treating this expression in the same manner as equation (36. provided no solute separates in the solid phase. it frequently happens that N is greater than N 2 .15) may be obtained by writing k for the distribution ratio N^/N 2 of the solute between solid and liquid phases. that is to say. The problem of the variation rf the boiling point of a solution with composition.9). Freezing point u van't Hoff. determine the distribution of the solute between the two 11 phases from freezing point measurements.16) . If the latter remains constant in the small temperature range between T. 5. If the solute is nonvolatile. phy*. which applies to a 36e.x (3<U4) at constant pressure.
Provided the solution is dilute enough for the solvent to behave ideally in the liquid phase. so that the vapor in equilibrium with the solution contains both constituent's. v Xw.17) gives where A/fw . of formula by analogy with equations .18) T is the boiling point of the solution and T is that of the pure solvent If the system does not contain an inert gas this at the same pressure. By assuming this quantity to remain constant in a small temperature range. The results given above may be used for determining the molecular weight of a solute from the rise of boiling point of the solution. can be written as (36. and the vapor behaves as an ideal gas. the elevation of the boiling point.17) is the molar heat of vaporization of the solvent at the specified temperature and pressure.22).19) and hence for a very dilute solution.9) and (36. for the temperature is then the tive.T where Q \ (36. A# weight Mi. and writing TQ. the boiling point of and hence T the solution is greater than that of the solvent. integration of equation (36.8)].344 THE PROPERTIES OF SOLUTIONS 36e liquidvapor equilibrium such as would exist at the boiling point of a solution. If the rise of boiling point T T is represented by 0. equation (36.11). The presence of a nonvolatile solute thus raises the boiling point. In NI is negar T must be positive. consequently. By treating same manner as the analogous equation (36. it follows that for a dilute solution [cf. normal boiling point. this equation becomes where N( for this result in the T the mole fraction of solvent molecules in the vapor phase. If the solute is volatile. The molal boiling point (36. it is readily found that for a dilute is . (36.16). Because NI is always less than unity. constant pressure is that of the atmosphere. elevation constant X is equal to #ToMi/1000A// v where v is the molar heat of vaporization at the boiling point T of the pure solvent. it is necessary to make use of equation (34.
the equations (34.23) thus 34f. As indicated at the . may bo or the molarity c. at the given temperature and pressure. m It should be noted that since the solute does not necessarily obey Raoult's law. the saturation solubility N2 in mole fractions. if k is larger than unity.16).21) can be seen from this expression that if k is small. 34i.4) will be applicable. 6 It = Xm(l  *) (36. equal to NJ/NJ.21) and (34. this can be converted into a form analogous to equation (36.36f Solution DILUTE SOLUTIONS 345  A// p where k. if the solute is k is positive. 1 On the other hand. or of a pure solid in a liquid solvent. of course.23). and Fit is molar heat content in the saturated solution.. is the distribution ratio of the volatile solute between the vapor and the solution.23) In this expression. Temperature and Solubility in Dilute Solutions. which gives the influence of temperature on solubility in dilute solution. and then (36. cannot be identified with a latent heat. It will be seen in 44b that it is actually equivalent to the differential heat of solution (cf 121) of the solute in the saturated solution under the given conditions. although it satisfies Henry's law. lower boiling point than the solvent. This is. equation (36. For a dilute solution this is usually not appreciably different from the integral heat of solution. for a very dilute solution. If the solution is dilute. and the presence of the solute results not appreciably volatile. of common occurrence in the distillation of mixtures of two volatile liquids. 36f. as was done in The numerator on the righthand side of equation (36.22) becomes where Hj is its partial dT ?" RT* (36. it is not permissible to replace R* by the molar heat content of the pure liquid. viz. . as might in a rise of boiling point would be negative.P the molar heat content of the pure gas or solid solute. so that the solution has a be the case for a volatile solute. As before. For a saturated solution of a gas in a nonvolatile solvent. that is to say. It is thus possible to determine the heat of solution of a sparingly soluble gas or solid by measuring the solubility at two or more temperatures and then utilizing the integrated form of equation (36.28) reduce to TT. since these quantities are replaced by the molality proportional to one another in dilute solution.
Show that for a liquid mixture exhibiting positive deviations from Raoult's law.096 565.454 597.844 579. Buck and Parry. respectively.43 and 551.10) are related by and a$\ = cri. Chem. respectively. (ii) the vapor. 2422 (1941)]: (1) and 1nitroSoc. 3.00 544mm. solute.8) equation. the vapor pressures of carbon tetrachloride and benzene are 617. Give in full the derivation of the statement in the text that heat is evolved upon mixing two liquids which form a system exhibiting negative deviations from ideal behavior. 0.) . respectively [Scatchard.03 mm.6 and 0. p? as 200 mm. the values are 312. At 70 C. derive expressions for the total vapor pressure of a liquid mixture in terms of the mole fraction composition of (i) the liquid. total pressure at the beginning and end of the process. and (3 as 2. tfi/3j Prove that the constants in the van Laar equation (35. Am. 02 = ]8i + 71 and 71 = . must be greater than unity. Would the separation of the two components by fractional distillation be more efficient at high or at low temperature? 4.765 589.2 0. Plot the values against the mole fraction composition of (i) the liquid.282 590. 712 (1940)]. Mochel and Wood.4.. The total vapor pressures of mixtures of chlorobenzene propane (2) at 120 C are as follows [Lacher. 0. J.9) take the form Pi " Nip?e*0 N i and pz Hence. the activity coefficient of each constituent.9 NI P 545 0.0. 5. /.4 1.. 6. Derive expressions for log 7. 9..8 by using the results of the preceding exercise.722 7.04 and 271.507 597.9). on the basis of the usual standard state.7) and (35..10).2. when the vapor presCalculate the sures of the pure components are 802 and 252 mm. 1.. the assumption is made that one of the phases consists of either pure The same result would apply to a sparingly soluble liquid solid or pure gas. where 7 is the activity coefficient a/N. whereas for negative deviations it must be less than 8. since the actual deviations are small. determine the total vapor pressure at mole fractions 0. Soc. (Note that at the end of the vaporization the composition of the vapor will be identical with that of the initial liauid. 62.. 2. (ii) the van Laar equation (35. Assuming ideal behavior. Am. 0. at 50 C.1 0.346 THE PROPERTIES OF SOLUTIONS 36f outset.34 mm.6 0. (ii) the vapor. plot the curve giving the variation of the (mole fraction) composition of the vapor with that of the liquid at each temperature. provided the solvent did not dissolve in EXERCISES it to any appreciable extent.2 0. the equations (35. unity. A mixture of 1 mole of ethyl bromide and 2 moles of ethyl iodide. Chem. Taking p? as 100 mm.2 0. Show that in the twoconstant Margules equations (35. which behaves ideally. 63. is evaporated into a closed space at 40 C. Plot the results and determine the value of ft in the simple form of the Margules Estimate the partial pressure of each constituent in equilibrium with an equimolar liquid mixture.675 596. on the basis of (i) the simple Margules equation (35. If the vapors behave ideally.
01685 at 15 and 0. and hence obtain the necessary data for 760 mm. SO 2 in 100 g. 612 (1940)]. /.8. and hence draw conclusions as to the reliability of the various approximations.0 mm. at 44. Show that in dilute solutions Henry's law takes the form m = kp..01256 at 35 C. of benzene under these conditions. [Plot the total vapor pressurecomposition curves for various constant temperatures. Calculate the mean differential heat of solution of the gas in the range from 26.20 C..2 C. 17.. 16. Soc. A# + A# . Determine the mean differential heat of solution per mole of nitrogen in the saturated solution in this temperature range.8 T.8 atm. at 35.g.. at 39. The melting points of benzene and naphthalene are 5. where Determine the 40. 34f). 70. Chem.benzene and 0. and the heats of fusion are then 2. and consider how v you would expect this to differ from the heat of condensation.0 mm.8 to 47.4 and 80. The absorption coefficient of nitrogen is 0. for a solution containing 1.000 g.540 cal. of (i) the liquid.6 C) is 38.0 mm. The pressures of sulfur dioxide in equilibrium with a solution containing 0.6 C.490 [Chadwell and Politi. Estimate the ideal solubility of the gas in a liquid at 25 C and 1 atm. of fusion of ice is 79.6 C.0 mm.0 C.0081 in point (216.8 C. . and the.EXERCISES 10.540 cal. pressure as a function of the mole fraction composition.0 C at a gas pressure of 70. 761 (1934)].9) and (36. SO 2 in 100 g. at 47..09 g. mole*"1 Assuming the system to be ideal and the heats of fusion to remain constant. (36.. use the foregoing data to test the validity of the law for the sulfur dioxide solutions at 35 and 45C. i.23) may be replaced by a. 347 several temperatures The vapor pressures of nhexane and nheptane at 80 1062 427 90 are as follows: nhexane nheptane 50 401 141 60 566 209 70 787 302 100 C 1407 589 1836mm. if the gas and solution behave ideally? 12.0 C. when the liquid mixture is in equi Assuming A# .0009 in ethanol. N 2 in equation (36.7). (36. at C and 24.8). (ii) the vapor. at 33. T is given by A#/ = 4. Am. 1291 (1938)]. where m is the molality of the solution and p the partial pressure of the solute.~ l Test the applicability of equations (36.6 atm. i. at 41. 96. The calculations may also be made at another pressure. Show that for a dilute solution.e. allowing for the variation of the heat of fusion with temperature. pressure which will be dissolved by unit volume of solvent at the experimental temperature under a partial pressure of the gas of 1 atm.4. 0. A#/ is 4. 15. the pressures are 70.11) to the results. pressure.g. 13.2 C). Account for the results. Am. .. 14. Phys. The vapor pressure of liquid ethylene is 40. determine the temperature and composition of the eutectic system. The heat of fusion of the hydrocarbon anthracene (CuHio) at its melting 1 Its mole fraction solubility at 20 C is 0. ideal solubility of naphthalene at 25 C.5 mm. 124. 62. draw the curve representing the boiling points of the mixtures at 1 atm.2 C [Beuschlein and Simenson.. at .0 mm. 560 mm. .360 and 4. J. /. at the melting point (80. 57.6 and 0.e.4 C and 147. Chem.360 molal solution of urea in water The heat is 5. water are 49. 0.80 cal. The absorption coefficient (of solubility) a of a gas is the volume of gas reduced to C and 1 atm. hence. g. How many grams of ethylene should dissolve in 1. Soc.0 mm. 60.51 g. at 26. 0. 795 ideal behavior.7 cal. The freezing point depression of a 3.2. The molar heat of fusion A/// of naphthalene at the absolute temperature is a constant [Ward.5 mm. e. Chem. change noted (cf. g.] 11. e. water.
The solubilities of stannic iodide in carbon disulfide at several temperatures are as follows [Dorfman and Hildebrand..29). calculate the solubility of the supercooled same temperature. the eutectic temperature is 30. give all the stages in the derivation of equation (34. Chem. 10~3 mole per 1000 g. Calculate the ratio in which the iodine distributes itself between liquid and solid . .20). Chapter IX). 22. 373 (1938). mole" 1 .) 21.] 18. the solid which separates is a solid The heat of fusion of benzene is 30.5 X 10~3 mole water 1000 (Saylor. J. 729 (1927)]: 12. Show that for an ideal system of two liquids. Exercise heat of fusion of solid nitrobenzene at its melting point The XI). m. Show that if a solution is dilute and obeys Henry's law. 49. J. Starting with an equation of the form of (34. 19.0 40. phases in the vicinity olf 5 C.5 C and approximately 3..394.770 cal. Compare the result with that obtained by analytical determination as follows: the solid phase contains 0. 24. [Use equation (34. In R\Tm T)' where point of the solid and A/// is its heat of fusion (cf. hence. benzene [Beckmann and Stock. benzene has a freezing point 0.945 g. Chem. and the liquid 0. treated as an ideal gas. (The experimental values are 143. the difference between the free energy per mole of mixture and the sum of the free energies of the separate constituents.0 C g..56 per 100 g. A solution of 9. i.400 C).2 cai.e.33). g.14 g. is given by AF = HiRT In NI + KzRT In N 5 Hence. [The experimental value is 13. 120 (1895)].129 below that of pure benzene (5. Chapter 20. of iodine in 1000 g.0 25. Soc.2 C.2 C and that of naphthalene is 80. per 20. Stuckcy and Gross. 49.6 Liquid at the Tm is the melting X Temperature Solubility 10. Am.800 cal. mole" .348 THE PROPERTIES OF SOLUTIONS librium with both solids.. Soc. phys. Am. the moial solubility of the solid (w. Calculate the molar heats of fusion of the two components of the system. JR(NI In NI + NI In NJ) (cf. solve the problem in 34e. Exercise 1. 17."" 1 solution of iodine in benzene. and w{ and wi are those in the vapor. the free energy of mixing. Show that the weight composition of the vapor.7 C) is 2. in equilibrium with an ideal solution is given by where Wi and w 2 are the weights of the constituents in the liquid phase. AS .] g. A ) y nd of the supercooled liquid (mi) solute at the same temperature T should be given by . use the result concerning the heat of mixing in J 34a to show that the entropy of mixing two liquids forming an ideal system is . assuming idoal behavior.2 C when the mole fraction of the naphthalene in the liquid phase is 0. a graphical procedure will be found convenient for obtaining the required solution. and the vapor behaves ideally. Z.01 58. Chem. 1 C is The solubility of the solid in water at (5. 60. The melting point of pdiohlorobenzene is 53. 23. water.317 g. iodine per 100 g.53 67. solution Estimate the melting point and heat of fusion of stannic iodide.
this is not the case for the partial molar free energy and entropy. p and (dSi/di*i)T.EXERCISES 349 25. Derive expressions for (dfju/dxi) T. the volume change accompanying the fusion of 1 mole of solid solute What conclusion may be drawn concerning the sign and magnitude of the effect of pressure on solubility? 26. Show that although the partial molar heat content of the constituent of an ideal solution is independent of the composition ( 34a). Show that the variation with pressure of the solubility of a pure solid forming an ideal solution in a liquid is given by In N8 \ (d dP )r where AV/ at is " A Vf ~RT* T and P. .p for an ideal solution.
equation (26. the activity of a substance in any state is a relative property. then. as indeed it must. knowledge of activities and activity both theoretical and practical interest in the study of solutions. the free energy increase accompanying the transfer of 1 mole of the substance from the first solution to the second. which is the thermodynamically important quantity. expressed in terms of the activities. 850 . is given by [cf. As seen above. will have the same value. As seen in 31b. and in the other case.2) Mthe chemical potentials are = = & + RTlnc& $ + RTlna'f. as may be seen in the following manner. therefore. a/c is equal to aj/o. It follows.CHAPTER XV ACTIVITIES AND 37. however. ACTIVITY COEFFICIENTS STANDARD STATES 37a. from the fore going equations that in one case. The nature of the standard state is of no thermodynamic significance. if and " M? in terms of the alternative standard state. standard states. Let a and a represent the activities of a given substance in two different solutions. let a and aJJ be the corresponding values for another standard Since these activities are relative to the activity in the chosen state. If // is the chemical potential (partial molar free energy) of the substance in the first solution and /*" is that in the other solution.29)]] AF = /' By M ' M' equation (31. Choice of Standard State. and so the free energy change for a given process. the present chapter will. the values being in terms of a specified standard state. under such conditions that the compositions remain virtually coefficients is of A unchanged. it follows that a/c must be equal to aj/a. the actual value being relative to a chosen standard state. be devoted to a consideration of the methods by which these quantities may be determined. irrespective of the choice of the standard state. and and /i" = / in terms of the one standard state.
so that for a gas the activity is identical with the fugacity. in . this is equivalent to choosing the gaseous system at very low total pressure as the reference state and postulating that the ratio of the activity of any 37b. it is the constituent present in excess. solvent of a solution. the difference depending on the corresponding values of M2 and M?. The activity of the pure liquid (or pure solid) solvent. dilution of a solution the mole fraction N* of the solute tends to zero and that of the solvent. the activity coefficient a/p. are chosen for the two phases. without affecting its constancy. defined by a/N.37b STANDARD STATES 351 In view of the foregoing arguments. the effect of the choice is merely to alter the value of the equilibrium conIt may be pointed out that the acstant. while for this substance in the phase Mix equilibrium with phase I. that at 1 . M potentials in the two phases in equilibrium for the given substance + RT In a M? + RT In a ft . then approaches unity. If the chosen standard states are identical. the activity With increasing coefficient. the most convenient standard state is also the one used in earlier sections. It is quite permissible. L Gases. is taken as unity at each temperature. and hence. tivities of a given constituent of two phases in equilibrium are equal when However. for a constituent in phase I. i. although the chemical potentials must be identical (cf. being then equal to unity. Thus.. when different standard states referred to the same standard state. it is evident that the standard state chosen in any particular instance should be the most convenient one in the given circumstances. It follows. Mi  + RTlnaa II. M and M are the same. On the other hand.the corresponding reference state is the pure liquid (or solid) at 1 atm. The chemical i. the activities in the two phases.. tends to unity. must be the same. will be equal.e. that is to say. 28a).e.. i. As stated in 31b. in fact. if the standard states selected for the phases I and II are not the same. to choose different standard states for a given substance in two (or more) phases in equilibrium. therefore. Convenient Standard States: constituent to its partial pressure. For gases and vapors the most convenient standard state. pressure. at atmospheric pressure. aa and a$ will be different. Solid or Liquid Solvent. and since the activity of a gas is almost invariably defined so as to be identical with the fugacity. The determination of the fugacities of gases has already been discussed in some detail (Chapter XII). which is almost invariably employed in thermodynamic studies. = MP + RT In ap.e.. NI. For a liquid or solid which acts as the II. consequently aa and a/j. MI = MII. it is not necessary to consider the subject further. is the one referred to in an earlier section ( 30b). the activities are not equal. As seen earlier. The standard state of unit activity is usually chosen as that of unit fugacity. since these are the chemical potentials in the standard states.
a 2 /N2. see also. i.e. In other words. The activity is consequently defined so that at the temperature of the solution and 1 atm. Rev. pressure ai/Ni approaches unity as the solution becomes more dilute. thus. as is often the case for solid solutes.1) that for an ideal solution the activity of the solvent should always be equal to its mole fraction. Hence. moles per 1000 g.352 ACTIVITIES AND ACTIVITY COEFFICIENTS 37b aim. just as for the solvent. pp. the reference state is chosen as the infinitely dilute solution. at 1 atm. pressure. pressure may be taken as a measure of the departure from ideal (Raoult law) behavior. provided the pressure is not too high. N. 10. with the postulate that at the given temperature the ratio of the activity of the solute to its mole fraction.. it is more convenient to choose an entirely Different standard state.e. solvent. 3. Since the activities of liquids are not greatly affected by pressure. Adams. the activity of the solvent is equivalent to /i//i where f\ is the fugacity in a given solution and /? is numerically equal to that in the standard state. because the compositions of dilute and moderately dilute solutions are usually stated in terms of molality... approaches unity as N2 tends to unity. 256 et scq. For a nonideal solution. .e. If the solution is of the type in which two liquids are completely. >1 Njt as N 8 >0. Ni basis of the chosen standard state. i. pressure at the given on the By temperature. 1 B.. it is seen from equation (34. miscible. Chem. c provided the total pressure is 1 e m. (37. and its deviation from this value. pure liquid at 1 atm.. Goranson. Randall. J. Solutes: A. Infinitely Dilute Solution as Reference State: Composition in In the first case. therefore. or in terms of molarity. Pure Liquid as Standard State. the standard state of the solute is chosen as the pure liquid at atmospheric The defined activity coefficient <Z2/N 2 then pressure. in. this conclusion may be accepted as generally applicable. equation (31.1) 1 G. Chem. In many instances. or almost completely.. Several different standard states are used for solutes according to the circumstances. particularly electrolytes or where dilute solutions are under consideration. "Thermodynamics and the Free Energy of Chemical 9 Substances/ 1023. in these circumstances the activity coefficient ai/Ni should he unity at all concentrations. 107 (1937). then becomes unity at atmospheric pressure.e. so that there is no essential difference between solvent and solute. i.5). especially when the solute has a limited solubility in the solvent. but the others are more frequently employed. moles per liter of solution. 1 (1936). pressure m. * 1 as NI > 1 and N2 * 0. the deviation of <ZI/NI from unity at 1 atm. Lewis and M. i. gives an indication of the deviation from ideal behavior.. Phye. Mole Fraction. Three such states are used: one is based on compositions expressed in mole fractions.
the reference state is the infinitely dilute solution. Because the compositions of solutions.3)]. e. /2 = N 2 fc This result is identical with Henry's law [equation (36.2) would. i. for the pure solute (cf. For nonideal solutions. equal to for all solutions obeying Henry's law. in the study of which the activity concept has proved of the utmost significance. (37.37b STANDARD STATES 353 The standard state is here a purely hypothetical one. a*/Ni approaches unity.e. although the behavior of a solute in solution may deviate considerably from Raoult's law. however. hence equation (37. of the solute in any solution may thus be used to indicate its obedience of Henry's law. but certain thermodynamic properties. or a 2 will equal N 2 . and so it is preferable to define it in terms of a reference state. The activity coefficient TN. Consequently. C. 1). it is seen that the activity a* of the solute and its fugacity /* may be related by a2 = or /2  a 2 fc. especially of electrolytes. pressure and Henry's law and Raoult's law would be identical ( 36a). whole range of composition. when N approaches zero.2) In dilute solution.* alternative standard states have been widely used. the value of the proportionality constant depending on the chosen reference or standard state. were ideal over the whole range of composition. just as is the case with gases ( 30b) . it might be regarded as the state in which the mole fraction of the solute is unity. 02/Na. infinite dilution (cf. the activity would always be equal to the mole In this fraction. it almost invariably satisfies Henry's law at high dilutions.2) can be written as as N* > 0. Fig. . partial molar heat content and heat capacity. this is not the case for the molarity. event. because the volume of the solution is affected by a change of temperature or pressure. * . HI. are those of the solute in the reference state. Composition in Molality or Molarity. and so on the basis of the present standard state. However. for the study of not too concentrated solutions. If the solution behaved ideally over the 37d). 24. k in equation be equal to the fugacity of the pure liquid solute at 1 atm. a 2 /N 2 will be unity. The significance of the foregoing definition of the activity of a solute may be seen by making use of the fact ( 31b) that the activity is proportional to the fugacity. even when N 2 = 1.. are expressed in terms of molality or molarity. ie. the proposed standard state would represent the pure liquid solute at 1 atm. If the solution (37. since it is independent of temperature and pressure. the standard state has no reality. according to the postulated standard state. In the event that the composition of the solution is given by the molality of the solute. pressure. the activity a* The use of the molality is to be preferred in thermodynamic studies.. Representing this constant by I/A. the standard state under consideration has some advantages over that in III.g. A.. of course. this manner has been It is for this reason that the activity coefficient defined in called the rational activity coefficient.
in accordance with equations (37. however. moles of solute per liter of solution.. which define the standard states. and even if the soluIn such solutions TN and tion obeyed Henry's law ym would not be unity. but not necessarily unity because of failure to obey Henry's law. and although the latter still indicates the adherence to Henry's law. like that of TN. x thus. a*/c. . of the infinitely dilute solution. At high dilutions the molality of a solution is directly proportional to its mole fraction ( 32f). and hence dilute solutions in which the activity of the solute is equal to its molality also satisfy Henry's law. T and TN differ. is a measure of the deviation from Henry's law. be m 7 appreciably When the composition of the solution is given in terms of molarity. i. the molarity of a very dilute solution is proportional to its mole fraction. ~>l c as c+0. represents the compliance with Henry's law. will different. respectively. a 2 /m 9 is then unity at atmospheric pressure. but in which certain partial molar properties are those of the solute at infinite dilution. however. The definition of the activity is consequently based on the postulate that 52 m 1 as w>0. The activity is defined in such a manner that at the given temperature the ratio of the activity a 2 of the solute to its molarity c. heat content and heat capacity. (37.e.4) The standard state is again a hypothetical one. defined by a 2 /c. the molality of the solution is no longer proportional to the mole fraction of the solute. at the temperature of the system. at high dilutions TN . pressure.g. Thus. been referred to as the "hypothetical ideal 1 molal solution". it corresponds to a solution containing 1 mole of solute per liter. TO and TN are both unity at infinite dilution. T and T approach one another. As in the preceding case. and hence for such solutions the activity coefficient yc.. but at appreciable concentrations the three coefficients differ.. approaches unity in the infinitely dilute solution at 1 atm.3). It has e. like Tm. (37.1) and (37. does not. i. With increasing concentration. the standard state chosen is analogous to that proposed above. the departure from unity of the activity coefficient y m equal to a^/m. At infinite dilution the activity coefficients TN and ym are both unity.e. . the former.3) The standard state is here also a hypothetical one. it is equivalent to a 1 molal solution in which the solute has some of the partial molar properties. i. the actual relationships between them will be considered in the next section. their values approximating to unity.354 ACTIVITIES AND ACTIVITY COEFFICIENTS 37b of the solute being defined so that its ratio to the molality m. In dilute solutions the values will also be approximately equal. and the values are approximately equal in dilute solutions.e.. As seen in 32f. Under such conditions. At appreciable concentrations.
37d STANDARD STATES 355 37c. of solute in terms of molarity is thus c/[c 2 )/Af J. is required. respectively. This is deter mined by the ratio of the activities in the two solutions. It is evident from this result that in dilute solutions. at constant pressure and composition. M + lOOOp* 2) * ' In very dilute solution.5) reduces to N* = m*M = c*M i i Tooo (37 6) ' /orr N The difference of the free energy of the solute in the solution represented by N. without the necessity of introducing 7i*.5) (37. The mole fraction N of solute is then equal to m/(m 1000/M i). must have a definite value irrespective of the standard states . By treating y m and y c in an analogous manner.. (37. the number of moles of solute is c. the activity a may be represented by N7x. rnvm and cy c depending on the particular standard state. since the solution is dilute enough for the activity coefficient to be unity in each case. The general expression for the variation of the activity coefficient with temperature. or vice versa. Relationship between Activity Coefficients of Solute. e. for a solution of molarity c. where MI is its molecular weight. when c and m are less than about 0. ( 37a). m* and c*. m* and c*. a/ a*. For a solution of molality m. it is found that ym This expression of is 7c p  O. Partial Molar Heat Contents in Standard and Reference States.6) it is found that t = y m (l + 0. It follows. the number of moles of solute is whereas the number of moles of solvent is 1000/Mi.001*0/0 = + 0. equa tion (37. but a* is equal to N*. therefore. (lOOOp slight rearrangement of these results then gives m + M ^ m* and i mMi + = 1000 c(M l __ + cM i A . the values of YN. 37d.7) when the conversion 7m to 7c.g. 7m and yc are almost identical.1.. On the other hand. Q> more convenient than equation (37. m and c. viz. where p is the density of The mole fraction the solution and a is the molecular weight of the solute. c* and hence by V* utilizing equations (37. and that in the very dilute solution N*.001c(M Po M.Q01cM 2 Po .8. the molality the molarity c*. the density po being that of the pure solvent. that a* N* m* and P y. when the mole fraction of solute is N*.) which gives the relationship among the three activity coefficients. may be derived by a . and the number of moles of solvent is (lOOOp cAfa)/Mi.
37b.9) is zero. it follows that At infinite dilution. It should be understood that the foregoing conclusions apply. since this is the derivative of the heat content with respect to temperature. Activity of Solvent from Vapor Pressure. Since the volume of a solution changes with temperature. that the standard state is always defined in such a manner as to make the activity coefficient equal to unity in the reference state.e. pure liquid for a solvent or infinite dilution for a solute. moles per liter. 7* is indepressure.9) where /? is the partial molar heat content of the substance i in the given It will be observed from solution and /?? is the value in the standard state. where the infinitely dilute justification for the remark in solution was chosen as the reference state.6). so that. and mole fraction are independent of temperature. In the reference state.e. for it is only then that the activity coefficient in the reference state is unity at all temperatures. pressure. the discussion in 37b.356 ACTIVITIES AND ACTIVITY COEFFICIENTS 38a procedure similar to that used to obtain equation (31. Hence. at 1 atm. C. in which 7* is y m or 7N. Since the molality . In order to avoid the possibility of misunderstanding. and at the same time p becomes identical with po. Consequently. The activity of any constituent of a solution is given. e. in general. so that the lefthand side of equation (37. pressure.. noting that in the latter c is merely a numbed. the partial molar heat content of any constituent of a This is the solution is the same in the reference state as in the standard state. by definition. and (37.. therefore. pendent of the temperature. by the ratio of the fugacities.9) i. strictly.7) or (37. ifc'j /<//?> fi being the value in the solution and/? is that in the standard state. must change at the same time. it may be stated here that the partial molar free energy and partial molar entropy of the solute in the standard state are entirely different from the values in the infinitely dilute solution (see Exercise 24). the molarity. does not give the variation of y c with temperature. the temperature variation of activity coefficients expressed in terms of these quantities. The same is true for the partial molar heat capacity at constant pressure. i. III B. equation (37. ye is equal to unity at all temperatures. at 1 atm. in this case also. 7x or y m is given by / i_ V frO /V JBT2 ' (37.8). the standard partial molar heat content of the solute is equal to its value in the infinitely dilute solution at 1 atm.. however. DETERMINATION OF ACTIVITIES 38a.g. 38. . that the partial molar heat content of the solute in the standard state is equal to that at infinite dilution. from this equation. at all temperatures.
Chan. At so that the low pressures. DETERMINATIONS OF ACTIVITIES 3... } where p\ . Hirst and Olson.. of mercury at 20 C. the water vapor may be regarded as behaving ideally. 36.) 38b. 51. based on equaFor dilute solutions. Replacing the and 'See.. without appreciable error.0177. ibid. 2398 (1929).016 moles of solvent. 0. by the respect ive vapor pressures. The equation (38. Problem: An exactly 1 molal aqueous solution of mannitoi has a vapor pressure of 17. et al. J. pressure. L<ochcr and Hunt. and k is a constant.0000 find that the solvent obeys Raoult's law. Soc.57 puro liquid at tho Siuuo temperature and 1 aim. 63. If the solvent solute are essentially miscible. 2422 (1941).535 mm.1) thus provides a relatively simple method for determining the activity of the solvent in a solution. it is tion (38. Buck and Parry. the standard state of the latter may be chosen as the pure liquid (cf 37b. 1 lie fugacitics may be replaced. where /2 is the fugacity of the solute in the given solution. 63. the activity may then be determined by a procedure identical with that just described. III A) . . At the same time. and so it is not surprising to aqueous solution is only 1. Hildebrand. to solutions of organic liquids and to mixtures of molten metals. 3011 (1927). 2452 (1915). A molal aqueous solution contains 1 mole of solute and 1000/18. 2020 (1914). ibid. By equation (37. water in the given solution.38b viz. Am. the effect of the external pressure on thr.2) the activity a 2 is equal to /2 /fc. the vapor pressure Calculate the activity and activity coefficient of of pure water is 17.222 mm. it has been applied to aqueous solutions. 49. more convenient to use the infinitely dilute solution as the reference state. for example. Lacher. 545 (1920). 37. vso thnt it is possible to write is the partial vapor pressure of the solvent in equilibrium with the solution in which its activity is a and p? is the vapor pressure of the pure solvent at the same temperature and (approximately) the same pressure. at the same temperature. activity ni/iy he neglected.. 1754 (1941).9823 = 0. Activity of Volatile Solute from Vapor Pressure. ibid. the mole fraction of solvent is thus  = 55.51 9S23  The activity and mole fraction are so close that the activity coefficient is virtually (It is of interest to note that the mole fraction N2 of the solute in a 1 molal unity. 2 The activity coefficient at any composition may be obtained by dividing the activity a\ of the solvent by its mole fraction NI.1) in the form a 2 p<t/p?. If the vapor pressure of the solvent is not too high. however. 42.
Chcm. is the activity of 38c.2) takes the *? By combining this result with equation concentration. pure solid solvent in terms of the pure liquid solvent.3) This expression may be put into a modified form by dividing each side so that by N. for application to electrolytes. chosen. it partial vapor pressure follows that of the solute. Activity of Solvent from Freezing Points. Randall and Young. XXVI. which can be tyform (38. infinite dilution. to the standard state respectively. ref. Expressions exactly analogous to (38. if the activity at any composition of the solute is known from other measurements. 088 . 1112 (1921).2) it is seen that at an appreciable p. ** Hi f RT In &t) 1 Lewis and Randall.. 50. p$ (38. 43.4) for the evaluation of the activity or activity coeffi p*/N 2 for a number of solutions N2 = 0. see Chapter Soc.3) and (38. also idem.2) can be evaluated by means of the vapor pressure of the solute in the same solution. If a. by equa tion (31. Am. such as those described below.2) The value of k may be derived by utilizing the fact that at high dilutions the activity of the solute. ibid. an alternative procedure can sometimes be adopted. TN If = N2 / ^v N2/ Nf trapolated to is determined and the values are exthe result is equal to p*/N?. which is required in equations (38. represented by aj....358 fugacity /* ACTIVITIES AND ACTIVITY COEFFICIENTS 7>a 38c by the measured.2). as the standard state. is equal to the mole fraction N?. respectively. so that if pj is the corresponding vapor pressure. such as would be necessary to obtain pf/Nj. equation (38. 1. cient.4) are obtained for the and activity coefficient based on a 2 /m or a 2/c becoming unity at All that is necessary is to replace N 2 (and N?) by or c. at (38. Thus. the constant k in equation (38. according When it is not possible to make accurate measurements of the partial vapor pressure of the solute at low concentrations. The method has been utilized to determine the activities activity m and 8 activity coefficients of hydrochloric acid in aqueous solution.3) and (38. fjL 9 it is possible to write. (1028). at the same temperature and 1 atm. Chapter XXII. pressure. J.
and M* is that of the solid at the temperature T.. the activity of the solvent at the freezing point must be the same as that of the solid phase in equilibrium with it (cf.30) for an ideal solution.7) since AH/ refers to a constant (1 atm. applicable in the form of (12. If the constant pressure. is chosen as 1 atm. the variation of the activity ai of the solvent at the freezing point of solutions of varying concentration. the same standard state was chosen for the solid as is conventionally adopted for the solvent in a solution. Over a short range of temperature the heat capacities may be taken as constant. Hence. graph. so as to obtain *ln and then the result . (38.6). so that integration of equation (38. the temperature difference T may be replaced by 6. is given by equation (38. allowance must be made for the variation of AH/ with temperature.7) gives AH/ .8) where L is used. consequently. the lowering of the freezing point.38C DETERMINATIONS OF ACTIVITIES 359 where MI refers to the chemical potential of the liquid in the standard state._ \ dT (38 5) ' where the partial molar heat contents have been replaced by the corresponding molar values. As in 36b. for simplicity. at 1 atm. assuming pure solid solvent to separate.25). (Cp): ~ (Cp)  = * c* (38J) where (Cp)i and (Cp) 9 represent the molar heat capacities of the pure liquid and solid solute at 1 atm.5) in the form dlnai AH/ which may be compared with equation (34. for the molar latent heat of fusion at TQ. By the Kirohhoff equation. the fugacity of the solid will be identical with that of the solvent In the preceding parain the solution. pressure. applicable to a.) pressure process. pressure. T making use 9 differentiating with respect to is of equation (26.Lo + ACP (T  To). 37a). since they refer to pure liquid and solid. so that 3To . then the numerator on the righthand side is equal to the molar heat of fusion at this pressure and the temperature T. At the freezing point of any solution. Upon dividing through this equation by 3T. and H. the freezing point of the solvent.*. instead of regarding it as constant as which dealing with dilute solutions in 36b. is when = [^ff^ ]. For the complete integration of equation (38. _ t . since the system is in equilibrium. / 3lna.
10> is " K=** In order to simplify integration of equation (38. Z/o is the molar heat of fusion of ice at C and 1 atm.. the terms involving 3 ^. it is possible to determine the activity of the solvent ai in any solution.* to 01. Since T is equal to To 0.10) becomes ~ dlnai = 21 + + " ' (Lo ~ (38  n) and this can be integrated between the limits of ai from unity. this equation is equivalent to <38 .12). thus. 16 K. * It should be noted that is it is at this point that the postulated standard state for the solvent introduced. i. Inserting these values into equation (38. By means of equation (38. etc. viz.e. .6) gives 7 1 1 " .. the device 2 of expressing l/(To 0) in the form of a power series."1 mole"" 1 so that ACp is 9 cal. and dT to dO. "" a ai " RTl 4+ Since ^ is usually small. for ice as 9 cal. . from a knowledge of the depression of the The procedure may be illusfreezing point.8) becomes (38. the corresponding values of the freezing point depression being zero and 0.10).12).. With water as solvent.""1 mole" 1 . can be neglected and the foregoing expression gives the activity of the solvent at the freezing point of the given solution. mole"" 1 . .LO OACp iff.360 ACTIVITIES AND ACTIVITY COEFFICIENTS 38C equation (38. pressure. used Hence equation (38. thus.9) and substitution in (38. respectively. deg. deg. (Cp)i for water may be taken with sufficient accuracy as 18 and (Cp). pure solvent. 1438 cal. and certain other properties. trated by a consideration of aqueous solutions. further. with T equal to 273.
If a( represents is the activity of the solvent at a variable temperature T".38C it is DETERMINATIONS OF ACTIVITIES found that In ai 361 = 9. Determine the activity of the water in this solution at the freezing point..13) may be written liquid at 1 aim. The results obtained from equation (38. integration of equation *T" 7 (38. of the water important to note that because of the low mole fraction of solute.1 molal or less.345) 2 0. e. The latter applies to the activity of the solvent in a solution of constant composition.1 molal aqueous KC1 solution is 0.454 X 10~3  5.3478 X 10~3 1.g.) f It is also the differential heat of dilution of the given solution (cf. as it is for dilute solutions. and a" the value at some standard temperature T". In this case.2 X 1QV. which to the same temperature. It is desirable. about 0..e.. known as the relative partial molar heat content of the quantity S\ sol vent.3  5.345 C. It is consequently the common practice to take the activity of the solvent as unity in any dilute solution. is usually represented by the symbol LI.15) If the relative partial molar heat content LI of the solvent (i. i. the differential heat of dilution) is small.12) give the activity of the solvent at temperatures which vary with the concentration of the solution. f which will be described more fully in Chapter XVIII.5) and (38. In ai  2.2 X 10~ ft X (0.. the activity is very close to unity in the 0.e. The //?.. The former gives the variation with temperature of the activity of the solvent in a solution at its freezing point.702 X 10~ 3 X 0. 25 C. The Problem: The freezing point depression of 0. e. pure and fi\ is its partial molar heat content in the solution. to adjust the results so that the values for the different solutions refer This can be done by means of equation (31. with reference to pure water as the standard state.702 X 10. activity ai can thus be readily calculated from the freezing point depression at atmospheric pressure.14) gives dT  (38 .9966.13) should be clearly understood. the activity coefficient of the * It is important that the distinction between the similar equations (38.345 3. .303 log ai = = logai at It is 9.1 molal solution of electrolyte. which varies with the composition.6). for the present purpose becomes /dlnoi\ where H\i is Wifli . the molar heat content of the solvent in its standard state. therefore. 44b.g. hence equation (38.
applicable at the freezing point. since the same standard state is used in each It follows. by changing the external pressure.16) as H H B . Because boiling point determinations on solutions have been carried out over a considerable temperature range. is similar to equation (38:6). = Lo ref. pressure at the given temperature. . p. that the variation of the activity of the solvent case.17). at constant pressure. therefore. AH AHV (38>17) This expression.362 ACTIVITIES AND ACTIVITY COEFFICIENTS 38d solvent does not vary appreciably with temperature. its sign. At the boiling point. 3. at the boiling point for solutions of differing concentrations. in order to evaluate the integral in equation (38. and by treating (38. it is possible to obtain equations of the same form as (38. is given by Aquation (38. The procedure has been mainly used in connection with the study of the activities of solutes.12). as given above.in an analogous manner to that described in 38c. particularly electrolytes.  M? + RTlna g.15). however. it is necessary to use a more precise expression than equation (38. The symbol 6 now represents the rise of boiling point. The activity aa of the solvent in the vapor (gaseous) state can be expressed in terms of the pure liquid as the standard state. at 1 atm. bO  cffi  de\ (38. tion V of the solvent at its normal boiling point. it is necessary to know L\ and also its variation with temperature. or if the solute is nonvolatile.9) to represent the variation of &HV with temperature. except for the negative sign. of the pure liquid at 1 atm. For this purpose the empirical relationship 4 AH.17) . and hence the activity ai of the solvent in the former will be equal to that in the latter. For other solutions. compensates for the negative sign in equation (38. as in 38c. and differentiating with respect to temperature.. 4 38cL Activity of Solvent from Boiling Points. being opposite to that of the lowering of the freezing point. if the #? is equal to the molar heat of vaporizapressure is taken as 1 atm.11) and (38.18) Lewis and Randall. Upon dividing through by T. thus. The treatment for the determination of activities from boiling point measurements is exactly analogous to that given in the preceding section in connection with the freezing points of solutions. the liquid and gaseous phases are in equilibrium. pressure. and it will be described more fully in 39c. it is found that where M? is the chemical potential / V dT p~ RT* (38 16) ' If the vapor behaves ideally. the partial molar heat content g of the gaseous solvent may be replaced by its molar heat content Q Further. as is usually the case with electrolytes.
Am. the electrolyte is an aqueous solution of a salt of the metal.. etc. Measurements. as will be seen later.F. the thallium molecule contains x atoms and z is the valence of the thallous ion in the cell solution. ibid.e. dissolved in mercury. 43.386 DETERMINATIONS OF ACTIVITIES 363 6. ref. The activity of the solvent in the solution can then be calculated directly from the elevation of the boiling point. 37a). Soc. c and d are constants. 54. By making measurements at various pressures it is possible to obtain the values over a range of temperature. The free energy change is dependent upon the activities of the substances involved in the cell reaction. Soc. 1. i... of the same metal.e. Activity from E. i. 500. Smith. the result may be put in the where form <38 ' 19) the constants 6'. (1939).. 1351 (1941).20) activities of the thallium in the two amalgams. Chem. thallium. 233 (1921). The cell may be represented by  Tl amalgam (N) Thallous salt solution T1 amalgam (N 2 ). Thus (cf. by means of equation (38. 61. . 63. of a reversible galvanic cell is related to the free energy change of the process taking place in the cell.F.g.14) or (38.17) and integrating. c'. Chapter XXII. e.. /. mole fractions N and N. The free energy change accompanying the transfer of 1 mole of thallium from the lefthand electrode to the righthand electrode is equal to the difference in the partial molar free energies (chemical potentials) of the thallium in the two amalgams. e.M. etc. provides a possibility for the evaluation of activities. but the general principle is of wide applicability. the effect of pressure on the activity being usually neglected. c. Chem.. It was seen in 331 that the E. 2625 (1932). thallium. it requires the passage of xz faradays of electricity in order to dissolve 1 mole of thallium from one amalgam electrode.. The method has been largely used in the study of electrolytes. further reference to this subject will be made in 44g.. Upon insertion of this expression in equation (38..g. The results can then be used to calculate the relative partial molar heat content of the solvent..M. It will be employed here to determine the activity of one metal when dissolved in another metal. idem. being derived from actual heat of vaporization measurements at various temperatures. Am. has been proposed. see also. If where a 2 and a are the Saxton and Smith. in a liquid alloy or amalgam. (38. Li. 1123 Lewis and Randall.F. 8 Consider a galvanic cell in which the two electrodes consist of homo geneous liquid amalgams of different proportions. which are related to 6. A* = 7 M2  M2 = RT In ~ a2 2 .M. 5 38e. and hence the measurement of E.15). J.
In the special case where FE.24) that . this N2 or ! ~ Kl ln ** + 1* <& 1 (38.364 ACTIVITIES reliction AND ACTIVITY COEFFICIENTS 38e by the Tl. of the galvanic cell (38.. data being obtained from thallium amalgam cells at 20 C. since log (a 2 /N 2 ) will then be zero.EF + In ai.00326 throughout.F. i.23) " g0/ (38 24) ' now constructed in which the composition (N 2 ) of the constituting the righthand electrode is varied.M. in accordance with the chosen standard state. and to deposit (33. in accordance with 37b. III B. (E) of each cell is measured. of the appropriate cell. When N 2 is zero.P. with N 2 constant and equal to 0.22) gives the ratio of the activities in any two amalgams directly from a measurement of the E. (in amalgam) ~ xTl** (in solution) H.36) as it on the other by the reverse change. so that AF is equal to it with that this result follows equation (38. and the corresponding value of the term in parentheses on the righthand side of equation (38.e.xzFE.M.F. the metal is thallium. equivalent to N\ F represents the faraday and E the observed under consideration.F. usually the more dilute amalgam.22) The E. the series of cells is A amalgam .20).22) may be written as In a 2 = . so that the activity coefficient a 2 /N2 is unity at infinite dilution.24) is plotted against the mole fraction N 2 Such a plot is shown in Fig.21) is where xz is AF = . Comparing E. both x and z are unity. the value of a 2 /N 2 is unity. is energy accompanying the transfer process The increase of free therefore given by equation (38. The E.M. is maintained constant. Although equation (38.NFE = .M. it is evident from equation (38. the following procedure may then be used.xzt. of the cell is thus seen to be independent of the concentration of the thallous salt in the cell solution. at infinite dilution. and is determined by the ratio of the activities of the thallium in the two amalgams constituting the electrodes. it is frequently desirable to express the actual activity of a metal in a given amalgam with reference to a particular standard state. Suppose the latter is chosen. while that of the lefthand electrode (N). Equation (38. becomes and subtracting In N^ from both to sides. 25.
e.02062 0. .7259 1. 6.e.196 7.01675 0.3 0.15667 0.231 1.4689. 25. 25.1 0.674 3.003396 0. Some of the results obtained are quoted in Table .11118 0. TABLE XXVII. In other words.003396.042 1.04555 0. ref..1 ft? 2.3 3. in any amalgam can then 3. the intercept on the vertical axis for N* in Fig. 2. 7 Data from Lewis and Randall.000 1.4689. so that a is 0.24)] by adding log a.13552 0.1045 3.2701 0. In this manner a 2 /N 2 and hence a 2 for any amalgam within the experimental range can be determined. It is evident that except in the most dilute solutions these are quite considerable.4240 volt 0.2610 3. 25.776 2.log a.. N2 1.5592 2.4860 2.2772 0.0086 0.3558 0. ACTIVITY OF THALLIUM IN AMALGAMS AT 20 C EF N2  i *** log N. is equal to i. 7 XXVII.9177 3.811 4. the corresponding ordinate in Fig. 2. The value of log (a 2 /N*).1680 0.08170 0. . which is . to the term in parentheses.268 The departure of the values of a 2 /N 2 from unity indicate tho deviations from Henry's law.7184 2. the logarithm of the activity coefficient TN.08624 0. equation (38.707 a* (2.6 0.00326 0.4 Mole Fraction (N*) FIG.04856 0.38e DETERMINATIONS OF ACTIVITIES 365 the term in parentheses in this equation will be equal to log oj. i.2 0. that is.4689) 0.321 6.17352 2. Determination of activity of thallium in amalgams be obtained [cf.
of the  cell H (pure liquid) Thalious salt solution T1 amalgam (N 2). could thus be calculated directly from the E.F. (38. measurement.0061 and E is . If it had been required to determine the deviations from Raoult's law it would have been necessary to choose pure liquid thallium at 20 C as the standard state of unit activity. and a 8 is 2. since thallium melts at 302 C.984 X 10~ 4 .11118 volt at 20 C.e. 2.M.25) since the activity of the thallium in the lefthand electrode is now unity.F. "2nSSs +*"" Hence. By plotting the values of a 2 /N a given in Table XXVII against N 2 .3026B is equal to 1.24) becomes  * 1. 1. and a s for the thallium in the rightis hand amalgam. since Na is 1.0. that The value of a 2/N 3 is then found to be 8. Calculate a a/N. on the basis of the new standard state. i.. However. It will be seen in ( 45d) that if the E.811. it is possible to extrapolate the results to N 2 equal to unity. O*/N* is 0. when N so that log NI is is 0. is in volts and F is in coulombs.3. requires infinitely dilute solution.0. that the ratio of the activities of a given component in two solutions is independent of the chosen standard state.4488. hence.16 ~ lt>gN ' As noted above. a* to be unity when N* is unity.16 K.0986.M.3. The activity a 2 of the thallium in an amalgam.00326) Thalious solution T1 amalgam (NI 0. and is. is 0. The activity . log aj is 2.M. the activity a 2 with reference to the standard based on the The new reference state. is 8.811 X 0. 293.M. R should then be in (int.22) as would be given by equation E  ^Ino. In this case the E.366 ACTIVITIES AND ACTIVITY COEFFICIENTS 38e Problem: The E.11118 volt.F. when N.4689.3.) joules. equation (38. however. and so the corresponding activities in the various amalgams can be obtained by dividing each of the results in the last column of Table XXVII by 8.F. instead of that employed in the preceding treatment. to pure liquid thallium.0986 = 0.2772.00326.0986) 0. This is a direct consequence of the conclusion reached in 37a.. and F/2. of the cell TL amalgam (N . (38. and an alternative device is used to obtain the activity in the amalgam with reference to that of the pure (supercooled) liquid thallium as unity. hence at 20 C. the cell depicted cannot be studied at 20 C.984 X 10 X 293.
58.M. and z is the valence.F.268 X 0.M.4. a 2/N 2 calculated in this manner the departure from ideal behavior is seen to be relatively small.424 is For a solution obeying Raoult's law. By varying the proportion of A in the righthand electrode. of the cell Metal is A (liquid)  Fused salt of A  Solution of A in metal B (liquid) given by =. it is seen that a 2 in Table XXVII is 3.3. The same principle as that just described has been used to evaluate the activity of a salt in a liquid (fused) mixture with another salt. 462 (1929). 51. with mole fraction of thallium exceeding about 0.268. It is thus possible to deelectrolyte is pure fused silver bromide. J. 77. ibid.. 233 (1940). the N galvanic cell Ag(s)AgBr(N 2 ) in fused LiBrBr 2 (0). Am. The E.27) ceil when the activity of the silver bromide is unity. Problem: Calculate the activity coefficient which indicates the departure from Raoult's law of thallium in the amalgam containing 0.. purpose the electrolyte consists of a fused salt. 58.. 49. (38.F. instead of an aqueous solution. Consider. Chem. with reference is equal to xz. in which the reaction is the combination of silver and bromine to form silver bromide at mole fraction N 2 (or activity a 2) dissolved in fused lithium bromide. Electrochem.424 mole fraction of thallium. 2084 (1936).RT IneiA. The activity coefficient is thus given by q2 ~ 8.26) where <JA is the activity of the metal A in the righthand electrode. of the i. (1930). where x is the number of to pure liquid A as the standard state. 722 (1927). Seltz.M. Although the method of obtaining the activity of a metal in a metallic solution from E. Soc. the value in terms of pure liquid thallium as the standard state is then equal to 3.. 52. for example. 54. 45d) = where < Sna f 2. measurements is not usually possible at ordinary temperaFor this tures.F.F. Trans. atoms per molecule of A. In general the E. Strickler and Seltz. et al. directly unity. determinations have been made over the whole range of composition from pure A to pure B. when the ' Hildebrand. measurement by means of equation (38. For this amalgam. 1848 (1936). 4257 (1932). termine the activity a 2 of the latter salt in various fused mixtures. varying in 8 = O). . (38. 1) to pure lithium bromide (N composition from pure silver bromide (N* is E the E. 4641.e. the deviation from Raoult/s law is of the order of a few per cent only. Salstrom. 2653.. Sac. 4650..3 3. 4665.268/8.M.M. it has been used considerably for studies at higher temperatures. ibid.26). of this cell is given by (cf.F.386 DETERMINATIONS OF ACTIVITIES 367 coefficients a 2 /N 2 calculated in this manner show that in the more concentrated amalgams. The activity <ZA can thus be obtained directly from an E.
0. The treatment is quite general. An alternative method. this 0.F. becomes (38.F.e. . Experience has shown that the procedure just described is not too satisfactory.M.. evaluate the activity or activity coefficient of the other constituent.984 X 10~ 4 X 773 log a 2 a2 The activity coefficient a 2/N 2 .7188/0. since T . tion (38. M? M..7865 volt when the electrolyte is pure AgBr.e. and can be employed whenever the activity of one constituent of a solution has been determined by any convenient method.27). (38. 38f Activity of One Component from that of the Other Component.211. the E.30) where a\ and a{ are the activities of the solvent in two solutions in which the mole fractions of the solute are N 2 and N. especially when NI approaches zero. viz. and converting the logarithms. [equation (34.  1. the E.7)]. which is then equal to N 3 also approaches zero. equation becomes 0. In equation (38. and log as has a large negative value.29) this and upon integrating. In this way the ratio of the activities of the solvent. loga 2 . can be determined from the known activities a* of the solute.7188. the standard state being taken as pure liquid AgBr.5937 1. By plotting NJ/NI for any solution against the known value of log a 2 the area under the curve between the limits of N and N 2 represents the integral on the righthand side of equation (38. NI (38. indicating positive deviation from Raoult's law.2)].8085 E = is is 0. This result is applicable at constant temperature and pressure irrespective of the standard states chosen for the in two constituents.F. any event. under the latter conditions a 2 for the solute. which has been found to .M. since M? is constant..7865 0. . at a specified temperature. ai/ai. i.M. it is seen that for a binary solution.8085 and E* is 0.368 ACTIVITIES AND ACTIVITY COEFFICIENTS 38f Problem: At 500 C. is 0.7865. of the cell described above is 0. respectively.28) where NI and N2 are the mole fractions of solvent and solute. By N2d/*2 = combining the GibbsDuhem equation in the form NI^MI for the the chemical with expression potential. + + + Njzd In a = 2 0.30).28) gives v A 2 slight rearrangement of equa dlnai = dlna 2 . i. is 773 K. In the present section it has been seen that E. Calculate the activity coefficient in the latter case.8085 when the mole fraction is 0. respectively. measurements can be used to determine the activity of one of the components of a homogeneous It will now be shown how the same results can be used to liquid system.5937. RTln a [equation (31.
693 0. it is found that og ! _ i Ni og & Ni . is the following. in accordance with the standard state usually chosen for a solvent. TABLE' XXVIII. 1 for NI that is. N2 The area under the curve from zero to any composition of log (ai/Ni) for the solvent at that composition. and the data required for the evaluation of the * The experimental pressure is assumed to be 1 atm.950 0.986 0.800 0. i. be more suitable.900 0.e.600 0.500 To illustrate the application of equation (38. then the activity a( of the solvent is unity.704 1.33) to calculate the activity or activity coefficient of one constituent of a solution when that of the other is known.352 1.937 0.28) the result In NI Nl + N** In = N2 N2 0. .31) Upon integrating and converting the logarithms. (38.440 0. Nl (38.866 0.734 0.989 0. and determining the area under the curve between the limits of N and N 2 the difference between the two corresponding values of log (ai/Ni) can be obtained. use may be made of the results for the thallium amalgams given in 38e. + + N2 = U. if the composition N{ and N 2 represents infinite dilution. h N2 =n N NI 2 In NI If this is + Njjd In N2 = 0.38f DETERMINATIONS OF ACTIVITIES Since NI 369 a binary mixture._ JN ..000 0.990 0. and hence.33) N2 gives the value ACTIVITY OF MERCURY IN THALLIUM AMALGAMS AT 20 C 1. Ni By plotting log (a 2 /N 2 ) against N 2 /Ni. is subtracted from equation (38. dNi rfN2 = 0. The values of a 2 /N 2 for thallium at various compositions are available (Table XXVII). l as before.* ai/Ni is then unity and log (ai/Ni) is zero. N = 1 and N = 0. ^.553 0.999 0.000 0. Further.790 0.000 0.855 0.950 0.700 0. so that equation (38.32) becomes ^. .
370 ACTIVITIES AND ACTIVITY COEFFICIENTS 38g The activities of the mercury (ai) at a number integral are plotted in Fig. Analytical Procedure for Calculating Activities. 0. the deviations of the results in the second column. the simplified form of the Margules equation (35. replaces /?. i. 39e.6 0.e.. 9 The standard state is pure liquid mercury at 20 C and 1 atm.e.9) becomes tivity coefficient of where /J. constituent 2.8 log (a. pressure.. ref . respectively. Since the activity ai is equal to /i//J. 26. If the activity or acone constituent of a mixture could be expressed as a function of the mole fraction. ai/Ni. 6. that is. pure liquid at 1 atm. Actual use of this procedure will be made in 38g. 26. y\ and 7*. 39f . i. the fugacity in the standard state. of rounded compositions obtained by means of equation (38./N. Actually the integration is not necessary for the relationship between the expressions for ai/Ni and a2/N 2.) Fio. The general method may equally be employed to determine the activity of the solute if that of the solvent at a number of compositions is known. If the pressure is 1 atm. and the procedure described was used to calculate the activity of the solvent. 9 Lewis and Randall. instead of graphically. pressure at the experimental temperature. are determined by the GibbsDuhem equation. i. . hence. 39b. is known. Determination of activity of mercury in thallium amalgams In this treatment it has been assumed that the activity 6f the solute. from unity indicate the extent of the departure from Raoult's law since the measurements were made at atmospheric pressure.33) are given in Table XXVIII. the integration might be carried out analytically.4 0.e...
Buck and Parry.0. "Solubility of Nonelectrolytes/' 2nd Lacher and Hunt. 2. at 500 C. H. 45 et eeq.5035.31NJ. utilizing the relationship between the constants 02 ( 35d). Laoher. pressure.5937.84N 2 ) 2 + ' giving activity coefficients of the tin in amalgams of various compositions. 1936.34) (38. see also. By means of E..211 when N 2 is 0. .5937)'. if it was found that a 2/N 2 is 1. " Of. = 0'N. ed. for the second constituent. J. 10 Problem: Assuming the simplified Margules equation to be applicable to the fused LiBrAgBr system. it is found that g = " N! 0.. and hence a/N for the other constituent is readily found. ref.22NJ (0. The results are expressed to a close approximation by log (a 2/N 2 ) = 0. hence. which is the same in both cases. log 1. it is seen that 371 by equation or N Similarly. the activity coefficient a 2/N 2 of cadmium in an alloy with tin has been determined at a number of compositions at 430 C. If a/N for either constituent for any composition is known. the value of can be determined. can be expressed ai where /3'. measurements. the activities of mercury (component 1) in liquid mixtures with tin (component 2) at 323 C.211 0' = &' X (1  0. Thus.38g DETERMINATIONS OF ACTIVITIES (31.F. use the result obtained in the last problem in 38e to derive general expressions for the activity coefficients of LiBr (OI/NI) and AgBr (a2/N 8 ) as functions of the respective mole fractions.217/3.26Ni g __ ~~ +N 2) 2 Hence. is equal to 0.  0. Hildebrand.5). The standard state in each case is the particular substance in the pure liquid state. so that the variation with composition of the activity coefficient of the tin in the same system is given by 0. determined by vapor presby sure measurements. (38. 2. Better results are obtained by using the van Laar equations (35. The standard state in each case is the pure liquid metal at 323 C and 1 atm.10).31NJ. ref.35) .846N? 3. In the problem mentioned. log (ai/Ni) The foregoing method involves a single constant and can be used when the deviations from Raoult's law are not too great. pp.M.
Because of experimental difficulties this procedure has not found practical application. i. is equal to the partial molar volume of the given constituent. (dM.372 so that ACTIVITIES AND ACTIVITY COEFFICIENTS r/1 38h log * *Nj log v 3  O.'JoN. i. for there will be a tendency for the solvent to pass through the membrane into the solution. of interest. ever. the chemical potential of the solvent in the solution at P will become equal to that of the pure solvent at Po. and hence measurement of osmotic pressure should provide. increase of pressure from P to P increases the vapor pressure in the solution.37) */PO 27m) of the solvent In physical terms. both at the same pressure. in the fused LiBrAgBr system. thus equation (38. for constant temperature and composition. If P and Po are the pressures on the solution and solvent. the activity coefficient of the LiBr in the same system is given by the analogous expression This gives the activity coefficient of the AgBr By log = NI log 7l = 0. so that it becomes identical with that of the pure solvent at PO.. equations (38. the solvent in this case. the pressure on the solution must be increased above that exerted on the solvent. the osmotic pressure of the solution.N.5035N*. is The osmotic pressure of a solution 38h. In order to establish equilibrium. respectively. and the righthand side that of the solvent in the solution when the pressure has been increased from P to P.. but the thermodynamic treatment is..oO.35). at the same pressure PO. related to the activity of the solvent in it.26). If a solution and the pure solvent. when equilibrium is attained. a method for the determination of activities. the two values will not be equal. = M + I PidP. the system will not be in equilibrium. (38. If MO is the chemical potential of the pure solvent and M is that in the Howsolution. Osmotic Pressure and Activity.* It is therefore possible to write dP. pressure which must be applied to a solution to prevent the passage into it of solvent when the two liquids are separated by a semipermeable membrane.36) is equivalent to // Mo * (cf. a membrane permitting the free passage of the molecules of solvent but not of solute.36) the lefthand side giving the chemical potential of the solvent at PO. then the difference P Po is equal to n. if the pressure on the solution is raised from P to P./dP)r. (38. According to equation (26.e.e. in principle. neverThe osmotic pressure may be defined as the excess theless. are separated by a semipermeable membrane. for this is the condition of equilibrium. .34) and (38. as seen above.
Fi = 7 is [1  (P  Po)]. i. and hence fi/f? may be replaced by ai.1)]. may be replaced by p\/p?. the result is same pressure Making the substitution pure state and in the of the equations VidP.42) According to equation (38. (38. may be expressed in terms of their respective fugacities [cf. pressure P.F H(1  all). at the of the solvent in the PO. If (38. a is of the order of 4 X 10~ 5 atm.40) it is necessary to know how the partial molar volume Vi of the solvent in the solution varies with the external It may be supposed that the variation is linear. the accuracy of equation (38. (38..e. the procedure is not convenient. (P  Po)[l  %*(P  Po)]. = M? + RT ln/P and M = M? + RT ln/i. equation (31.38h where Vi 9 DETERMINATIONS OF ACTIVITIES 373 is the partial molar volume of the solvent in the solution. MO viz.40).40) In order to integrate equation (38.39) becomes VidP.41) becomes P .38) where f? and f\ arc the f ugacitics solution. Since such measurements are not easily made.38) into (38.RTlna. . /? is identical with the fugacity/? of the solvent in its standard state. 1 atm. and so the osmotic pressure can be derived from vapor pressure measurements. respectively. (38..42) may be tested by using the known activity of the solvent to calculate the osmotic pressure of the solution.41) PO is equal to H. so that equation (38. di. Provided the vapor pressures are not high. the activity of the solvent in the solution. The chemical potentials /io and p of the solvent in pure solvent and solution. so that at any pressure. which is equal to / i//i.39) the pressure PO is 1 atm. (38.42) it should be possible to determine the activity of the solvent in a solution by means of osmotic pressure measurements. (38. the osmotic pressure of the solution. (38. where a a constant and Vo the pressure PO.. Nevertheless.37). except for solutions of high .1 and may be neglected. so that equation (38. For aqueous solutions. the result is is the partial molar volume of the solvent at If this expression is inserted into equation  fo = P As seen above. and comparing the result with the experimental value.
3 2. The E.00 and that of the solution as 1.00 119mm.0 0.670 0.M.793 0. Chem.. suggest a possible procedure for determining TN in a case of Express log y log y\ 0'Nj.9.05976 volt at 327 C (Strickler and Seltz.432 0. 2020 (1914)]. 0. 2) : Ni pi 0. 11 C obtained in this TABLE XXIX.460 62.2. Am. 2.3 f r 0. J. Soc.~l . 27. et al. Compare the activity coefficients TN. ref . 8).4 95.542 0. 0.374 osmotic pressure.. Obs. cc. with mole fractions 0. Show that if the vapor cannot be treated as an ideal gas.247 0. The mercury Na(Bi) (pi) in 0.463 0.005 g. by using the appropriate form of equation Pure liquid bismuth should be taken as the standard state.47 aim. J.4 0.2 139. etc.0 Calc. 2. assuming the solvent to be nonvolatile so that p* represents virtually zero total pressure. Soc.9 of bismuth. 0. 0.F. Trans. in the same electrolyte? (Use results of Exercise 5. OSMOTIC PRESSURES OF SUCROSE SOLUTIONS AT 30 C Osmotic Pressure Molality 0. 7*.765 0.119 19.33).47 atm.8 and 0.691 86.650 0. Chem.289 41. .092 [Hildebrand and Eastman. Derive the constant ft in the following data were obtained in a study of the vapor pressure of equilibrium with bismuth amalgams at 321 C: simple Margules equation.5 231.0 3. taking the density of the solvent as 1.0 4. Roy.770 is PbCU in LiClKCi fused PbBi(Z) in which the 0. ACTIVITIES AND ACTIVITY COEFFICIENTS 38h manner are given The results for sucrose solutions at 30 in Table XXIX.0 58. 0.2 138. hence. each component as a function of the mole fraction of the type (Plot log y\ against N* and determine the slope. indicating the 5. 295 (1919).M. /Sac. respectively. 27. Am.4 1.1. 36. A218. 38.  alloy.) (38. and ye in an aqueous solution containing 0.1486 0.0 EXERCISES 1.) 3. The partial pressures of chlorobenzene(l) at various mole fractions in mixtures with 1nitropropane at 75 C are as follows (Lacher.. osmotic pressures from Frazer and Myrick.0 6. of the cell Pb(Z) is  mole fraction of bismuth ref. What would be u Vapor pleasures from Berkeley. this type.5 96.563 0. Buck and Parry.583 76.187 28.840 0.0 0.0 2. 1920 (1916). 6. Calculate the activity and activity coefficient of the lead in the liquid standard state employed.1 1.9 0.908 0. at 321 C of a cell consisting of two bismuth amalgam electrodes.4. the B. Determine the activity coefficients ai/Ni of the mercury in the various amalgams and by plotting NI/NJ against log (ai/Ni) derive the activity coefficients of the bismuth at the mole fractions 0.4) for the activity coefficient of a volatile solute would become TN = (/2/N 2 )/(p?/Nj).1 mole of phenol per liter. Phil.347 0. 4.2 58. equation (38.F.1 and 0.278 0.6.0 232.937 0.
Chapter XIV). et al.781 10"" ) 0.. provided the pure liquid is taken as the standard state in each case. the free energy of transfer of 1 mole of silver chloride from the pure fused state to the lithium chloride solution in which its mole fraction is 0. 43. 3206 (1939).M.690 * 0. atom of cadmium from the saturated more dilute amalgam at 25 C? Show given by liquids (cf. taking pure solid cadmium as the standard state.EXERCISES 375 7. Table XXVIII). Chem. 1278 (1938). (ii) two volatile liquids. of a similar cell. at a given temperature.. The following results were obtained at 500 C for the E. method at 20 C (cf.1 8 11.. that for a nonideai liquid mixture.644 9. 8. the free energy of mixing per mole NzRT In a 2 . Soc. Am.15 0. 60." Justify this