A TREATISE ON HEAT (Including Kinetic Theory of Gases, Thermo- dynamics and recent advances in Statistical Thermodynamics) BY M.N. SAHA, D.Sc., F.R.S. Late, Pauay PRroresion oF Puysics, Carcures Uxtveasn'y AND B. N. SRIVASTAVA, D.Sc., F.N.I. PROFESSOR OF GENERAL PHYSICS, INDIAN ASSOCIATION FOR THE Ccnivarioy oF SemNce, CaLcurra FOURTH EDITION THE INDIAN PRESS (Pustications) PRIVATE LTD. ALLAHABAD AND CALCUTTA 1958 Price Rs. 38°00PrintED AND PUBLISHED BY THE INDIAN Prgss, Private Lp, ALLAHABAD, CALCUTTA, VARANASI FIRST EDITION 1931 SECOND EDITION 1935 THIRD EDITION 1950 FOURTH BDITION 1958 PRINTED 18 INDIA All rights reservedPREFACE TO THE THIRD EDITION The Second Edition has been out of stock for a long time causing great inconvenience to the vast majority of our readers and particularly students. We regret very much this inconvenience but the delay in bringing out this new edition has been due to various factors beyond out control—the second world war, the difficnlt post-war conditions and so forth, We have however taken this opportunity to rearcange the book in a more satisfactory form and have largely rewritten the subject matter and have tried to bring it _ uptodate. The plan of the book has been somewhat altered to enable us to give a fuller anck more advanced treatment of the various topics. After the first two chapters dealing with Thermometry and Calorimetry mote or less in a phenomenological way, the ghree main methods em- ployed in the theory of heat have been developed viz., the Kinetic Theory method, the method of Thermodynamics and that of Statistical Mecha- nies in Chaps. IIT to TX. These methods have been applied in subse- quent Chapters (X to Xfil) tu the derivation of Equation of State; pheno- menon of Change of Phase, production of Low Tefpperature and Thermal Expansion, and in Chaps. XV & XVI to the problems of Radiation and Specific Heat. ‘Theemodynamics of quantum-mechanical systems is dealt with in Chap. XVIL while the application of thermodynamics and quantum statistics to Chemical Equilibria ig considered in Chap. XXVIH. The Appendix contains numerous useful Notes as in the last edition but new Notes have been added on Thermal Diffusion and Low Temperature Physics on account of the importance which these subjects have attained during post-war years. Though statistical mechanics has been introduced much earlier, care has been takea to see that the study of the subsequent chapters does not become difficult and with this end in view statistical mechanics. has been very sparingly employed until Chap. XVIT. ‘The student may thetefore omit Chap. IX in the first reading. On account of the com- prehensive treatment of the’ various topics it is hoped that the book will be useful to the student, the research worker, the engineer and the physical chemise alike.vi PREFACE ‘The authors take this opportunity of expressing their gratefulness to numerous friends who pointed out.the inaccuracies and shortcomings of the previous editions and offered suggestions for improvement. We are very thankful ia particular to the late Prof. R. H. Fowler for his valuable suggestions and criticisms. It is earnestly hoped that this cooperation will be continued. Cancurra January, 1950. THE AUTHORS PREFACE TO THE FOURTH EDITION Tt is with profound gricf that I present this edition. Professor Meghnad Saha, the senior author of this book, died suddenly on 16th February, 1956 during the course of publication of this book. His death has removed the inspiring personality which originated the idea of writ- ing this Treatise and planned and executed it with such perfection. Fortunately, however, the preparation of the present edition was begun in early 1955 and I had fally discussed with him the various lines of improvement as well as the new topics to be included some of which were even written out with his collaboration. The few changes made therefore are almost as he would have wished them to be. Several portions of the book where notable progress has been made in recent years have been fully revised and brought up-to-date. Chapter XII as well as Note 17 dealing with low temperature physics have been rewritten and considerable new material added. Produc- tion of very high temperatures which has gained importance during recent years for purposes of atomic energy has been discussed at some length in Chapter XVIII. A new Note has been added (Note 21) to give the basic principles and methods of the Thermodynamics of Irreversible Processes as it was considered desirable to familiarise the student with this most notable progress in Thermodynamics during the last twenty years, To facilitate quick consultation an explanation of the Symbols and Notation has been given at the end. With these improvements it is confidently hoped that the book will be found more useful by the vast majority of its readers, Catcurra, Marcu, 1958. B. N. Srivasrava.PREFACE TO FIRST EDITION (TEXT BOOK OF HEAT) ‘This book is largely based on the lectures which the senior author had been giving to the Hons. B.Sc. and M.Sc. classes for the past twelve years. It is intended to give a full, up-to-date and concise account of not only the classical parts of Heat, but also such allied subjects as the Kinetic Theory of Matier, Quantun Theory, Statistical Mechanics and Theories of Thermal Tonisation (State of Matter at High ‘Temperatures). ‘The inclusion of the last two chapters has been a deviation from the orthodox practice but is pro- babiy justified by their growing importance, Full and copious references to original treatises and papers have been given. It is therefore expected thar the beok will be helpful not only to the advanced students all over the world preparing fir their degree course, but will also be found helpfal by the research workers in Physics, Physical Chemistry and Astrophysics as a book of information and references. In spite of the care taken in the preparation of the book, it is feared that omissions of impostant results have been many, and the authors will be thankful if these are brought to their notice, Besides the vatious authors and publishers to whom we make oar grateful acknowledgement on the next page, our best thanks are due to the students of the B.Sc. Hons. class (1931), siz. Messrs. K. K, Bhargava, R. N. Rai, and B. N. Joshi, for preparing the Con- tents and the Name Index, to Mr. N. C. Chatteriee, M.Sc., of the Banaras Hindu University, for preparing the Subject Index, to Mr. S. C. Deb, Research Scholar, for verifying the calculations in last Chapter XIV, and to Mr. G. R. Toshniwal for help in writing Chapter VII. ALLAHABAD Aueusr, 1931 THE AUTHORS viiFOREWORD TO THE TEXT BOOK OF HEAT ‘The influence of temperature on the physical and chemical be- haviour .of matter forms a field of study of the highest practical and theoretical interest. In recent years, our knowledge of this subject has vastly increased, and the field of research covers a great range of temperatures, commencing from the lowest possible and extend- ing upwards, apparently without any limit, except that of practical attainment, Recent astrophysical researches—-which are by no means in the natuze of unsupported speculations—indicate the existence of immensely high temperatures in the interior of stellar masses. T. senior author of this book has been the pioneer in that fascinating region of research which deals with the progressive breaking up to the atoms and molecules of matter into theic constituent parts at high temperatures. The well-known Saha ionisation formula forms the starting point of much recent astrophysical research. It has_also a beating on the electrical phenomena occusring in flames, electric arcs, and other high-temperature conditions in the laboratory or workshop, and therefore possesses high practical importance. ‘The familiarity with thermodynamics and its applications to physical and chemical theories which “led Professor Saha to these classical researches has also made him a most successful expositor of the subject. His experience in the lecture-room and laboratory, first at Calcutta and later at Allahabad, has helged him to produce with the assistance of the junior author, a book in which freshness and widch of outlook are combined with clearness and accuracy in detailed exposition, By undertaking the necessarily laborious task of producing a systematic and up-to-date treatise on the Theory ot Heat, Professor Saha has earned a claim to the gratitude of the wide cicle of readers—both in and outside of India—who, it is confident- ly hoped, will study this book and appreciate its merits. 210, Bowazar SrREEr, Cancurra. c. V. RAMAN. L4ra Juny, 1931. viiiACKNOWLEDGMENT Tt is @ pleasure to acknowledge out grateful thanks to our aumerous Friends and colleagues who have rendered help inthe ‘prepa- tation of the book. In particular our thanks are due for Chapter XIT.—to Dr. A. Bose of the Indian Association for the Cultivation of Science fot making importance suggestions. Chapter XifI.—to Dr. S. C. Sirkar of the Indian Association for Cultivation of Science for helpful suggestions. Chapter XVU.—to Dr. R. N. Rai, Reader, Delhi University for going through the chapter and offeting valuable suggestions. Chapter XVII—To Dr. S. R. Palit of the Indian Association for Cultivation of Science, for valuable criticisms. Norgs 15 & 16.—to Prof, D, S$, Kothari, Scientific Adviser to the Defence Ministry, Government of Indiaand Dr. R. N. Rai of Delhi University. for writing out these notes. ores 17 & 18.—to Dr. §. Datta Mazumdar, Lecturer, Calcutta University for help in writing out these notes. We further acknowledge our indebtedness to the following authors, publishers and societies for allowing us to reproduce diagcams which have appeated in the works mentioned below. In some cases we have mentioned the particular figures in this hook and the corsesponding, figures in the works from which they are reproduced. Miller-Pouillets, Lebrbuch der Physik. Henning, Temperaturmessung. Nernst. Grundlagen des nesen Warmesaizes. Jellinek, Lehrbuch der physikalischen Chemie. Watson, Practical Physics. ing, The Steam Engine and other Heat Engines (Canbtidge Univer- sity Press.) Burgess and Le Chatelier, The Measurerment of High Temperatures. Philosophical Magazine. Procecdings of the Physical Society of London. Astrophysical Journal. Physical Review. Bulletin of the Bureau of Standards, Journal of the American Chemical Society ixACKNOWLEDGMENT Journal de Physique. Le Radium. Laiden Communications. Proceedings of the Koninlijke Akademie der Wettenschappen, Amsterdam. Proceedings of the Royal Society, London. Chap. II. Figs. 7, 8, 185 Chap. XIV, Fig. 21. Philosophical Transactions of the Royal Suciely. Chap. V1, Fig. 105 Chap. Tl, Figs, 2, 3; Chap. XIH, Fig. 15. Zeitschrift. far Physi, Chap. 1, Fig. 4; Chap. Hl, Figs. 11, 25, Chap. XI, Figs. 6, 15; Chap. XV, Fig. 15; Chap. XVI, Figs. 3, 5. Plysikatische Zeitschrift. Chap. U, Fig. 23; Chap. UI, Fig. 18. Annalen der Physik, Chap. UW, Figs. 9, 13; Chap. TH, Fig. 23; Chap. X, Fig. 8 Chap. XI, Fig. 14; Chap. XII, Fig. 4; Chap. XVI, Fig. 15. Handbuch der Physik. Cbap. VIII, Vig. 1; Chap. X, Fig. 7; Chap. XU, Fig. 12; Chap. XIV, Fig. 11; Chap. XV, Fig. 30. Reproduced by the kind permission of Messes. Julius Springer & Co., Berlin, Handbuch der Experimentol-piysk. Chsp. XI, Figs. 16, 19; Chap. XII, Figs. 7, 15, 17, 29; Chap. XIV, Figs. 3, 14, 17; Chap XV, Figs. 4, 13, 14, 19, 21, 22, 23. Beer Griffiths, Methods of Measuring Temperaiure. Chap. 1, Figs. 5, 6, 7; Chap. XV, Figs, 24, 25, 26, 2 from diagrams on pp. 83, 52, 34, 84, 85, 90 and 115 of the book respectively. Engines, Chap, IV, Figs, i, 11, 14, 16; Chap. XH, Fig. 2 respectively from pages 107, 195, 211, 213, 239 of the book by the kind permission of Messrs. G. Beli & Sons, Limited, London. Partington and Shilling, Specific Hear of Gases, Chap. I, Figs. 17, 19, 22, 24, 25 respectively from pages 108, 127, 76, 84, 143 of the book. : Preston, Theory of Heat. Chap. Il, Figs. 6, 16; Chap. XV, Fig, 27. Reproduced from the said book by the kind permission of Messrs. Macmillan & Co. Andra THE AUTHORS.CONTENTS Page CHAPTER 1. THerwomrery poo » TI. Canortwerey Poe . 9 WL) Kiwerc Taeony or Marten 5... 109 » TV. Hear Enoives Soe 225 We Firs Law or THermoprnamics =... 27 » VI Suconp Law or THERMODYNAMICS. . 302 » VIL Generar TrexmoprnamicaL Tneoreys . 323 4» VEIL. Trmasopywastcar EQumrrta oF — Prystcan AND CHEMICAL SYSTEMS Loe 339 » IX, Sravistican ERMODYNAMICS OF MAXWELL- Bourzwann Sysrexts Loe 8 »X. Equation oF Srare vor Iupenrecr Gases. 396 » XT. Cuanon or Sravn (Puase) ss. 442 » XL Propucrion or Low ‘Trrenarenes 485 XIU, Tserwan Exranston So 545 XIV. Connucrton of Hear. . 368 XV. Rapravion oe 8 ee »XVE. Spscirro Hear oF Gasts, Liguips awn Sonips, 703 3 XVI, Taersopynasics 07 QuaNTuMwEcHAMcal Sysrems . . . . . . 744 » XVEL Tasaaopynamics or Cyemican Equiceria 779 APPENDIX Nore 1. Proor or Maxwric’s Tupores or Equtran 2. Depuction or Maxwe.e’s Law or Drsrausy Vetocrrizs By THE METHOD oF CoLtisions . 847 3. DerINitE INTEGRALS USED iN THE Kinetic THEORY oF Gases reCONTENTS Page 4. Exrertmenrat Proor or Maxwetr’s Distrisut1on Law vrom ine Foire BReaDrH or SpecrraL ‘LINES : . 855 5, Depucrion oF MaxweLt’s Mean FREE Para e . 857 6. Dererminarion oF AvoGADRO NUMBER AND THE Si1ZE of MoiEcuzEs. 7 . : . 7 8 - 860 7. Syiatine’s Formura : oe - 865 8 Proor or Liouvmie’s THEORFM. . 866 9, Proor or BourzMann’s THrorem S=£ L0G ¥ . 867 40. BNerGy or Oscriators IN A Frecp or Raptarion . 868 11. Nucuear Spry FRom Morecriar Spectra . - 872 12. Tauies or Emsrem ano Desye Funcrions . . 874 13. Companion wir Repevition . 876 14. InvEGRALS UseD IN B.E. AND F.D- Srawsrics . 877 15. Wave-Mecuanics ano New Srauistics a . 879 16. Mernon or Darwsn AND FowLer . . . 893 17. Low Temperature Puystcs anp Liguip He WW. . 896 18. THerwar Dirrusion . : . . a ~ 910 19. Occurrence or ELEMENTS AND THEIR ISOTOPES 23 20. Srnam anp AMMONIA ‘TABLES . » 927 21. ‘Tem THenMopyYNaMIcs or IRREVERSIBLE Procasses - 930 “Taw.e OF PHYSICAL CONSTANTS . . ee O50) Sympos snp Norarion . . 7 . 940 AUTHOR IND! rr ) SUBJECT INDEX . . : : bog . + 954 LIST OF PLATES FacinG Pace Puare I X-ray powder phorographs of _seaphite at various temperatures Il, (@ Continuous prismatic spectrum; (#) continuous Il. grating spectrum; (-) solar absorption spectrum (grating); (d) emisson spectrum of hydrogen;. (¢) spectrum of a-Auriga; (f) flash le of 1905 eclipse 7 . 636 spectra of different classes of stars. . - 700CHAPTER I THERMOMETRY 1-1. Concept of Temperature.—The sensation of heat ot cold is a matter of daily experience. By the mere sense of touch we can say whether a substance is hotter or colder than ourselves. The hot body is said to possess a higher temperature than the cold one. But the sense of touch is merely qualitative, while scientific pre- cision requires that every physical quantity should be measurable in numerical terms. Further, the measurements must he accurate and easily reproducible. This requires that the problem should be handled objectively and the sense of touch should be discarded in favour of something which satisfies the above criteria. Let us sce how this can. be done. When two bodies are brought in contact or communicate with each other through a wall, it is found that, in general, there is a change in their properties, such as volume, pressure, etc., due to exchange of heat. Finally a state is attained after which there is no further change as long as external conditions do not change. This is called an equilibrium state of the combined system. The two bodies are then said to be in thermal equilibrium with each other. Now consider two systems A and B separated from each other by an adiabatic wall, but each is in contact with a third system C through a wall which allows heat to pass (diathermic). Experi- ments show that when such an arrangement is set up, both A and B reach thermal equilibrium with C with appropriate changes in their properties. Then if the adiabatic wall between A and B is replaced by a diathermic wall, it is found that no further change occuss in A and B showing that A was also in thermal equilibrium with B. These experimental facts may be stated concisely in the following form : Two systems in thermal equilibrium with a third are in thermal equilibrium with each other. This law of thermal equilibrium is the basis of the existence of the concept of temperature. In the above example the system C may be taken to be an ordinary mercury thermometer with which the bodies A and B are simultaneously or successively in thermal2 THERMOMETRY fl equilibrium. All these three bodies may be said to possess a pro- perty that ensures their being in thermal equilibrium with one another. We call this property temperature. The temperature of a system is a property which determines whether or not a system is in thermal cquilibrium with other systems. Evidently this tempe- rature can be measured by observing some such property of any one of these systems which varies with the addition of heat. Heat causes many changes in the physical properties of matter some of which are well-known, ¢.g., expansion, change in electrical xesistance, production of electromotive force at the junction of two dissimilar metals, etc. All these thezmometric properties have been utilised for the measurement of temperature. The earliest and commonest thermometers utilise the property of expansion. Mer- cuty-in-glass is universally employed as a thermometer for ordinary purposes, Lut though it is simple, convenient to use and direct- reading, it is not sufticiently accurate for high-class scientific work. For the quantitative measurement of temperature we must select a standard temperature interval between two easily reproducible fixed temperatures just as we select the standard of length (metre) to be the distance between two fixed marks. ‘The two fixed temperatures selected for this purpose are the melting point of ice and the boiling point of water. The next step is to sub-divide this standard tem- perature interval into sub-intervals by utilising some thermometric property and call cach sub-interval a degree of temperature: On the Celsius scale this standard interval is divided into 100 degrees. The itd step is to assign some arbitrary value to the temperature of one of these fixed points and reckon all temperatures from that point, On the Celcius scale the lower fixed point is called 0°C. It will be seen that the empirical temperature scale so defined is more of iess arbitrary and any number of such sc ted, In fact this devise merely setves to register temperature rather than measure it since multiples of temperature can have no meaning with reference to the temperature unit. It is on! temperatures and on the basis of Carnot’s principle that it becomes possible to active at a measurement of temperatures by the definiti of a ratio when the absolute zero of temperature is also fixed. 1-2, Mercury Thermometer.—Everybody is familiar with the ordinary centigrade thermometer. It consists of a glass bulb con- s may be selec- with absolute91-2] MERCURY THERMOMETER 3 taining mercury to which a graduated capillary stem is attached. ‘The freezing point of water is marked 0°C. and the boiling point 100°C. and the interval divided into 100 equal parts. This scale was first introduced by Celsius (1742) and is now adopted for all scientific work. ther scales in ordinary use today are those introduced by Fahrenheit (1714) and Réaumur. But Fahrenheit was the first to choose mercury as the thermometric substance on account of its many advantages. It does not wet glass, can be easily obtained pure, remains liquid over a fairly wide range, has a low specific heat and high conductivity ; it is opaque and its expansion is approximately uniform and regular, But we must not forget its several drawbacks. ‘The specific gravity and surface’ tension of mercury are large, and the angle of contact with glass, when mercury is rising, is different from that when it is falling. The range of an ordinary mercury thermometer is limited by the fact that mercury freezes at —38-87°C. and boils at 356°C. but the upper limit can be raised to about 500°C. by filling the top of the tube with nitrogen under pressure. The thermometric glass must be of special quality : it should be stable and should rapidly return to its normal state after exposure to high temperatures. The glasses generally employed are verre dur and Jena 161 for better-class thermometers and borosilicate glass 5911 and 156511 for high-temperature work. Thermometers have, however, been constructed of quartz containing mercury under pressure, and these can be used up to 750°C. Mercury thermometers are generally employed for rough work. If they are at all used for accurate work, various corrections must be applied to get the true temperature. The important ones among them are the following :— (1) Calibration Correction. This is due to want of uniformity in the bore of the capillary tube. (2) Correction due to change in the fundamental interval from 100 to 100-445 (say) where 5 has any value. (3) Correction due to shift of the zero. This is very important since glass after exposure to high temperatures returns to its normal state only after a very long time. (4) Exposed Stem Correction. Part of the stem and hence the con- tained mercury does not acquire the temperature of the bath,4 THERMOMETRY {I (5) Correction die to changes in the size of the bulb caused by variable internal and external pressure. (© Correction for thetmal expansion of the material. For details concerning the application of these corrections and other useful information see Glazebrook, A Dictionary of Applied Physics, Vol. 1 (Article on Thetmometry) ; Temperature, lis Measurement and Contral in Science and Industry (1941), pp. 228—256 (Article by Busse). 13. Special Types of Liquid Thermometers.—The ordinary metcuty thermometer is not suitable for certain purposes 5 for this reason special types of thermometers have heen devised. They are modifications of the ordinary thermo- meter designed to serve the particular end in view. For meteorolagical purposes thermometers are required to indicate the maximum and minimum temperatures to which they have been exposed during a certain period. Six devised a combined maximum and minimum thermometer which is indicated in Fig. 1. The buib A and part of the tube is filled with alcohol up to the level B, then with mercuty up to C above which agein there is alcohol up to D. The glass indexes I, I have each an iton wire attached (shown separately), and placed above B and C in each tube. When the temperature rises, the alcohol in A expands and the expanding mercury pushes upwards the indes above C to its maximum limit. With a fall in temperature this index is undisturbed while the index above B is pulled upwards by the contracting alcohol, but Fig. 1.—Six’s maximum and is left behind when the temperature rises. The ‘minimam thermometer: ; 55 wire attached to the glass index prevents it from falling under its own weight and enables its position to be adjusted from outside. For determining the temperature of the air in meteorology, the Aspi- ration thermometer has been devised by Assmann. It consists essentially of a sénsitive mercury thermometer whose bulb is protected from solar radiation by a double-walled jacket. By means of an aspirator a current of air is kept circulating past the bulb. ‘The bulb thus takes little time to acquire the temperature of the atmosphere.61-3] SPECIAL TYPES OF LIQUID THERMOMETERS 5 The clinical thermometers in ordinary use are mercury thermometers of short range of the maximum type. ‘The stem just above the bulb has constriction which the mercury passes when its temperature tises. On cooling, the mercury is unable to force its way back. ‘The range of tem- peratures is 95°F. to 110°F., and the bulb is very thin and the capillary bore very fine. The mercury thread is rendered easily visible by constructing lens-front thermometers. For accurate work, such as the determination of the boiling and melting points of organic substances, several short-range thermometers are employed between the range 0 and 450°C. They are called chemical thermometers. Benzol and Toluol thermo- meters are amongst the many that are in use. The Beckmann thermometer, indicated in Fig. 2, is used to measure smail changes of temperature with a high degree of accuracy. The stem is here marked from 0 to 5 representing approximately degrees centigrade and every degree is divided into 100 equal parts.” There is a reservoir at the top of the instrument (shown separately at 4) to enable the range to be varied. To set the thermometer to any desired range, the bulb is heated to expel mercury into the reservoir and the instrument gently tapped when the mercury column breaks neat the reservoir and some mercury is transferred into it, Next the Beckmann therinometer is im- mersed along with an auxiliary thermometer in a bath whose temperature is varied till the mercury stands at the 0 division of the former. The temperature corresponding to the zero of the Beckmann thermometer is thus observed on the auxiliary thermometer, and by varying the amount of mercury in the bulb this is adjusted to be near the desired range. The value of each scale divi- sion varies with the quantity of mercury in the bulb and a correction curve for different settings @ Fig. 2.—Beckmann thermometer of the’zero is supplied with the instrument from which the correction at any point of the scale may be obtained. The true value of a scale6 ‘THERMOMETRY a division may also be obtained by calculation if the expansion of mercury and glass be known. 1-4. Gas Thermometers.—The fundamental disadvantage of liquid thermometers is that two thetmometers containing different liquids, such as mercury and alcohol, and graduated as on page 3, will agree probably only at 0°C. and 100°C. and at no other tem- perature. This is due to the fact that the expansion of the two liquids is not regular and similar. Thus the mercury thermometer of page 3 would give an arbitrary! scale of temperature. Moreover, the corrections to be applied to it (p. 3) are uncertain and known only approximately. Hence for accurate work the mercury ther- mometers ate calibrated (see §1:12) by actual comparison with a resistance thermometer throughout the entire range. Even then the metcury thermometer is rarely used for accurate all standard work gas thermometers are employed. Gases possess several advantages as a thermometric substance. Their expansion is large so that gas thermometers will be more sensitive and the expansion of the containing vessel will necessitate only a very small correction. They can be obtained pure and remain gaseous over wide ranges of temperature. Further, the scales furnished by different gases are nearly identical since the expansion of all gases is found to be almost perfectly regular, Thus the temperature ¢ given by the relation ¢ 100(X1—X)!(Xto0—Xo) Where X may stand for the volume or the pressure at the temperature denoted by the subscript, is found to yield nearly identical values whatever gas we may use as the ther- mometric substance. As will be shown presently, on extrapolation to zero pressure, i., to the state of a perfect gas, these scales of temperature become absoutely identical. Further, it will be shown that the temperature scale furnished by a perfect gas is absolute and universal ; it does not depend apon the properties of any particular work, and for } The volume % of a certaia mass of mercury at any temperature ¢ lying between 0 and 100°C. as measured on the perfect gas scale is given by the relation Uy = Uy (LF 1-B182.104 # + 078.104), ‘Yhus the relation is not linear and the readings of the mercury thermometer as calibrated on page 3 will not agree, even after applying the corrections mentioned, on page 3, with those of « perfect gas thermometer even in the range 0 — 190°C,§1-4] GAS THERMOMETERS 7 substance. It 1s for these reasons that gas thermometers are used as primary standards with which all others are compared and calibrated. The theoretical bases underlying the use of gas as thermometric substance are the laws! of Boyle and Charles. Let the gas be initially at pressure p,, volume v, and temperature 4,°C. If we perform the change by first changing the pressure from p, to py and next the temperature from /, to 4, have from these laws, ear aig P= pw, = Us where v' is the intes! ediate volume aid a the coefficient of expan- sion at constant pressure. Combining these two equations we have fit) dt “Pits That which is the gas equation. Experiments show that the volume coefficient of expansion a is nearly the same for all the permanent gases of nature and is abso- a) lately identical for all of them if their Uchaviour is extrapolated to the state of zero pressure, ie., the state cf perfect gas. The value of a for a perfect gas from the hest recent determinations is 00036608. A-gas thermometer filled with a gas at vanishingly iow pressure will then give the same scale of temperature what- ever the gas. This is called the Avogadro scale of temperature of the gas scale ‘The temperature f=: — Ifa, i.e, 1s degrees below the ice point is by definition called the absolute zero® Tf we measure temperatures from this zero, the ice-point is given by I/a, the steam point by (I/a)+160, and generally any temperature #°C. by (I/a)-+# = T°K. The scale so obtained is called the Absolute Scale or Kelvin Seale and will be denoted by °K. Hence equation (1) becomes Preliminary experiments show that these laws are obeyed by the so- called permanent gases in nature. More accurate experiments (Chap. X), however, reveal the fact that such gases obey these laws only approxi mately and not rigorously, and in some cases considerable departures are observed. A perfect gas is defined as one which will obey Boyle’s law and Joule’s law (Chap. Il) rigorously. 2 The absolute zero thus defined is shown from thermodynamic consi- derations (Chap. VI) to he the iowest temperature possible. Hence the idea of this absolute zero is very important (see further $111).8 THERMOMETRY fi bee Peal, 2 where the suffix 0 denotes the quaostities at 0°C. The quantity Povoi' fy is known as the gas constant and varies as the mass of the gas taken, but is the same for equivalent gram-molecules of all perfect gases. For one gram-molecule’ this quantity is usually denoted by B. Hence the equation can be written generally in the forin pi~sn*RT where »* denotes the number of gram-molecules or of the gas. We have already stated that the real gases do not obey the perfect gos laws. How can,we then find the value of Ty and R? The method of doing this will be indicated in section 1:10. There vit is shown that for a perfect gas a = 0-0036608 per °C. whence Ty = 273-16 degrees and R == 8°314x 10" ergs per degree. Equation, (2) furnishes two ways of measuring temperature. The pressure may be kept constant and the volume observed at different temperatures giving us the constant pressure thermometer ; of the volume may be kept constant and the change in pressure noted, a principle utilised in the constant volume thermometer. 4-5. Standard Gas Thermometers.—The constant-pressure air thermometer has been defended by Callendar on various grounds : (1) the apparatus and the calculations are simple ; (2) the internal pressure on the bulb does not increase as the temperature cises; (3) accuracy of the result depends upon the accuracy of weighing. Nevertheless the instrument does not give concordant results and has been replaced by the constant-volume thermometer as a standard. The normal thermometer selected by the Bureau International des Poids et Mesures and everywhere adopted today is the constant-volume hydrogen thermometer filled with gas at a pressure of | metre of mercury at the temperature of melting ice. It consists essentially of two parts: the bulb enclosing the invari- able gaseous mass and the manometer for measuring the pressure. Fig. 3(a) represents the thermometer! diagrammatically. 1 A high-precision constant-volume gas thermometer has been des- ctibed by Beattie and co-workers (Proc. Amer. Acad. Arts and Sciences, 74, 327, 1941).§1°5] STANDARD GAS THERMOMETERS. 9 ‘The bulb C isa platinum-iridium tube one litte in capacity, 1 metre in length and 36 mm. in diameter. It is attached to the manometer by a capil- lary tube of platinum one metre in length. The manometer consists of two tubes A and B, and the stem of the baro- meter R dips into A. The barometer tube is bent so that the upper surface of mercury in it‘is exactly above B and these levels can be read off by a catheto- meter furnished with three telescopes. The number of observations to be taken is thus reduced to two. B con- sists of two columns of mercury separated by the steel-piece H and both these columns communicate with A. By raising or d y lowering the mer- Fig. 3(a).. —Constane ‘volume hydrogen thermometer, cury teservoir M, the mercury surface in the lower part of B is just made to touch a fine platinum point P [shown magnified in Fig. 3())], projecting from the steel-piece H, and thus the volume of the enclosed gas is kept constant. : The thermometer described above is suitable for measuring temperatures up to 500°C. For higher temperatures certain modi- fications are necessary which will be discussed in section 1-25. The range of gas thermometers with proper modifications can be extended from —260°C. to 1600°C. We shall now deduce a formula for converting the observed Pressure readings into corresponding temperatures. If py, P19 F.210 ‘THERMOMETRY {L denote the pressures indicated by the manomieter at the ice-point and the ‘steam-point respectively, and T,, the ice-point on the absolute scale, then whence 1 tw Po_ g Tent 100 gimr ae: where f is the coefficient of expansion at constant volume, and is known when pp and pyoy are determined experimentally. ‘To find the absolute temperature corresponding to any cbserved pressure Py we have Ay oot i= 7 1 3 = @) since Ty = 1/2. ACCURATE GAS THERMOMETRY 1°6, Gas Thermometer Corrections---In the preceding section the equation was developed on the assumptions (1) that the whole gas attained the temperature to be measured, its volume remaining constant and there being no disturbing factors; and (2) that the gas obeyed the perfect gas laws. Actually, however, none of these assumptions is trne and consequently corrections are necessaty. First we shall cotrect for the former. Here the chieft sources of cztor are the following :— (@) The gus ia the ‘dead space’ is not raised to the temperature of the buib. The ‘dead space’ consists of the space inside the capillary tube and in the manometer between the mercury level and the steel-piece H. Its initial and final temperatures are also different. (0) Increase in the volume of the bulb C with rise of temperature. (© Change in volume of the bulb due to changes in internal pressure. (@ Change in density of mercury on account of temperature changes. Let V4 denote the volume of the bulb and H, the pressure of the contained gas at 0°C. If the volume of the dead space be v and iss temperature throughout the experiment be # while a denotes the volume 1 There ate about 25 corrections in all and the task of correcting for aii of them is extremely tedious and laborious. For the method of applying these corrections Guillaume’s Thermometrie de Precision may be consulted,§1-7) PERFECT GAS SCALE il coefficient of expansion of the enclosed gas, then the volume of the whole gas at NTP. will be - v (ot phate When the bulb is heated to °C. and the pressure hecomes Hy+h, the same volume is given by {4 byf)--bh | v_ | Hath Fat) 760 * where y is the coefficient of volume expansion of the bulb and b the coefficient of internal pressure. bh denotes the increase in the volume of the bulb due to the increase in internal pressure by #. Bquating the above two expressions we get whence a= th Vol +y8)-+bh be \taé _, @ v= UM TPs ipar Since 0, the temperature to be determined, occurs on the right, the uncorrected value of 8, viz., 0= h/ Hed is substituted there to give a more accurate value of 8. This valué may be again substituted on the sight to give a still more accurate value of 8, The process can be repeated indefinitely. This is called the method of successive approximations and is very commonly employed in Physics. Generally the process need be performed only once or twice as the result then obtained attains the accuracy permitted by the observations theiselves. 1-7. Perfect Gas Scale—We shall now cortect for the second assumption, viz., for the departure of gases from Boyle’s law. In order to-do this we must know the actual equation of state (Chap. X) of the substance. We shall denote by #, and f, the temperatures as actually recorded on a constant-volume anda constant pressure thermometer containing a real gas, while # will denote the corresponding reading given by a per fect gas thermometer, ‘Then from definition bi-Po tye PPo 0, ee = neo 2 and = a cath 5 9 5 6 8) If the quantity of gas is the same in both the thermometers (j-e., at O°C. the pressure and volume in both is Pp, v4), then if the gas obeys Boyle’s law we have oe w= PUP» + + 712 THERMOMETRY a Thus multiplying (5) by vp and making use of (7) we get = PAKPYe 100 ~ (0 — Pe ° and multiplying (6) by p, and using (7), (P—(P%Yo_ 199, F)r0—-P%0 Thus for a gas which obeys Boyle's law the temperatures read on a constant pressure and on a tonstant volume thermometer are identical, and each is given by (Pe (Pr)o x 100. 6 a - (Pieo= Fo ‘We shall now consider the equations of state of a real gas. As will be clear from a study of Chapter X, the number of such equations de- daced from theoretical considerations is very large, nevertheless none of them shows a complete agreement with the experimentally observed fects. Under the circumstances the most satisfactory procedure is to write down the equation of state for every gas from the observed experi- mental data as far as they are available. As this procedure involves a knowledge and measureraent of the temperature, the equation is usually expressed in the for: t= pus ATBP+Cp+DP +... + which was first suggested by Kamerlingh Onnes'. The constants .4, B, ODee... are complicated functions of temperature but are indepen- dent of the pressure, and are found by performing the compression experiments on the actual gas, #2., by noting the volume at different pressures (Chap. X) and substituting in equation (9). For out present purpose we are concerned only with the numerical values of these con- ‘stants at Cectain fixed temperatures and not with their dependence on the temperature which would require a measurement of the temperature. Holborn and Otto® have catried out very careful experiments on 2 aum- ber of gases between the range -183°C. to +400°C. and have given the values of the constants A, B, C.....at different. temperatures. For oxygen at O°C. they find that pu = 100130— 30143 x 10-*p-+3-6898x10-%?..., . (9a) where p is in metres of mercury and v=1 when p=1. Thus the constants 4, B, C ... ate in rapidly decreasing order of magnitude. ‘The D term is generally negligible and at the pressures employed in gas thermometer C is also negligible. ‘Thus the equation simplifies to pu = A+Bp. “"Y Leiden Commun., No. TL, 1901. 2 Zeits. f. Physik, 33, 9, 1925.§1-7] PERFECT GAS SCALE 13 From this form of the equation, it is easily scen that’ at infinitely low pressures (p-+0) the gas obeys Boyle’s law ( pu=.A) and would thus behave like a perfect gas. From theoretical considerations given in Chapter X, the same conclusion follows. Hence in order to obtain the readings corresponding to a perfect gas we make observations on a real gas and extrapolate the readings to infinitely low pressure. This method was originally given by Berthelot but he used for this purpose his own equation of state and extrapolated graphically and also algebraically to the state of zero pressure. Using Kamerlingh Onnes’ form of the equation the extrapolation becomes very easy and is illustrated below :— Using the constant-volume thermometer let us find any temperature ¢, say, the boiling point of sulphur. ‘The temperature, as observed on this thermometer is, from definition, given by Do "= Peo Po We then perform the compression experiments on the same gas at the two fixed points 0°, 100° and at C. (the temperature to be deter- mined). We have then x 100. Py Uy = Agt+Bobor roses = Avy +Broron | a) Pe = Art Bip where vy is the constant volume and the constants Ay By Are Broo Ay By ate obtained from the results of the compression experiments. Then from definition Upbr 00 = — 2 x 100 VoPro0— Yoho )+Bipr—BoPo) _ an Pines PP ec a A Bipr— Bop Ar— Ag) 00 [i ene aol = ty ByPi— Boho _ BrooPra— Bobo = taal 4 Pe Pome |, with the help of the binomial theorem and by neglecting quantities of the order (Bpg/-4)%. We have put (.4,—49)100/(Ayoo— Ao) = fim the temperature that woul! be piven by the same thermometer if the initial pressure was infinitely low (p)-r0). Hence immo = tige 2 Aywo-Ao This is the onrrecciow to be applied to the reading fy of the constant- - ay4 THERMOMETRY i volume thermometer in order to reduce it to the temperature fj which would be given by the same thermometer if the pressure were intinitely small. All the quantities on the right-hand side except /jim, are known. We thus see that 41, the temperature to be determined, occurs in the cor- rection term. Since, however, the value of the correction is small, we can substitute 4, for fy, on the right and employ the method of succes- sive approximations as already explained. To find the magnitude of the corrections at any other temperature, the value of the correction at a large number of temperatures is found and then an interpolation curve drawn from which the correction at any temperature can be read. Constant-pressure thermomeier —The temperature ¢, recorded by this thermometer is, ftom definition, given by (6). Multiplying by the con- stant pressure py we have ty = Paee=Po% 100, PoVso0- Por and making use of (9) as before, we get (ArmA PBB) 99, eee _ » (12) which gives the required correction. We can draw an interpolation curve as in the previous case. It will be seen that the value of fy, is the same whether we use a constant volume or constant pressure gas thermometer and is given by 100 (A,~-AQ)|(Ayoo—Ag). We can, therefore define the perfect gas scale (Celsius scale) thus : Lim (pu), — Litt (pu) po po Lin Pion 08) a 100 Equations (11) and (12) enable us to obtain the corrections for the temperature range --183 to 4 400°C. for’ which the compression experiments have been performed by Holborn and Otto and consequently the necessary data are available. Above these temperatures due to lack of experimental data this method is inapplicable and a theoretical - equation of state must he employed—-a method which was used for all temperatures prior to Holborn and Otto’s experiments, Above 450°C.,§1-8) PERFECT GAS SCALE 15 however, the correction irself is smaller than the errors of gas thermo- metry (Sec. 1-6) and is, therefore, generally neglected. ‘A very good method of obtaining the corzsction to be applied to the real gas scale is to perform the Joule-Thomson experiment (Chap. XI). ‘The principle underlying this correction will be explained later. Unfor- tunately, however, the existing data on Joule‘Thomson effect are not sufficiently copious to enable us to apply this method and the method given above is almost universally employed. 1B. We give below (Table 1) the corrections which have to be applied to an actual gas scale in order to convert it to the perfect ' Table 1.—Gas Scale Corrections. —_—————_— Constant pressure Constant volume Tem- perature . : ie °C. Helium | Hydro- {| Nitro- | Helium | Hydro- | Nitrogen gen gen gen | —260- . . oe +0°041 . —240 oe 7 +0°033 | +0°117 — 220 . os . +0°026 | +0-089 —200 . +0-020 | +0-069 . —180 . ap -- +0°015 | +0:054 Ee 183 | 40-029 | +0°265}... 40-019 | +0°039 . =100 | 0-005 | +0-053.| +0399 | +0-008 | 40-015 | +0°052 = 50 | +0-002 | +0°016 | +0-112 | +0-003 | +0-003 | +0-015 = 25} 40-001 | -+0-007 | +-0-039 | +0-001 | +0-002 | +0-006 0 |. + 25] -0-000 ; -0-003 | —0-020 = 0-003 50 | 0-000 | -0-003 | -0-025 — 0-004 15 | 0-000 | ~0-002 | ~0-018 +-0:003 125 | 0-000 | +0-003 | +0-025 +0:005 150 | 40-001 | +-0-008 | +0-056 +0-011 175 | 40-002 | +0-013 | +.0-090 +0-018 200 | 40-002 | +0-020 | 4-0: 132 40-027 225 | 40-003 | +0:027 | 4-0-178 +0°038 250 | 40-004 | 0-035 | +-0-225 +0°050 275 | 40-005} .. | 40-274 | 40-019 |. +0-063 300 | +0-006 ao 0-320 | +0:023 56 40-080 350 | +0-008 . | 40-430 | +0-034] .. +0°110 400 | +0-010 o +0-550 | +0-046 + +0°150 450} 40-012] .. | 40-670 | 40-061} .. +0°190 — SOS gas scale. Values of #-#, and #4, are given in the table. The16 ‘THERMOMETRY {h pressure of the gas at (°C. is 1 metre of mercury. The corrections for temperatures between —260° and —180°C. are given by Onnes and Cath, and those between —183° and +450°C. by Holby and Otto.® A glance at the table shows that the corrections are smallest for helium and largest for nitcogen and except for helium they ate less at constant volunie than at constant pressure 1-9. Comparison of Different Gas Scales.—It will be now shown that the scales so furnished by the different gases, when reduced to zero pressure, coincide. Let u8 calculate the value of the quantity (4,—4q)] of for the different gases for various values of #, The necessary data are given by Holborn and Ottot who measured these temperatures with a platinum thermometer, whic. was standardised by comparison with a helium thermometer throughout the range, and thus essentially gave the helium scale. ‘The values of (4;—4,)100/Agfaci) 80 obtained are given in table 2, and are seen to be quite constant and equal to 0-36604 for all gases. Putting (4,~A,)/Aotae) = aand making use of this Table 2—Values of 100 “440 Ay F hel) i Value of 100 (4¢—Ay)/-o finer Gas ———_—-——_— —183° | —100° | —50° 100° | 200° 400°C. Helium. .] 0°36605 | 0-36604 | 0- 36602 036605 | 0° 36604 Hydrogen | 0-36604 | 0- 36604 | 0-36604 o0 0° 36604 +: Nitrogen. . . 0- 36604 | 0- 36604 | 036693 | 0- 36604 0-36604 Neon ..| 0°36604 | 0° 36604 | 0: 36603 | 0+ 36604 | 0- 36605 | 0- 36604 Argon... a 0-36604 | 0-36604 | - 0- 36604 i experimental result we can write for any other gas Ap= Ag(tatun), 6 6 s+ GA) or Lim (pv), = Lim (pu)y (I+rataue) «+. + (15) pore poe 1 Leiden Commun., No. 156 (2), 1922. ® Zeits. f. Physik, 33, 10, 1925. 3 For corrections according to various other authors see Temperatere, Its Measurement and Control in Science and Industry (1941), pp. 56-57. « * Zeits, f. Physik, 23, 77, 1924 ; 33, 25, 1925.