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Up to now we have dealt in turn with the mechanics ofsingle particles, systems 0/ particles, rigid bodies, andfluids. In each case, we tsed one form or another of Newton's laws to analyze the dynamics a/the system and [a/allow ill time the motions a/individual particles or elements of the system. Beginning with this chapter, we broaden our perspective to deal with systems that are too complex io treat in terms a/the motion a/individual particles, These systems usually appear disordered because a/the large number of particles involved and the many differeni ways they can share the energy available to the system, To analyze such systems Ive use the principles a/thermodynamics, In our study of thermodynamics lVedefine a nl'lVset of physical variables to describe the state 0/ a system, and we deduce a nelv set of laws that govern the behavio; q( systems. We also show how it is possible to understand these Ilell' laws on the basis oj our previous laws 0/ mechanics. A central concept a/thermodynamics is temperature. In this chapter we define temperature and discuss its measurement.




A liter of gas contains about 3 X 1022 molecules. Let us
take the simplest possible case and treat the gas molecules as point particles that collide elastically with one another and with the walls of the container. If we specify the initial vosition and velocity of every particle, we could then apply Newton's laws and deduce the position and velocity of each particle at any future: time. Given that information, W~ could calculate certain measurable properties of tlie system, such as the net impulsive force exerted on an clement of area of the container. We call this the microscopi: description of the system. Because the number of particles is so large, it is advantageous to treat the system using average values of the microscopic quantities. T11is approach is called statistical mechanics and is discussed in ('hapter 24. .'\ different approach is based on the following question: Can we describe the system, including its interacti(~0:; with its environment, in terms ofa small number of overall properties that are measurable by relatively easily

performed laboratory operations? In the ("l~.e of a gas confined to a container, we cau indeed obtain such a descriptiou in terms of the macroscopic quautitics-vpressurc, volume, temperature, quantity of matter, and internal energy, among thers. Fur systems other than a gas, we can d fine and measure different macroscopic variables. For instance, j 11 a ferromagnet such as iron, the particles interact not by impulsive for;; in collisions but by magnetic forces; in the macroscopic description of a fClTOmagnet, the magnetization must be includ ed among the macroscopic quantities. Macroscopic properties can usually he measured directly in the laboratory, for example, the pressure of a confined gas or the magnetization of a piece of iron. We can also easil y measure the variation of any such property with the temperature and derive an equation ofstate that describes the dependence of the macroscopic variables 'on one another. For any system the macroscopic and the micr 'scopic quantities must be rela eel because they are simply differcnt way" of describing the same situation. ln particular, we' should be able to express one in terms of the other. The pressure of a gas, a macroscopic quantity, is measured


using a manometer.





Chapter 22

Temperature of copper might be an example. Such a wall is called diathermic. (The word "diathermic," loosely translated from the Greek, means ','heat passing through." You can think of "diathermic" as meaning "conducting.") When two systems are placed into contact through a diathermic wall, the exchange of energy causes the macroscopic properties of the two systems to change. If the systems are confined gases, for example, the pressure might be one of the macroscopic quantities that change. The changes are relatively rapid at first, but become slower and slower as time goes on, until finally the macroscopic properties approach constant values. When this occurs, we say that the two systems are in thermal equilibrium with each other. One way of testing whether bodies are in thermal equilibrium is to bring them into contact through a diathermic wall and to observe whether the macroscopic properties of the systems change with time after they are brought into contact. If no changes in the macroscopic properties arc observed with time, the systems were originally in thermal equilibrium. It might, however, be inconvenient or even impossible to move two systems so that they would be in contact with one another. (The systems might be too bulky to move easily, or they might be separated by a very large distance.) We therefore generalize the concept of thermal equilibrium so that the systems need not necessarily be brought into contact with each other. The separated bodies can be said to be in thermal equilibrium if they are in states such that, if they were connected, they would be in thermal equilibrium. The way to test whether such separated systems are in thermal equilibrium is to use a third system C. By placing C into contact with A and then with B, we could discover whether A and B are in thermal equilibrium without ever bringing A and B into direct contact. This is summarized as a postulate called the zeroth law of thermodynamics, which is often stated as follows: If systems A and B are each in thermal equilibrium with a third system C, then A and B are ill thermal equilibrium with each other.

sure is related to the average rate per unit area at which the molecules of the gas deliver momentum to the manometer fluid as they strike its surface. In Section 23-3 we quantify this microscopic definition of pressure. Similarly (see Section 23-4), the temperature of a gas (also a macroscopic quantity) is related to the average kinetic energy of translation of the molecules. If the macroscopic quantities can be expressed in terms of the microscopic quantities, then the laws of'thermodynamics can be quantitatively expressed in terms of stat istical mechanics. This accomplishment is one of the landmark achievements in the development of physics. As we proceed through our study of thermodynamics, this theme of the relationship between macroscopic and microscopic variables will arise frequently.

Consider the two systems A and B illustrated in Fig. I a. They are "isolated" from one another and from the environment. By "isolated" we. mean that neither energy nor matter can enter or leave either system. For example, the systems might be surrounded by walls made ofthick slabs of Styrofoam, presumed 10 be both rigid and impermeable. The walls in this case are said to be adiabatic. (The word "adiabatic" comes from the Greek for "cannot be crossed." You can think of "adiabatic" as meaning "insulating.") Changes in the properties of one system have no effect on the other system. We can replace the adiabatic wall separating A and B with one that permits the flow of energy (Fig. Ib) in a form that we shall come to know as heat. A thin but rigid sheet



Figure 1 (a) Systems A and narc separated by an adiabatic wall. The systems have different temperatures 1'.1 and T,1' (b) Systems A and B are separated by a diathermic wall. The systems, having come to thermal equilibrium, have the same temperature 1".

This Jaw may seem simple, but it is not at all obvious. If A, B, and Cwere people, it might be truethatA and Crnay each know B but not know each other. If A and Care unmagnetized pieces of iron and B is a magnet, then A and C are each attracted to B without being attracted to each other. The zeroth Jaw has been called a logical afterthought. It came to light in the 1930s, long after the first and second laws of thermodynamics had been proposed and accepted. As we discuss later, the zeroth law in effect defines the concept of temperature, which is fundamental to the first and second Jaws of thermodynamics, The law that e~tablishes the temperature should have a lower number, so it i~'called the zeroth Jaw.



Measuring Temperature


ten two systems are in thermal equilibrium, we say that :y have the same temperature. Conversely, temperature .hat property of a system which equals that of another item when the two systems are in thermal equilibrium. r example, suppose the systems are two gases that inil\y have different temperatures, pressures, and volaes. After we place them into contact and wait a suffi:ntly long time for them to reach thermal equilibrium, eir pressures will in general not be equal, nor will their .lurnes; their temperatures, however, will always be ual in thermal equilibrium. It is only through this argu-

There exists a scalar quant ity called temperat ur ' whic I IS a prope;:tyO/ all thermo 'ynamic systems in eiiiii71 num. \VO systems are 111 ierma equt I rium if and only ijthelr temperatures are equal.
The zeroth law thus defines the concept of temperature and specifies it as the one macroscopic property of a system that will be equal to that of another system when they are in thermal equilibrium. The zeroth law permits us to build and use thermometers to measure the temperature of a system, for we now know that a thermometer in thermal contact with a system will reach a common temperature with the system.

ent based 011 thermal equilibrium that the notion of tern-rature call be introduced into thermodynamics.
Although temperature in its everyday use is familiar to Iof us, it is necessary to give it a precise meaning ifit is to ! of value as a scientific measure. Our subjective notion [temperature is not at all reliable. For example, suppose ou are sitting indoors in' a chair that is made partly of oth, wood, and metal. Touch the various parts of the nair and decide which is "coldest," that is, which is at the iwest temperature. You will probably decide that the ietal parts are coldest. However, we expect that all parts f the chair have been in the room long enough to come rto thermal equilibrium with the air and should all thereore be at the same temperature as the air. What you are. esting when you touch the metal. is not only its temperaure but also its ability to conduct heat away from your presumably warmer) hand. In this case your hand is givng a ·subjective and incorrect measure of temperature. -urthermore, that subjective judgment will change with .imc if you hold your hand on the metal, as your hand and .he metal approach thermal equilibrium with one an-

In Chapter I we described a two-step procedure for establishing a measuring standard for a physical quantity: we define a base unit, and we then specify a procedure for making comparisons with the base unit. For instance, in the case of time, we defined the base unit in terms of the frequency of light of a certain wavelength emitted by cesium atoms. To make I second takes 9,192,631.770 of those vibrations. We can (at least in principle) use tills scale to measure a human lifetime or even the age ot the universe by counting the corresponding number of vi brations. Temperature is one of the seven base units (see Table I of Chapter I), and we might therefore attempt to treat temperature as we treated other base units in the SI system: establish a standard and relate all other scales to the standard. However, temperature has a nature different from that of other SI base units, and so this scheme will not work in quite that simple a form. For instance, if we define one period of vibration of the light emitted by a cesium atom as a standard of time, then two such vibrations last for twice the time, and any arbitrary time interval can in effect be measured in terms of the number of vibrations. But even if we define a standard of tempera. ture, such as that of water boiling under certain conditions, we have no procedure to determine a temperature twice as large. Two pots of boiling water, after all, hilve;h ••• .same temperature as one pot. There is no apparent way using only this standard that we can relate the temperature of boiling water to that, for example, of boiling oil; no amount of boiling water will ever be in thermal equilibrium with boiling oil. To establish a measuring scale for temperature we adopt the following procedure, which differs from the usual procedure for the SI base units: we find a substance that has a property that varies with temperature, and we measure that property. The substance we choose is called the thermomelric substance, and the propert.y that depcnds on tempera lire IS ca cd the thcrmo/lwlne nroprrtv,

You can also test your subjectivity by soaking one hand in cold water and another in warm water. When you then grasp an object of intermediate temperature, you will find that the first hand senses a higher temperature than the second. You can be somewhat more objective in comparing two different samples of the same material at different temperatures by touching each with the same hand, which may distinguish the "hotter" from the "cooler:" This procedure might reveal which object is at the higher temperature, but it is hardly sufficient to be quantitative about the difference. It is therefore necessary that we carefully specify an objective way of measuring temperature, which is our goal in this chapter. In practical use of the zeroth law, we wish to identify system C as a thermometer. If the thermometer comes separately into thermal equilibrium with systems A and B and indicates the same temperature, then we may conclude that A and B are in thermal equilibrium and thus do indeed have the same temperature. Another statement of the zeroth law, more formal and more fundamental, is the following:




. • Anders Celsius (1701-1744) was a Swedish astronomer who.' or the 'cdlor' of a'larrtp filament. in addition to developing the temperature scale named for him. The linear behavior in this case means. defined to be 100°0. (4) To determine a temperature on this scale. . . 98. such as the normal freezing point (O°C = 32°F) and boiling point (100°C = 212 OF) of water. Transferring between the Fahrenheit and Celsius scales is easily done by remembering a few corresponding points. employs a smaller degree than the Celsius scale. we need only one calibration point P. To determine a temperature on this scale. 0/ one a/these substances leads to an individualte'mpe~~ture scale that is defined only/or that substance and that does 1101 necessarily agree with other independently defilled temperature scales. The Fahrenheit scale. where the thermometric property also has a value of zero. 1 is set to zero. We choose the simplest possible relationship between T and X. Daniel Fahrenheit (1686 . and the normal boiling point of water. used in the United States. all of which vary with temperature. We describe the accepted universal scale in Sections 22-4 and 26-5.Tt was also originally based on two fixed points. -.1 Examples might be the volume ofa liquid (as in the common glass-bulb mercury thermometer). 1824. The choice.horma: freezing point of water. The temperature Tis some function of X.6°F (normal human body temperature). a contemporary of Celsius. electricity and magnetism.496 Chapter 22 Temperature . which we express as 9FO = aX+ b. including not only thermodynamics but the law of conservation of energy. 5C. • Lord Kelvin (William Thomson. in which the thermometric substance may be mercury and the thermometric property may be its volume. Note that the degree symbol (0) is used to express temperatures on the Celsius scale. respectively. His-scientificcontributions were so highly regarded that he was accorded the honor of burial in Westminster Abbey in London. we choose two calibration. the constant b in Eq.points. arbitrarily detine the temperatures T. the interval between which was set to 100 degrees: the freezing point ofa mixture of ice and salt. . These two points were used to calibrate thermometers.. The Kelvin Scale* On the Kelvin scale. the linear function given by T(X) = points: the:. 32 OF and 212 "F.' and other 'temperatures were then deduced by interpolation or extrapolation. differences in readings are given in FO or Co (Fahrenheit degrees or Celsius degrees). defined to be O°C. was a German physicist who invented both the alcohol and mercury. for example. and the normal human body temperature. and its zero is set to a different temperature. acoustics. that the intervals between degree markings on the glass tube of a thermometer are of uniform size. in effect. the Celsius scale (formerly called the centigrade scale) is used for all popular and com mercial and most scientific measurements. in which case T(X) = The Celsius and Fahrenheit Scales* In nearly all countries of the world. the length of a strip or metal. the pressure Of a gas kept at constant volu me. . and a particular relationship between that property and a universally accepted temperature scale. and by making use of the equality between an interval of9 degrees on the Fahrenheit scale and an interval of 5 degrees on the Celsius scale. the normal freezing and boiling points of water turn out to be. At that point. The Celsius scale was originally based on two calibration aX.' the electrical'resistance 'Of a wire. Each individual temperature scale can thus be calibrated against the universal scale. and measure the corresponding values XI and X2 of the thermometric property.1736). In this case . T(X). The relation between the Celsius and the Fahrenheit scales is (2) The degree symbol is used in expressing temperatures on the Fahrenheit scale. (3) Note that these intervals are expressed as FOand CO. Let us assume that our particular thermometer is based on a system in which we measure the value of the thermometric property X. Removing this disagreement req-uires the adoption of standards for the choice ofa particular thermometric substance. one of the calibration points is defined to be at a temperature of zero. the temperature is defined to be T" and the thermometric property has the measured value Xp. observed by means of the length of the mercury column in a thin glass tube. as. and T2 at those points. made measurements of the length of the arc of a meridian that verified Newton's theory of the flattening of the Earth at the poles. (I) where the constants a and b must be determined. This linear scale means that every interval of temperature llT corresponds to the same change S X in the value of the thermometric property. On this scale.1907) was a Scottish physicist and engineer who made fundamental contributions to a wide variety of subjects. I I . /lVI as OFand "C. liquid thermometers and used them to study the boiling and freezing points of liquids. Readings on the temperature scale are given in OF or °C (degrees Fahrenheit or degrees Celsius). a particular thermometric property. The most familiar examples of this type of scale are the Celsius and Fahrenheit scales used in common thermometers. and hydrodynamics.

(. (~.. .11)' general agreement. .16 K)(I.:ig::-. but the zero of the Celsius scale IS sluftc d to a more convenient value Today we no longer use tv.. I hi" choice h di 'U~' 1 III Ih next section. 2) 1 he temperature t the triple point has been set b) intcmatlonal agreement 10 be 1~.d)Hli.O.2n) 5:C • __ 0". or for tt) a -.OO· and 99. where . CdSlU . we choose for eur calibration the temperature at which ice..•• a"".1 The Kelvin.975·('. I ahrenhch - temperature (5) (6) .16 of the temperature of the tl ph: p in 01 water. arer and the normal boiling point of water. Vial ( 320·F 1hcrmomeler wen li t. r1 .! fixed pcietsto deftne the Cclsius scele.-:n::-:"~::-rE::-'-:-:>"l~'~1K t".. whi h is very close to the normal Ireezrng point of water. is called the triple f aim 01 war 'I (Fig.lIlt\" f the thermometric substance. .. . 1 392R" . Celsius.o. R 4. and the relationship between the ( elsius temperature 1~: and the Kelvin temperature 'I I \lOW set as 7~"""T-273. with the resistance R 'IS the thermometric property X We life not given the value of R.t = (273.u:":. Find the platinum resrstance temperature 01 boiling water. 7.\IId c ~_-3'-<-'·"1""'C""""'''''' ~1 r----~-ll Abl. 92 between the trip!' poim of \>.. ~hi h is identical with the ideal gas : n per' rure scale di cussed in the next section.Olute [. \Vith this choice of calibration point. other thermometric properties and thermometric substances might bi e ditlerent temperature readings (see Sample Problem I) 10 elnninate this confusion between the readings of <hffetl:nl thermometers. I () ) (.J92)'~ J80 2 K. and water vapor C01. 01 This.::"·:.16 K.16 K) ~ Al! • (7) Sample Problem 1 Tilt: resistance 01 a reruun plaunu 11 wire increases by a factor of I. Solution We use Eq.\. the Kelvin scale is defined. Figure ~ compares th enheu."-".15.\ temperature determined from Eq. but w do know that at the boiling POint of water. we choose as an accepted stand .:. Other thermometers will give dulcreru value example. The size of the degree is the •• me on the CdMUS and the a Kelvin scales. instead. can be determined indcpendcruly ot the a. The e perimental values arc r tively. 8..-' Figure:. The freezing and boiling ponus of water are measured on the Kelvin scale arid then converted t sius using Eq. The kel••m IS thus d 'tmed as 1/273.. I'his point. h! Hi equilibrium. 7 is valid only for IhJ! particular thermometric PI perty.213. scales compared.rd I PC t) pe )1'thermometer in \\ hich the temperature = T" f. value gives the "platinum resistance temperature" boiling water.TI1I'\:-:i~§=!tl. Fhus T(R) where A" IS the value of the thermometric property at the triple point. the temperature ix)lhn£ water 'l'. Eq 6 becomes 1(X) = (273.f"':oTlt.kelvin) is the Sf base unit of temperature on pc the absolute seale. liquid water.-" ••' CI K U~ -..'alet .· J d Vacu\lm lIa~k t I !ffi!k>. and Kelvin scales.

say. The dillerence between the pressure fl of the con ti ncd gas on the Iell branch of the tube and the pressure Po of the atmosphere on the right branch of the tube is indicated hy the height II of the column of mercury. The bulb JJ containing some gas is put Into the bath or environment 'whose temperature T is to he measured. gain we waul I hml a Wid" '. and calculate the provisional temperature Tofthe system using Eq I( . the vanation in readings between ~as lb. connected by a capillary tube to a mercury manometer. II cooI IS of a bulb of gla .l\ ••• r of. and with Ih: volume kept constant at Its previous value.(273. which suggests that we choose a gas as the standard thermometric substance. It turns out that as we reduce the amount of gas and t!1\ rd. of a system. 7. 0 em Hg.pgh. different thermometric substances all give the same temperature at the triple pouu. hut (as we have seen in Sample Problem 1) their readings at other pomts may differ. tor mstauce. 9. mtrogen. and mcusurm the temperature of the System using different ~inds or \ ires In Hi of differing materials. and thus p = Po . The smallest vanauon in readings h. or platmurn-ciridium (depending on the temperature range over which It is to be used). (constant 11. 1 Obi.:1 shows a diagram of the thermometer. .IS (such as rhat in the caoillar 11. Scale h 22··.1I0 J lefimte temperature scale.He it pressure.AS _ TU\lf>ERATURE SCALI~ The temperature of a system should have a well-defined value.' mornetcrs 1l~1!1I'.. we must select on particulnr kind of thermometer as the standard The choi e Will be made. which is dcterrmned USIOg the constant-volumc ga'.copper -cOn taman thermocouple is 440 K.:n the temperature is given pro VI tonally by 1'([1). we measure the gas pressure /1. valid only for that dc\ Ice [he accepted temperature of the normal boiling 1 'lilt ot \ ater IS )7. thcrm nnctcr described 10 the next section. ( I) (0 allow rOl the small volume change owing to slight contraction or 1:\pansion of the bulb and (2) to allow for the fact that not 1'1 the confined g. different kinds of &U~ is reduced I ) lien there ecrns to he something fundamental ~'\{ IIC bCI1. constant volume thermometer ut c ta nmr a ga at i \\pre ure 1 ct u therefore consider the pro} rue 01 the constant-volume ga~ thermometer. for example. its pressure dep nd on the temperature and increases linearlv with 11 • -ig temperature. porcelain. anauon in the measurements. in practice the apparatus is very elaborate. (9) thermometers using different gases. not all the basis of experimental convcmcn 'C. platinum. ut by inqumng whether the temperature R '/}{ FigUf~ 4 A constant-s olume -as thermometer. rile .1 particular thermometer proves to be u ctul !D Iorrnutating the laws 01 phYSICS. It the v lurne of a gas is kept constant. quartz. (10) tho r mornctru PiOJ ell I igure .\ I 5 . put into the bulb so that WIlNl the bulb is surrounded U) water at the triple POlOt the pressure ri. and we must make many corrections. mdependcnt of the particular means used to measure 11. I he COt~ taut-volume gaS thermometer \l c~ th: pre' sur ot a gas at constant volume as the > where II is the density of the mercury in the manometer. Results of such a test \\ \iuld ho« that the thermometers <Illgive different readIn' \\ c ought conunuc h .choosing a particular thermometric prop . and that p is the correct d \ alue 1 th absolute pressure at the temperature of the oath 1I11.16 K)£ P. as in Eq. According to Eq. Now we immerse the bulb In the system whose temperature Twe wish to measure.1\ "'11 immersed in the bath 1 e\ u assume that all con c II I have been ma Ic..11 defined D\ . found amongmnstalU·yolwncgas can be made to coi ncidc \\ ith J fixed reference mark. is equal to a def nite value. 'I he bulb 81\ immersed in a l ath \\ hose temperature is to be measured The difference between the pressure of the &:\S III tht' bull 111d atmospheric pressure is determined b~ the he: hI 11of Ill' col- r umn of mercury. We might imagine doing n series of measurements in which we simultaTIl'\1Ihl: use different thermoraetric properties to deternunc the t ~mperatur . by raising or lowering the mercury reservoir R. the mercury in the left branch of the U-tube Let a certain amount of gas. LiCI'! of these readillS 15a rernpcrctur •determined on a "private" seale.n •. THE IDEAL . uch :1" the resistance of n wire. thu keeping the confined gas at a constant volume.

: ro ofternper- ... It is absolutely ne essarv that us definuion hi: independent 01 the ropcrtics 01 i ccrlic material It wo lid 110l do.lllon 01 p:lT. We therefore define the ideal gas temperature scale: ·r-(273. Wc als show 110 I the IIk. (11) been achie ed.E. I'he absolute (em 01 temperature has defied all attempt 10 reach it e.. to have such a OJ IC quanuty as temperature dt!J~I\(...-fu----.II the pr pertics or anyone particular gas.~ o 20 40 60 ~__ 101 ~ Ill' eo 100 Per (em Hg) Fi ure 5 As the pressure of the nitr gen gas in a con iant-volurne gas thermometer is reduced from 0 em Hg to 40 nd then to 20. which IS the ideal gas temperature 7' of the system.':l111ng h) ll'IIlIl\!I.! nt .-o PI.. \ hich remains a gas at lower temp rarures than an~ lither gas.. lurne gas thermometer depend on the gas used at ordinary values of the r ference pressure. OUf stand rd thermometer is chosen to be a constantvolume gas thermometer using a temperature scale defined by Eq. 1\) obtain this temperature \\C rnu: t lISC low-pressure helium. as we ha 'C already done in 1 c II. and you alwnvs ~d the same :tIlS\\CI .-PI. \Ve cannot give e: I crim mal belov about I b}' means of 1lH. p. so that Pir has a smaller v: lue.ruturc calc in 'I W:1~ that is independ nt of the propcrues 01 11) paruc ular subst n e. 'ale..J un the c pan I it oln crcur . The lowest temperature Ih.rn Hg. on the propc IIII:) ora o-called ideal gas). say. X 101 (.! ut tempe 1· tures in which a gas th rmorneter may be u ed. II. also plotted in FIg. we can extrapol te the resulting curve to the Inter cction with the a is where p" . indep ·Il. pcrimcntally. The full range of the vertical sc le is about I K fur I. 11 10t:\ dep 'Hd on I he properties of gases in general (that is. for e. be expressed. '1011 can use any gal. 5.. We continue this same procedure.olume gas thermometers using different rases appr ch the same lue T.-f . The extrapolated v lue of <1 gas therm unctcr.. one an hich the laws otihcnno I> nauucs IOU. between the microscopic mouon of m can be measured with a gas thermometer IS about I K. \ scale.~ 2 'l ' ~ 1( IU J Hz ~Ie::'$p'_n_l_·t)(_)_h_ng.. as we how 10 Chapter 23.11 IS ~ OlIC itic temperature depends only on the general properties of gases and not 011 any particular gas. called the Kelvm uch a scale. which we can regard as the temperature of the system.. 'I e also show in Section ::b-5 that the Kelv III :. 5.tnllgul:ll( salt . Although there is a dir t onnection.I!\l!\'\ result of this measurern nt is plotted as a point in ig. \\ e chose the gas thermomcrer a o r standard instrument precisely because no su h sp . Then we return the thermometer to the unknown system. ample. obtaining results shown in Fig. The lines show that the temperature readings of a onst nt. We would like to define :i tem] . " n cutes and the ma -roscopi temperature. and calculate another provisional temperature T. reducing the amount of gas 10 the bulb and at each new lower value of JlI(ca\culaling the temperature T."He diluuon rcmvcrutor Aniabaric derna nelLl. The data points lor 2 nd the resulting straight-line extrapolation are shown in Fig..). X 10) urface of un Mehina point of tungsten freezing point of wat 'r ormal boiling point of '1 ~ 7" 10] 17 He Normal boiling point 01 He [ean temperature of univer-. oro. If rernpcrnture IS to be a truly fundanrental ph ~iC. hut icmj vr atures within a sm II range (I O'~ K) 01 absolute zero have (constant V).that the ah ilute temper turc . r any othcr su h "handbook" property. 40 .-..ll quantity. However. IS thermody n mi show in Section 26.thc electrical re isiivity [platinum.cilic properties of marenals art' involved in its 0ll'l auon.$m in ion lest rea 'enter of Sun lor 10' I(II (.•. lor tlus r son we can use units of kclvinsf r thcideal gu temper3tuTC. 5.e lIIe.( and the Kelvin ale arc identi :\1in the ran 'f. If we plot the values ofT a rainst p".I~ Ins an absolute zero of 0 K and that it IS impossible to (001 system below 0 K. measure the new value of P. \ e r peat this procedure with gases other than nitrogen In the thermometer. 5. • '0 v we I ·turn the thermometer lO the triple-point cell and remove some ot'the gas.O. pical conditions. II l~ not true 1I1:11 3\1molecular monon cease at the absolute It. the temperature readings of constant. . the temperature deduced for the system appro hes a limit correspondin to a pressure Other gase pproach the: me limit. as the retercnce pre ure is decreased. J able 1 1t~1 the temperatures in kelvin oi'variou I xlic ani pro I:'~~..16K) lim. Although our l mpcrature scale j.< .

Bolli ng point Triple point Triple point Triple point Triple point Triple point Melting point ON THE Substance lelium I !}drogen Hydrogen II ydrogen . The connection between temperature and molecular kinetic energy is based on classical concepts. In aircraft manufacture. 1 he "springs" are quite tift and not at all ideal ( • Problem 3 1. m. 27 (1990). trapolating beyond the highc t fixed point A new scale h s been adopted by the International Committee of Wci hts and Measures abo t every 20 years. 7. For practical use. M~(ro!ollla. Materials used for dental fillings have expan ion properne SImilar to those of tooth enamel.1n a thermometer ofa familiar type. You can often loosen a tight metal Jar hd bi holding it under a stream of hot water.8058 234. see FIg. 3. ~ Thi bollin point is for a pressure or t atm.16 302. the gas thermometer is used only to establish certain fixed points that can then be used to calibrate other more convenient secondary thermometers. As its temperature rises.. the bimetallic strip is coiled into J heli that winds and unwinds as the temperature change: ce fig.9146 Indium Tin Zinc Aluminum Silver Freezin point Gold Copper Freezing point Fre zi g point Fre zin point Freezin point Freezing point 429.20. 2 PRIMARY FIXED POINTS 1990 Il\. Preston-Thomas.025-17. to be used for interpolating between these fixed points and for c. the fixed points of the most recent one (1990) arc shown in Table 2. The adopted scale consi <.28c 24. by ele In . or freezing points are for a pressure of I atm. The International Temperature Scale Precise measurement of a temperature with a gas thermometer is a difficult task. • The: temperature of the boiling pomt varies scmewhat with tb pressure of the gas above the liquid. This scale consists of a set of procedures' for providing in practice the be t possible approximations to the Kelvin scale. In practice. the metal lid expands slightly r lative to the glass) r. 8.078 692.3156 273. AU other boiling points. Pipes at refineries often include n cxpan Ion 10 p. We can understand thi expansion hy considcrin simple model of the structure of a crystalline solid.7485 505.33 Freezing point 1357. while the quantum theory tells us that there i a nonzero lower limit t the molecular kinetic energy. . \: e have all seen e pansion lots in the roadways of bridge. as Fig." by H. The temperature scale gives the relationship between T and p that can be used \0 calculate: T ior a ilven p. as in the-calibration of industrial or scientific thermometers. We can thus visualiz he solid body a a microscopic bedsprin (Fig. the International Temperature calc has been adopted. rivet and other fasteners are often d igned so that they arc to be cooled in dry ice before in ertion and then allowed to expand to a tight fit. of a set offi cd point •• along with the Instrument . Thermal expansion is not alway desirable.9 ) 337. ). 90).5561 54.26. Ihe atoms arc held together in a regular arr . 6 suggcs . Thermometers and thermostats 111:1\ be based on the differences in expansion between the cornponents ofa bimetallic strip. requiring many months of painstaking laboratory work..TTER ATIONAL TEMPERATURE SCALE" State Boiling point Triple point Boiling pointb .1 force) which are like those that would beexerted by a t of springs connecting the atoms.04Sc 20. melting points.3584 83. 'con O"'Y en Argon Mercury Water Gallium Temperature (K) 3-5r 13. so that the pipe will not buckle as the ternpcratur nses. The familiar liquid-in-gla s thermometers arc based on the fact that liquids uch as mercury or al ohol expand 10 a different (greater) e tent than do their lus\ containers.500 Chapter 12 Temp rature ature.8033 17. This zero-point energy cannot be inferred from classical calculations.677 933473 1234. p.77 • See "The lnternauont I Temper ture Scale of 1990 (ITs. even at absolute zero.

T> To Figur 7 A bimetallic stop.element II ure thermometer based on a bimetallic strip. The mplitude of vibration is about 10-9 em. llo ' ver. the strip bends as shown. and the average distance be ween aioms . If the length of this lmear dimension is L.flng POinter ' to the temperature AL=uLtl/. and there are about IOn of them per cubic centimeter. linear expansion.alues for dif erent r I te rials Re nun this lor mula. bout one-tenth of an atomic diameter. the tom vibrate at larger amplitude. this change in length AL is TABLE 3 ubstance SOME AVERAQ!. Many thermo tats operate on this principle. It is Il n sufficie I to choose an average alue that CuI) e treated as a on \. At any temperature the atoms of the solid are vibraung. which coils or uncoils as the temper ture i changed. we obtain Q. the \ alue of u depends on the a tu I temperature and the referen e 1 mperarure ho n t determine L (see Problem 2}). The sinp is formed into helix.. and the frequency is bout lOll Hz \ h n the temperature IS iner ased.1nwrite -where different called the wet It/.'II( ') line. width.• C'\P IISiO/j h s r . or thickness. of a fractional eh nge in length per degree temperature change. l Ience we C. so that a has the meaning...: COEFFlCIE. L1 AR EXPAl SI r r 01: --------------------------~~-- .'1 and 10 the original length L.) This leads to an expansion of the whole solid body. In f able e li')t Ihi: o Chapter 15). if AT is small enough.. proportional 8e." 1' •• To a strip of steel welded together. usin the motion of the end of the strip to ma e or break an electrical contact. ( ee the discussion of the microscopic basis of thermal expansion at the end of this ection. is called a. increases. At temperatures higher than To. The change in any linear dimension of the solid. We find from experiment that. the change in temperature flT causes a change in length flL.ur C) \~ ith which measurern nts need t be made. (13) Helical bimetal . such as its length. Stri t1y speaking. change 6. at lower ternperaiures 11 bends the other way. its van non I~ usually negligible compared to the ac . consisting of a strip of brass and 3t temperature To.ot over a ertain temperature range.

howey r.dUldr). where its value is 999. ~A .1lure. \\ here we have used the value of a for steel from Table 3. which is the reason that lakes freeze fir t at their upper surface. if'we could maintain the same temperature variation (5 CO). ed in rubberlike substances and in certain crystalline solids over limited tcmr raturc intervals. the thickness. whether straight or curved. If you scratch your name on the plate.ralure intcrvals. V-3 tl T. to expre s temperature changes here. Every line. What is the maximum temperature variation allowable during the ruling? pansron increase A steel rule at two different temperatures I he exin proporuon in all dimensions the scale. (Note the use of C'. The order of magnitude of th expansion i about 1 millimeter per meter length per 100 Celsius degrees. Liquid ••typically expand with incrcasi ng tempe . and the potential energy nSC5 ~l~'epl} (F. that II. Thus.000 '!) crease of about Solution From EQ. lengthens in the ratio ex per degree temperature rise. somewhat weal-a attractive forces' take over and the potential energy nses more . the hole. we could achieve the same precision over a temperature interval of about 75 ". you should be able to show (see Problems 30 and 31) that to a high degree of accuracy the fractional change in area A per degree temperature change for an isotr pic solid is 2a. . tore that If the alloy in. 11 \C sho« Ih volume expansion curve for water. (0 obtain such an cxpan ion would require a temperature in20. the line representing your name has the same fractional change in ten th a any other line. we have 4£ (Xl. although not linearly. only the change in volume with temperature is signifrcant.lowly. or. strong repulsive forces come into pby. the numbers. because ex is positive.) (0) m ITTlT] 9 0 Fis:urc 10 • mple Probl m 2 A steel metne scale is to be ruled so that the millimeter intervals are ac urate to within about 5 X lO-s mm at n certain temperature. t a given VIbrational energy the scparation or the atoms changes periodically from a minimum to a . thermal e nansion of a solid su csts an increase in the average sepa uon betw en the atoms In the solid. and thc hole diameter.502 . as the atoms move: Ianhcr apart. The densit of water is a maximum at 3. their separation decreasing from the equilibrium value ro. (14) find that fJ IS rclauvely independent of the tempe r. cquiv lently. 12. The analogy to a photo-graphic enlargement i hown in Fig. ••• (II 4T- 5XI~smm. to. For all the subtanccs listed. the face diagonal. and the scale OIUSl be used within that same interval of temperature at which It wa made. the most common liquid. If we kl /1 represent the coefficient )f volume expansion for . except that a solid is threedimensional. r were used instead of steel.')g-C. P i not constant o\'er these large tern .. water e pands instead of contractin . Such an c pension with decreasing temperature is not observed in any other common liquid. The • temperature during the luling must be kept constant to within about 5 C'. tlLIL(-ex T) for a given tlTis the same for the length. their S~. Accurate measurements sh iw. that is.0 mm) -4. that is. if you have a flat plate with a hole punched in it.• experimental values for the average coefficient of linear cxpan ion of several common solids. and the thickne s arc all in rea! d bv the same factor.:[ .1 : ••uion mcreasm from the equilibn um \ 1Iu('. water. called I otropic. The expansion is quite analogous to a photographic enlargement. With these ideas to mind. we.•c like that of Fig. d( cs not behave like most other liquids. the percent change in length for a given temperature change is the same for all lines in the solid. X 1Q-4/C'XI.}liquid so that \ 1'/1' ( 161 fJ --. th If volume expansion being generally about III times reaicr than that of -ohds. 12. however.971 'gjm1 (The standard kilogram and meter were originally supposed to correspond to a maximum den. (The expansion hewn I greatly exaggerated.Chanter 22 1cmperature . it is obscr. the body diagonal. (That is. In FIg.could achieve an accuracy due to temperature chang of about 3 X 1O-~ mm.2aA AT.) As the temperature is lowered from 'C hI O·C. •••• hereas the change in volume of liquids with changes in orne level.. turc.5 C . otc that above -l' water expands as the temperature rises. The potential energy curve for t •••• adjacent atoms in :l o crystalline solid as a function of their internuclear separauon I~ an asymmetric cur . ' international standards do not correspond exactly to this \ alu ) Microscopic On the micro Basis of Thermal E pan ion (Optional) anti the fraction Ichang in volume V per degree temperature change for n isotropic solid is 3a. However. W' For many solid. ( 15) Because the shape f a fluid i not definite. As the atoms move close together. the change in Si7C consists of an c parisien as the temperature rises. not -C. ity for water 0 1000 kg/ml or I g/cml. temperature or pressure is very much smaller. Gases respond strongly to temperature or pressure changes.

Can one object be houer than anotherifthey are at the sarne temperature? Explain. \\cU and these modes of vibration allow the solid 10 CMtr3Ct as the temperature rises. Are there ph}sical quantities other than temperature th:u tend to equalize if tWO different systems ate joined? 6.) .QllnlftltH 503 01--1----. 4.I· t ture an73.:rgy (fl' f.h~l:Jnl'c.mon. gl\lIl~ "1.. • Q ESTIONS I. At $(iII higher vibrational energy the average separation is even greater. 5.Iflku!:n mass) of water a i1 function of us temperature.'S tlw temper. the . the average separation of the planes 01 atoms decreasing.I 100 Figure 12 Potential energy curve i~}r IWO adjacent .\pan\lon " .n me average ~p. J. H\ •.. Because the vibrational energy in- anal SlS TCm. I ne sp. shuv. Hence thermal c.. as suggested by Fig.4ivlO :I net ncp ."" ! ••.C Ih~ . 12.:-:lIi •• volume IS the inverse of the density (th mass per ' UOIt volume). Because the curve h :1\) mmetnc. and time? Think of a pendulum. mass.lf\g :1 minimum specific volume (Of a maximum density).\ -tiled Temperature l'C} Jot'LOH' consequence 01 the J.Jl1d.lS(.llY of water? 9. constant-volume p~ thermometer when the bulb ts •• the inplc-pouu \emp.\~II.tH'T<lg.. Can \\e define temperature as a derived quantity.. the average separation tr" r~) InCrC.jH\ 1<:lflik! contract us the tcmperatur e rises the . in terms of length.. equilibnum maximum value.cnoml' non thnt C' fl be treated \\ ith gre:lIet II1sigjll usin ' st: mil" l me chanics and qu 111 m theory. Why does the thermometer reading decrease II••a time'! 7.unpluude of the \ ibration. forJ the g:t ISO h:C!l and p~ ~Ol)l Ili~:1M /I .IS iure 1'1' 1. A piece of ice and a warmer thermometer Me suspended In an Insulated evacuated en losure so that the)' are not in contact. bsolute zero is a minimum temperature.::. ~ hich then contribute a l:lrg r sh. nd the vibrauonal cu.} curve were 'i) nuueu h': about the equifibnum separ.•.un\" valid if one assumes 111:\\ (lilly compresvioual (longl\udmal} modes ofvibraticn exist or that these modes predommate } lowever. in .:e (transverse) mode» a:.the coefficient of thermal expansion. these transversemodes of vibrauon may predominate over the longuudinal ones.J complc pl. Is temperature a microscopic or macroscopic concept? 2.. l ••uon trom "ytnmdl)- ol'thc HUh' I:hara: lc'fI.'I\\ B.H.Is there l\ maximum temperature? . It should be emphasized that the microscopic mllJeh lie potcnua! enCfr) curv 01 'vilLI.. For certain typ¢5 of crystalline Structure and In cerlain temserature regions.. Let III be the pressure lrt the bulb of a.!1 1 terms of the dem. :t 11 (. . for example.' ) increase creases as the temperature rises. The equilibrium separation l~ ro.t!!On would equal the equilibrium s<:p.!1 cller!?.un i the entire solid e I .tb. Some crj SMl1IIH: ~oluh.) I'he specinc volume (the volume occupied b :. What qualities make 1I particular thermomeuie suitable for use in a practicel rhermerneeer? pr PI.'I. the average separatlon being greater than the separation because orthe asymmetric nature of the potential energy curve. I ote that rt IhC·POLClltl.: separation between atoms increases wuh ternperarure.ln K and lelfl be lile pressure when the bulb h at room temperature Given three constant-votumc g:h Ihermometers. (b) An enlargement of the region near·\ "C.•tOIl1' m solid as :l Iuncuon (it their uuemuctear scparauon . thus the parti Its move slower and spend more lime :11 large separauons. re to the time a erage.jl:'1tion:n mailer \10\\ klf!.. The effect is enhanced because.\) presented here are ovcr-amplincauunv 0/ . the kinetic energy is smaller at larger eparauons. solids may vibrate If! shetlrlo\-.l. What diftkulties would arise if you defined iempcnuu •.

as indeed titey do. Mark each of the folio'>' ing statcments.. What causes water pipes to burst in the winter? 35. 1'10\ part of the structural $UPDOI t of the house'! 27. Chapter 12 Tcmperatvre em Hg. S ate some objections to usmg \ ater-in-glass as a therrnorne- TA . explain why 20. Why? What ered the pails? U.. What are the dimensions of 0:. alt three thermometers wm give the same value of T. the gas is also oxygen but Pj . Water expands when it freeze . Change (0 Celsius.. Explain why lakes freeze first at the surface J4. (2) The two oxygen thermometers will agree with each other but not with the hydrogen thermometer. Although the absolute zero of tempera ure seems 10 be c pcnrncntally unattainable. scale"? Discuss. 12. it gels stuck in the nng. and (f) liquid helium? 33. The Physics T(. by the way.){PcJ30 em Hg). The editor-in-chief ter. (3) Each of the three wtll give a different value ofT. A metal ball can pass through a metal ring.' oesirable In a gal>for such purposes".40 hydrogen and p) ~ 30 em Hg. Tc "" (21 .do you suppose he meant. ExpJllin why the apparent expansion of a liquid in a glass bulb does not give the true expansion 0 the liquid 29.true or false: (I) With the method described." by Albert A. Explain how the period of a pendulum clod. one contnming hot water.. You put two uncovered pails of water and one containing cold freezing weather.16 K)(P•• /20 ern Hg). 10 obtain still lower temperatures? Isn't this low enough for all practical purposes? water. (0) the Earth's upper atmosphere. Bartlett. How would (a) 'lB. and Kelvin scales. lhJI is. Fahrenheit.------. Fxplam the fact that the temperature of the ocean at ueat depths is vcry censtant the year round. \\'hltl would be the coefficient of linear expansion of such a lattice. you suggest measuring the temperature of the Sun. temperatures as low as 0. were heated? 23.00000002 K have been achieved in the laboratorv.(273. rather than the ball. Can a temperature be' assigned to a vacuum? 14.) 16.. can be ept constant with temperature b} attaching vertical tubes 01' mercury to the bottom of the pendulum. and what did be say litemlly? (See "Warmth and Temperature: A Comedy of Errors. 1985-1986. docs hotter necessarilv mean 111~hertemperalure. p. We are free .(II:Ju!r: November 1084. xpansioc for the freezing process? or . What would hap. mana("..517. A common mode! of a solid a sumec the alOlll'. one of iron and one 01 line.------. however. Considenng the clSIUS. A -----. consisting of 1WO different metal &trips riveted together. A bimetallic strip. Why would physicists strive. docs nny one stand outas "nature'.. (b) In the everu that there is a disagreement among the three thermomcters. 'll. v hy !l6? (lllni. prove It. Explain why the column of mercury fir:.50. be frecstandmg. 24. Two strips. at a temperature 01 about 4'('. to re POInts executing imnle harmonic rnouon about mean lattice POSInons. arc riveted together side by side to form a stratzht bar that ClWT when heated Why 1$ the Iron on the inside of the curve? 25. What can you conclude about how the mclung pomt otice depends on pressure from the fact that Ice floats on water? PROBLEMS Section 1. (tl) An approxiTean be obtained with 11. 26. outside in belowthe hot water will usually would happen ifYOll cov- degrees as the unn of'temperature change.1 descends and then rises when a mercury-in-glass thermornct r IS put m a flame 21. 10. TII ••• (27 3.lh used? When Fahrenheit degrees are used mstcad of CdSlUS of a well-known business magazine. wrote: "The polar regions mIght be three rimes warmer than now: . is used as a control dement m the common thermostat Explain how it works. lor C the gas is measured values of p for :mdpc. 430.J40 ern Hg). The the three thermometers are I'A' PII> mate value of'the room temperature each of the thermometers using ]8. (d) the Moon. Why is it much more difficult to make a precise determination of the eoefficienr of expansion of a liquid than of a solid? Jl. (c) an insect.-------Temperature to define temperatures measured b1 such n thermometer 10 kdvim (K) \0 be directly PlOp0t110tl31 0 the resistance R n~JMeasuring resistance thermometer is a thermometer in which the electrical resistance changes with temperature. explain how you would change the method of using them to cause all three to give the same value of T. The patl with begin to freeze first. Why should a chimne.) (See The Science )1/.. (c) the ocean floor. 15. :'1.. Is mercury-in-glass an improx emcnt? If'so.16 K. 19. discussing po sible warming effects associated with the increasing concentration of carbon 'dioxide in the Earth's atmosphere (greenhouse effect). pen if the ring.. Can we define: a coctlicient olume •. or is Ihls just an arbit racy convention? Celsius.16 K)(p.) I!. how? If not. the cocllkielll ot linear expansion? Does the value of 0: depend on the unu ofknf. Wht'n the hall is heated. Many medicine labels inform the user to store below 86"F. " What . Does our "temperature sense' hav e a built-in sense ordireelion: that iv. Is one gas any better than another for purposes of 1\ standard coostant ••volume gas thermometer? WhJ( properties UI\. originally cho: e the steam point as O'C and the ice point as IOO·C. docs the nurncncal value of 0: change? If so. Does the change in volume of an object when its temperature is raised depend on whether (he Object has cavuies inside. other things beina equal? 3(). p.

(0) On what Iaciors does A depend'? What are its dimen ions? (b) If at me instant show that it i 1-0 the temperature difference is A1'o.tti. . If the temper' ture difference J between an obje t ' nd its surroundings (6T. I he press ! di er nee t . .1$ sho n in PI'.'" t\ hatt 9. 13. with one juneiion held t O·C.. If) ur doctor tells you lhat your temperature is 31Q kelvins above <l olute zero. The minus ign appears bee use AT decrea ~ with time if AT is positive and increases if t:.\0 unknown tcmncrature to 1)1:measured hod the lll\knov. At what iemperat ire. on the Celsius .n tempera. ewion's law 01 C oltn' does not pplies: see the :>6. !Iov.t K). the PII:S ure ditleren <: IS <)0 mm Hg when one bath h..0' it I> 3 2 \: 'hat woul the gam be ar 28. The outside iemperatur IS -7 O·C. the lowe t Oftl~ t I \I re rdcd temperature I -70'r at Rogers Pas . ( ) In the continental United 'tateS. Wha temperature is indic led b ' the thermometer if ih bulb i plac d in n environment su h lh t Its resistance i other 4.Len the g.'lO fall b) n- 1 ' . A particular ga!>thermometer is constructed of two g:! -cuntalfllng but . and (c) lsius and Kelvin? mperarure i the Fahrenhelt scale re ding equal to (allv.. 6.) is .II the boiling point? Vhich pre.T . should you worry? Explain your anwcr. 1\'. the me readin : (al Fahrenheit and Celsius (b) Fahrenheit and Ke! -in. each of which i rut 101\) a water t> ih. A zrtain resistance thermometer is found to have resistance R of 90.on the Fahrenheit sc le. 986 'F. MOlltnna 1 xpre s this on the CelsIUS scale. Exprc thb on the Fahrenheit scale. Tv o consram.. the limiting value f the u tio 0 he pressures that of the Celsius nd (b) h If that of the Celsius? . BOth ont In enou 1 b'I that Pit 1 m Hg. It is an ev rvday ob nation that hOI and cold objects cool do n or warm up to the temperature of their surroundings. n I hV"1I to Ih' diagram. dilfercnc JAT --A(~:t) dl where A ' IS a constant. (d) ExpreSS the nor01••1 t Illllg point of oxygen. Ifthc!!.v. \0 45 Olin.2 mY."111M 'II! I 50S measured in ohms (n).one U ing nitrogen th WO! king nd Ihe other usina hehum.3 n when its bulb is pia ed In water 31 the triple-point temperature (27 J. A thermocouple at 1"'(1 Src/ion n-4 Tht Id('ul IIU 1emperature Seat« is termed rom two different metals Joined SU n. IS kept fit constant volume] 12.. Absolute zero is -273. much longer \\111 ': t e t r the insrde rernperat . :. approxi. What is the difi rence between the pee ure in the IWO thermometers II both are Inserted InIO a '" ter b. maintum constant vol me in the two bulb 1h re 1 no 5.tlh . the output voltage vanes linearlyfrom 0 to 2!10 IIIV as the ternperaiure of the other junction is raised from 0 to 510' • Find ine temperature of'the variable juncnon when the therm ouple output is 10. 10 . Ft 5.:momingtheheatcrofahousebrea down. zeroon the aiure auhe t rn i Iti 373. t a ti me tIler. that is. 3.183 . (n) f he temperature () n of the surf ce of the Sun I:> about '.T is neg tive This i known 'ell/on's law of cooling. ut the trrple POIllI alld the other IS \II .3stempe points in h: ay that a small voltage j produced wh n the t vo junctions are at different temperatures.h.olum gas thermometers arc as n I d.1 K. Th arn] 11 icauon or am of a transi tor amplifier m y depend in the temperature. ifan)" do the following pairs of scales t-i . Finallv. ( a result.0 CO? Assume that the outside temperature change and rhat pre ious problem..0·C if the gain depends linearly on temperature OH~r this limned range? 4. (b) L press I m I human body the two hul is mea ure b: a mercury man m ier ~ h \\1\ in the tigure. Appr priate reservotrs. the inside temperature drops (rom 22 to 1 • . The in for a certain amplifier at n »n temperature (200'C) is 300.15·c' Find absolute Fahrenheit scale.2 n! 2. (e) At what elsius temperature would you hnd a room to be uncomfortably warm? ( J Fil!Uft' J 3 Problem 1_. difleren e in pt suo _ vhen both baths re at the triple point of water.•. arl} In th. whereas at 5 . sure IS ihe higher 01 the two? See cling or \\ rrning of the obie maiely.T•••• not tOOgreat. In :1 p rticular iron-iconstantan therm ouple. 7. The pre sure difference IS 120 mrn H when one bath is at the tnpl polnt and the th r i at th 'lx)I\tng point of water. to this temperature t is proportional. the rate of <illJ .1 at the team point and at Ih triple point 01 v ter v.

at about which value it remains today. 15. 20. See Eq. A gJ Chupter i: Temperature cicnt of volume expansion of mercury and cr cicnt 0 linear expansion of tass. I l.17 m and the coefficient of lincar c pansion 10 6/('. the hange in volume of'u solid u n expan ion thr ugh a It mperature rise Tislti\cnby'~r'-3 I ~T.OO·C. When the temperature ora copper penny (which I not pure copper) is raised by 100 CO. 15. As a re ultofatemperat\lrcn~orJ::!· its center bu Ides upward. whcrefJis the coefficient of volume e pansicn of the liquid. 9..tI of a rc rangular plate l. so is the density p Show that the chanae in dcnsuy Ap With change in temperature 'l is given b.a bar wirb a erack at h~. Dens. 31.n a controlled way.v.t s cube ha an edge length of 33. th I if w neglect extremely small qu nuue . 33. (c) the volume. 26. (/1) III thle! 55. \ I ras nn has Figure 14 Problem 22. proportional to the temperature. Oy how much Ih ellur ha'i its area increased when its temperature is40' ? A ume that the glass IS free t expand. and (ff) the muss of the penny. l Figur. This was accomplished by fastening the source 10 one end 0 an aluminum rod and heating the centralsection of the rod I.8 m. Find (0) the increase 10 surface area and (b) the increase In volume when it is heated to 75. . l r. mass divided by volume.v.. ised h the dccav of radioactive elements raised the average internal temperalure (rom 300 to :'1000 K. Iter a temperature rise A J • SlJ illS longer by Aa and side "i Ion er by Sb. 2 em at 2S' .If the effective heated section of the rod In Fig. how that if the lengths OIIWO rods of dill inverseh proportional to th rr rc I '<. the UI\t.II\':C (a) r nt \ . lib. wherejJls thc coeffi- . 'eglccr the expansion of the glass tube. 1'1 nt on the temperature I [. (c) C'll ulate us coefficient of linear expansion. by how much has the radius of the Earth increased since it formation? 15.30 m? 28. an average coefficient of volume cxpansion 0 3. the height I: ch: ngcs by 6h ~ Ph I.dto\>e20. heat rele •. Soon after the Farth rorm« . Arod i me sun. Iepcndcnt. i 1 . at what onstant rate must the temperaturc of tbc rod be made to change if the source is to move at ~ constant speed of 96 nm/s? Figure 1 29. In a ertam c .t} Au blab (see fig.1 em at 20. a shown is 25 rises.: J 1<. and that JI is the volume of the bulb of mercury at O. ssumin .. its diarnet er mer . how that it (1' is dcpend I. t -12"C 160· is 530 em)? 21. Calculate the coefficient of thermal expansion for the material of which the rod i made. then -20'.3.161'. m length between them w III be constant 31 1\ tern rature (b) What should be the lengths of a steel and a brass rod 1\ O'C SO that at alltemperatures their difference in lcnath I 0.0·C. find . Assume that the cross section of the capillary is con tant at A. •• 01)""Eq. Both th rod and the ruler are placed In an oven at 270' where the rod now measures 20 II em using the arne ruler. car expansion at the same initial temperature. Con ider a rnercury-in-gla s thermometer.506' 18. that IS. J 4 is 1. pansion is <t.1tI1. n(T)dT] . If ihc n: ed distance /-0 . 27.0'C.lid 'lliCl~nls I hI! if its volume at how that when the temperature of a liquid in a barometer' change b) AT. A steel rod IS 3. and the pres urc is const nt.pcnment.ases by 0. It WJ necessary lobe able to mOve a srnal! radroacnve source at selected. Its coefficient 01 line r e. What is the volume of a lead ball.1 1111 ! the percent increase 10 «(I) the area of a face. I'I\lVe 32. 19.. Suppa e that the mercury JUSt fill the bulb at O.: 16 Problem a • \\ here Lo is the kngth :H u reference temperature rr>' 24.hcre((1 the c f1icient of linear expansion. m .OO'C Show that the length L of the mcrcurycolurnn in the capillary at a temperalure T. I window is 200 em hy 300 em at 10·C.0(') em to diameter at 25· . then an intcrior diarne cr of •. X IO-s K-I. th dilleren •..0.14. AI what common temperature vill ihe nng just slide onto the rod? 30. If the volume I' I~ ternpcrau.1 J~ T. in 'C.05 m long u ing a steel rulcr at a room temperature of 20·C. The area . extremely slow speeds. 2:\. Show that If we neglect the small qll.lO('C to which the: center :U.

t . [~1are Young's moduli of Ihe m.8 x to-t/C·. A n aluminum cup of I 10 ml L. At ~\h.\ 1 (a) Sho» that the rod Interface IS dtsplaccd upon hc.J -4. . until ns radius is increased by O.uerials Ignore dlOJnl:c~ In cross-sectronal urea .!yn:rin IS 5. 45. A pendulum clock wuh a pendulum made \)f bru ~ I de. 39 cvlinder placed 10 frictionless bearings is: set rotating ab0~( its axis '} he cylinder 1\ then heated.. il5 length Increases by 0.. aU at 20'C. where 0:. ends and then cooled.35'C7 (The coefficient of linear expansion of ~as$ b 9. l\compositebarofkngthL-/1 + L1ismntiefromnbarof materml I and length 1.0 X 10 "IC". 35. J7..'6. the rodficicnt of volume expansion of mercury is 1. is heated without mccharuc~t .tlxjcit~ is filled \\ ith gl}(l.092%. (b) r ind the strevs al till' mterface after he. How much glycerin.) .(Ul!. steel rod at 24·C I) boiled securely at holt. as shown In! arc Ihe coefficieurs of linear expansion and 1:'.! 8%. 'haptcr 14. 1\ '10-$/(" :lflclPI".' Sc\' Appendi« II {l'f ncnbt tng.:>1 Figure 19 Problem 4(. free! uI230 rev/s n avi T (b) . .t-t 507 -Pld. wi1!plll out of the cup if the tempel" turc olrhe cup and glycerin JSfaj~tl to 28'C? Vhen the temperature of a metal cylinder is raised from 00 to 100·C.28. rigid SUPJ)vHS. and (c) rotational energy? 40. I low much farther will the block Sink when the temperature angular velocity.~! . (II) Prove that the change in period Pofa physical pendulum with temperature j~ given bv L\ P"'" jnP 61' (b) A clock re:ndululll mad".. (b) A thin brass puuun aboui \"< ( en icular to it .. T .C'<lE!) 1 + F' •.'~.__II the clock IS used in a climate where the temperature averages 30'e.) (The coefficient of volume expansion of g. Explain the to the lime given by the clock IS necessary It ihc end of JU H'/> is the coeificient of velum mmus sign. expansion.2 X 10 »c-. Three equal-Iengrh straight r of aluminum. if the dock opera!\'\ . 19u fhe trmperature IS T and there IS no uuual )trt'~S the rods arc heated.lIn· bi all amount given by I WUrt: 17 PI oblcm 36.lh) L and cross-sectional arca-.4 shown in Fig. A 1. What is the percent change in the cylinder's (a) angular momentum.'oOI"CI until Its temperature increases by 170 C·.~ X I O-"/C" . 20 43.1t tcmperutur« will the angle ')PJ){) ire the mvar rod be 5'. rncmc formulas 40. without mechanical contact.0·C.. invar. An aluminum cube 20 ern on all edge floats Qf! mercury.T. CalcuJalt' the change III an ular velocity.Il 0'( V! 42. and Sled.1:). (b) -47.1ft' arranged end tu end 1>( tween nxed.Hint' l i~ur J 8 Problem J 7_ {a} T .II Its center.1 H14/C·. + O:zL11/L. days'} 41. 2aI liT. I:J.'nn at 2Z·C.alculale the densnyofwater a.. 110 w much will the height of the liquid column change when the IUb~ b heated to 310·C? Assume lh. A IS I. The density of . . t)j invar has a period of 0500 s and is ccurate "I 2(}.1 ..\\ (rll••••••Ll 44. forrn an cquilaterul tnangle with hinge PIl1~ at the vertices. 1 W{}rods o(dlilercH( mate rals but having tilt' arne It Ilf. signed to keep accurare IITnc :H 20 CHow much \~111 the error be. (t·.1:11 .:ndulullt rod 100 ern long How high must the mercury be in Ihe glass tube so thru the center ot mass of this pendulum will not nse or fall \\ IIh changes III to the bottom of an temperature? ('I he t'fll\\·set·1I0nJ} area or the tube 1\ l'(11. {a} Find the perceru change in d"n~iIY_ (b) Identify the metal.. attached to a bar of malena12 and length 1'2. Figure 17 shows rhc variation of the coefficient of votu me expansion of water be! ee1l4·C and 20' that their temperature increases by.) glass tube nearly filled wuh mercury is attached in tandem 11011 p.J gia~ flas is c srnplerely tilled by 89! g of such OJ omposae bar whose length is 52.. Ifany. 13 X 1O-6/C·. see rIg 19b. (a) Prove that the chan L1IUfC unif e in rotational inertia Iwith temperof OJ solid object is given by tl. 1\1 what tcmperuiurc will u begrn to )Idd? See Table 1. in secunds per h ur. [.lI1o. lit (a) Show that the effective coetheient of linear expansion 0: for Ihis bar is given hy (fJ) Usin steel and brass.. cury \\ hat mass of mercury is needed to fill the flask at . what approximate correction rises from 270 to 320 K7 (The coetliciem of volume expnn- sion of mercury 48. .t u 1~=(OIEj: .l'rubian« up wh .m·!OrIg vertical glass tube is half-filled w ith a liquid at 20. rm rod.•••ter at 4o'C IS 1000 kgjm'. .4 em and whose effective c cocthcrent of linear expansiou is. A I 100-C .

. Take 0: 6. As urne no bendin or separation of (he tow r .ur('20 Pro I 49..O~ (1IIf1/" [CTIlp r tur to that of the iron rrx' Neglect the ma a def1~IIY of 7.5 iO J-/P for the cabl and c mpute (0) the change in length of the cable and (b) th chanKc 1Il ~1 f r temperature ch: ngc from 10 to 90T. The distance between the towers ume e pansion of mercurv i~ I X I0 ~/ ~". Iron ha !OJ ylt'm' and coeff icnt af hncnr expansion equal to 12 1O-6/C·. 7 S orlh glass.} r the rnam span of the Golden Gale Brid C OC:1f 'an Fmnciscn is 4200 n (Fig.abolic sha for III cable. no a pa. ------------------------------------------------------Fif. 20t The sag of the cable half\\ay between the towers at 50' F is 470 ft. I he co lficicnt of v {_ 49.

."J n.' hid . Ifwe wish to change the pressure p.11./I. This approach ts considered In Chapter 24.Log gas and fOf ch!ltlgmg the supply to admrt different kmds of gas 5U9 ." d 'Jm" quantu it ' /"t'PUI/t'\. We assume mat we have au <. A gas supply permits additional gas to be added to the cylinder. • "a.such t11 t the t rnperature 01 the reserv if does not hange when our gas cylinder comes into therrn 1equilibrium viih it. 0:l'i1l8 to . volum». temperatur». The volume of the gas can be determined from a measurement of the height h of the piston above the bottom of the cylinder. u I. among others.T CHAPTER 23 KINETIC THEORY AND THE IDEAL GAS . ln vt. 1 PI TI.'(I\eit. so that there is no air pressure pushing down on the pi' Ion) The volume V can be changed simply by chang.! a mech"lU~m IS also provided for tell10\.l$ dcvt?ioped in the J Zth to J 9th (ell III' ies by Royle. (The "pace above the Piston is assumed to be evaeuated.r pr ·pcfll<s./1lI mm:!' 1 (l{p niclcs 11 \£'I\!.I.farr mot nuuter is made IIJI uJ particles (ouun or molecules). and Afa.· large numbe« of panicle: involved It 1.11 to tlPf!~ Ihi:' {<i"S qf lIIe hantcs (0 jiud ill. . ant! the temperature of the gas IS measured with a suitable thermometer. llrd kineri theory. We add or subtract weight on the piston.:h~ tv the c Iin er suitable devices for me suring these prop rtie .t' basic laws oftkermodynam! s deal with llle fetationslllJu between m croscomc propt!((iCS. whi h in equilibrium is balanced by the upward. JOllie. In It/lit it ". Cas ~lIllllft maintained at a temperature T.! . w _ s ppo the gas to be in contact with an ide. force due 10 the ~ pressure. and absolute IKelvin) temper. volume. We wish to arry out a series of mea uremen!'. lized devic called a thermal reservou. d 1\ ( ":OI'-'II.:ory !~J. Kinetic th..)1Ston exerts :l total downward force Mg on the gas. we assume th.'lfft $ $ err 1. J) lh·rnoulli. {h..11 II 23·1 f\. ut : ..'f"'. \Ve assume that I"e can easily ch nge the temperature of the reservoir. of tne macros: spic properties of the gas: the type and amount 01 gas and it' nressure. such as the pressure. Kronig.l. f!~ In this chapter.It s and (hell ovcrae« this behavior OWf u!l particles. Wi' consider an approacllw averaging C. which we can regard 4\S a bod.' folk» (he monon of represenuuive particles if I tl }.rll~. W also.:. Clousius. and tnterna! energv of an Ideal g. FiK Ire I ras is couf ned to a cylinder th I is ill contact with a thermal reservoir I th (adjustablel temperature 7~ The \. um III l \' 11 ve at our dlSPO I th ' me us to chang' any 0 these propenie For example. tur .> nI( tton of t'l ct I'paruc}.1ACROSCOPIC PROPERTIES 01" A GAS AND 'I'n IDEAL (~AS LAW Figure 1 shows a gas confined to a cylinder fitted w ith a movable piston. fht>reby changing the temperature of the gas.!I. Another appr(){lcit {(J averaging' IS stati rical mechanics.irrlll! use asrraging tedmiou.T/flll.. ta t: press th.\1/01 "'<ldIC.h The laws 'ay nmiling about the. in willen laws of probabilllY ale applied 10 suuistic I dtstrtbutiens of mol -cular properties.

thus "'Y 1'.\ different value if we had chosen different values of Nand Let us now conduct the following experiments g. Of V= CUT (p. I is a As we discuss in Section 23·S.. Furthermore. called Charles' law or Gay-Lussac'. (h> PlotllTlg J \ agains: p shows that the relationship i!. by replacing the gas in the cylinder with an equal number of molecules of a different gas at the same pressure and temperature. Keeping the number of partides S and the temperature r constant. 4) a direct relationship: the volume increases as the temperature increases.5J 0 Chartt'r 23 A'/fICW 'TIIN·ry mu! the {den/ Gns tog the posuion Of the \11"[\'1). At 0 given temperature and pressure. constant). __ p idea gas. f'u..?/ (lo} _ •. If we repeated this experiment with different constant values of p and 'T: wc v-ould still fwd Eq. that is. espedally at low density. I to hold. Mathew mattcally. Thus we would con . P :" I' C' (IV.1S is in contact with the thermal reservoir at a particular temperature T. we all ( w enough time. 311. Equation 1 is s. With the temperature and the number otparticlcs held constant.. and the weight on the pisron is constant). Equation 1. tile volume increases linearly with the number of particles.. we find that the new 1. Depond: !I( (II r on p.\0 determine N. (I) Here C is a constant. On the somewhat ideal generalization.)<. To check 101<:.lude that the volume occupied by a gas at a parucular pressure and temperature is indcpen lent of the type of gas or of the she or mass of its molecules.L L__ l_1---1__ 1_ . which confirm a 1V )- . Figure 3 linear rclauonshrp. to a sl._L-. (We a some that we know the mass of each molecule and the total mass of gas that is present in the cylinder. Of vc of the thermal reservoir). thereby changing the number of molecules N.Tconstant). the volu me depends only on the IIlimber of molecules.a5occupie the same volume.. Figure 2 The volume !'occupied by (he gas In fig J depends on the number of molecules N. We find (Fig. w hich ~ug. It holds to a very good approximati n for all docs follow Fq. 2 and determined b . there is a direct proportion between Vand N. . Keeping the temperature and pressure constant (that is... Depcndenco of V (JII T Keeping II and N constant. After each change. The data points appear to' follow a straigh.for the gas to reach thermal equilibnum and \0 acquire a new set of rnacrosconic therrnodynanuc van bles. We can generalize from the beha vior of these rea! gases to that of all idea! th.. e w instead plot p \ ersus V I. the volume !' decreases. u rs an idealization of the bchavi r of real gases • Gas 1 o Cas 2 " G<l53 v r CN (p.. hue. in the next section we 'on idel the microscopic properties of an 'f \ v (el) L. where the molecules are vcry fur apart and the volume occupied by the molecules themselves is indeed a negligibl small fraction of the volume of the container to which the gas is confined. T constant). and we measure the resulting volume rl by observing the height oruic piston. indeed an inverse linear one. 2. the g. we change the pressure (h} changing the weight on the prston) and mea urc the resulting \OIOIrH' The result i~ shown in Fig.-l. 1 exactly. and we measure the resulting volume V. Thus we ('. the total number of molecules.. j)e[lClIrlcIICI' of I' Ol! N. Lqu: lion 3 I'. Here C represents another constant._L_-1_t_ '.\ law and like Fq.)ffi~ ciently good approximation. 2 i called Bo)'I(". We therefore conclude p C( v-! ~or (u) The volume Voccupied by the gas tlpprars In depend inversely on the pressure 1'. jaw. real gases deviate somewhat from tillS ideal be 3. and we conclude that. as in Fig.\~!itS an mVt'!'Sc relationship: as the pressure p increases. I and 2. equal to the slope of the line in Fig. {31 where C" is yet another constant.) Figure 2 shows typical results of such experiments.(. and the amount of gas mirht be d\ang\~d by allowing gas to enter the chamber. N. vary the temperature T (by changing the temperature T. hut with a different value of' the constant C. we allow gas to enter or leave the chamber. mctimcs known as Avogadro's law.. the v alucs of fl Hod T. different gases follow the same lmear relationship. which would have . havior.. Like Eq5.. 3d..

e need not con vert p and into Sf units.Section 23·2 The ldeal Gas: A stod«! 511 v Equation 7 is called the ideal gas law ot Ideal gas equation oj tate. We can combine the three equations into a single equation that includes all three of the observed relationships. A model might begin with a t or simplifying assumptions that permit the system to be analyzed using an existing set of laws. + 20 K 16 L) V Wllt. 7. •. Experiments reveal that.3: V T. Previously in this text. An equation of state oT a system gives a fundamental mathematical relationship among macroscopic thermodynamic quantities. or (7) R=N"k = 8. decreasing the volume of the gas to 16 luers. as follows: NT-k.P. but if we have been clever at forming the model. The analysis might then lead to an equation or set of equations describing the original phy i al system. Assuming oxygen to behave like an ideal gas under these condition . 1) contains oxygen at a temperature of20'Cand a pressure of 15 aim in a volume of 22 liters. . I . By rewriting Eq. all real gases approach the Ideal gas abstraction described in Eq. very good apI proximation of the behavior of the system. the final result may prove to be •.111 univer (II gas constant. The constant R has the same value for all gases and is called . T constant). Eq uation of State Equations I. and imultaneou I) the temperature is rai ed to 25' .38066 X 10-2) 11K.) T= CUT The constant k in Eq. the final result may give us a way of studyin ' ~ the system in the laboratory and gaining still mort: msrght. 7.) r ' (~)N=CN V V (P. (kNT) C' p""'_ •••• - T constant).3145 J/mol·K. we have u e 1 a model (wuhout calling it one) to describe the motion of a complicated object as a point particle under certain circumstances. Iewtonian mechani s. 4 in a slightly different 1"0011. c . when the pressure and the number of molecules are held constant. (p. but we mUSII!X{lft':>S T in absolute (Kl'hill) ture units Thus Pr'" ( I:> atrn) tempera- V (5&) (5c) _ (273 273 + 25 K) (22 L •••21 atm. at low enough densities. w. (Sa) Because this is in the form era ratio. 4 as pV =kN n'T ". V (Tf) (v. they often inv ent a model A model i a simplified ver ion of the system that permits calculation to be made but sull yields physical insight. Figure 4 The volume V occupied by the gas varies linearly with the temperature T.: have (4) or PT. for c ample. In terms of the Avogadro constant NAJ the number of moles is (6) and we can rewrite Eq.1t (k. pV Sample Problem 1 An insulated cylinder fnted with u piston (Fig. 'IODEL When phy ideas want to under tand a complcx s. Because the model IS asrrnphficauon of nature. the final result is generally not a true or complete description of nature. and 3 summarize experimental results strictly valid only for our hypothetical ideal gas but to a high degree approximately valid for most real gases. 2. since the quanuiy of ga rernams unchanged. 4 is called the Boltzmann C01lis a universal constant with a value determined by c perirnent to be k"" 1. (N. It is more common to write Eq. here k is a constant. The piston is lowered. pV= where !lRT. tern. \\ e We e press the quantity of gas not in terms of the number of molecules N but in terms of the number oj moles n The mole was defined in Section 1-5.. what i the hnal pressure of the gas? Solution From Eq.Nconstant). 4 we can show that it is consistent with Eqs.1 hi IS the same limit that we discussed in connection with the ideal a temperature scale in Section 22-4. Whatis more important. (8) .

1 consists 0/ panlcles. For simplicity. How ver. vhich we call the ideal ga model prove to be entirely \ onsistcnt with the concept of the ideal gn' that w developed experimentally in Section 2 J-l. we con. less cornplc real ~. or between atoms in tI solid. Based on these assumptton . id r all its molecules to be Identical.• and l' •• When this particle collides with A I' it rebounds with 115 x component of velocity reversed. which is then available again as kinetic energy after such a brief time (th time between colli ion!'» that we can ignore this exchange entirely.( " Th re is no effect on Vy or VI' 0 that the change in the particle's momentum has only an X component.ncc our assurnpuon ls piau iblc.C~ s foi III the J1)o!rCIJ!"s would be a pr [ect of hope- ing a calli: ion.nds 01 times "mailer than that of the gas. each of area V. r hi III 6. 1\ .kr which is itself based on a kind of model thnt simplifies (under certain clastic conditions) the complicated internal processes in a solid under stress. this proc dure forms the basis of kind . In tha section we saw that. they arc extremely mall.t:1r. we consider a g. and see whether we need to modify this assumption. ume that the resulting large nurn- 1 r r collisions maintains the overall distribution of molccular vclo iti s and the randomness of the motion. To the extent that this is true a molecule moves with constant velocity between collisions.-t.•5. (9) BecauSe the total momentum sion. An. 4. that is.512 (I. 2.('[11cory.. That is. and the energy (If the collision can be absorbed by the molecules as internal cner y m n vaucty ofway . Call the fac normal to the x axis (Fig. 7. a..2mv(. called molecules. the macroscopic pro erucs tif real gases approximately follow n g ncral I csult. The molecules can C llide inelastically. In describing the motion. Even though there are many molecules. and that when a gas cond .Ilnplif' this problem by inventing a 'I It model Ih. We know that the volume occupied by a gas can he changed through a large range. Prom the rnrcroscorxc point of view our model of an ideal as includcs th followin a surnptions. which we resolve into components OX' r. the momentum imparted j conserved in the collito Al is + 2n1V~. y . F . in terms of the pnng force. 7 he volume of (he 1I1011'CII/(>. 11_. Dependingon the gas. 5) 41 and A1. Therefore the motion of a particular molecule is a zigzag path consisting mostly of segments with constant velocity changed by impulsive forces. Collisions of on molecule \ ith another or with the walls of th container conserve momentum and (we assume) kin lie energy.'1S in a cubical container of edge length L whose walls are perfectly elastic. Lat r we relate t hi micro copic descriplion to a macroscopic one.. Collisions are elastic and of negligible duration. A gas confined ill a container is an example of a complex system that is difficult to analyze using Newton's ln vs. A I:fl. momentum .nscs the volume occupied by the liquid may be thou .~- 3.lS.I' is a negligibly small fracfirm (Illite volumo on IIp/('cl hy the gas.of'valucs with lillie difficulty. we assume that cwtonian mechanics is valid at the rnicroscopic level. Kecpin track of these PIO\.initial momentum . each molecule may consist 0 one atom ora group of atoms. in r 23 Ktnetic Theory and the Ideal Gas have also sometimes modeled the force between atoms in a molecule. The molecules are ill random motion and obey New- ton's laws ofmotion. Molecules arc not true point panicle and do hav internal structure: thus some kinetic energy may be coovetted into internal energy during the collision We assume that the molecule docs not retain this internal energy. the ideal gas law of Eq. we assu me that the range of molecular forces is comparable to the molecular size and much smaller than the typical distance between molecules. H . The total number of molecules is larg '. 23-3 Let us now calculate the pressure of an ideal gas from kinetic theory.1l I cs th microscopic properties of the del. A molecule of the gas is shown moving with v locity l' toward side A r- . If tit . The velocity (rnagnitud and direction) of anyone molecule may change abru ptly on collision with the wall or another molecule. because there are S() ma Ii' molccul W' (mvx) = . The molecules move in all directions and with a range of velo ities. is an clement or a compound and is in a table tate. especially at low density.. w use I cwton's law to analyze the m chani s of the Ideal :as. W <. given by final I. particular mole ulc will follow a zigzag path bccau c of these colli ions. Consider a molecule of IIIa III with velocity v. Later we hall invcstigat the actual sile of rnolecul c. So <Jl'lmnab/r torccs act 011 (he melee ules except dur- Figure 5 A cubical box or edge L containing an ideal a.

However. We might therefore expect sound W:l\ t. nor does the transit time. This could happen in a gas of very low densil)" for example. over small regions 01 $P ce or large regions of space./L for all the particles. or 1600 Although we derived this result by neglecting collisions between particles.'l n tlftI"l"" 1838 m/s and sound travels at 1286 m/s.00 atm pressure. the average values of and are equal.' so that Eq. 14.1 ( 11) v. the rate at which momentum is imparted to AI by all the gas molecules.485 m/s and the speed of sound is 331 m/s. and we should take into account the varying density. See Section 17·3 and Problem 6 of uus chapter. we could have chosen . this same momentum. in hydrl.. V. We can ignore Iluctuntions. ).: (If the molecule strikes one or the other faces of the box on the way to Al. and p p =p (V. which we represent by i? Then (13) p-p~. the x component of its velocity does not change. U. the round trip takes a time 2L/vx which is the time between collisions with AI' The average impulsive force exerted by this molecule on AI is the transferred momentum divided by the time interval between transfers.. Tl1( pressure is therefore L == -L 111 (1)'2 The square root of Vi is called the root-tnean-souorc speed of the molecules and is a kind of average molecular speed.. that is.H!lfC 513 re- negligible compared to the time spent between collisions.erred only on the side A \I it follows from Pascal's law thai the pressure is the same on all sides and everywhere in the interior.) Using Eq.. 2 •••• ~ + + Because we have man.IS tIll' . gravitational effects might be significant. averages can be taken over suo •. we divide this force by the area of A I' n rmely. then Nm is the total mass and Nrn/U is the density p.. 12 is the average value of for all the particles in the container. If N isthe total number 01' panicles in the container.• _ m~ (10) x 2L/v. '2 Calculate the root-mean-square speed of hydrogen molecules lit O. Although we have calculated the prcssur c· ~. because momentum is conserved in collisions. 13 becomes P = lpiJi. v. kinetic energy from one molecule 10 the next one with which it collides. (This is true only if the density of the gas is \l ai.lm ' !840 mho £111/h This is of the order of a mile per ~cond... 1112 is that of particle 2. Thus R 'Ill' - 'p I 13p • In Eq 14 we relate rnacroscopi quanuty {the pressure xl + lP + .99 X 10 kg..1. in nit at we. u.l + v~ + .. form. Under these conditions hydrogen has a density p or8. These molecular speeds .). The average computed in a sm II region for a short time might depend on the time or n. For example.. so that the valu 's obtained in this way may fluctuate. '1)"••• . ".99 X lO-l kg/ml. 1 •. L' Kinetic Calculation ojillt! PI{. ) . Solution Since p . and the wall must receive the same impulse regardless of which molecules strike it.. the time spent during collisions is Table I gives the results ofuimilar calrulations for or Ie gases at room temperature. see Problem 38. particles and because they are moving entirely at random. The energy of the sound wa ve is car ried :\'.00 aIm'" 1.OO·C and 1.0 I 1 IO~ Pa..• f3P I)rm • .t time or over long times. These results are to be expected in terms of our model of a has. and the value of each is exactly one-third the average value of v2• There is no preference among the molecules for motion along anyone of the three axes. " I 3(1. 'Slon chosen. (12) p) to an average value ora microscopic quamitv (llhlt is.irc roughly of the same order as the speed of sound at the same temperature. to i} or v~. Because of the exchange of velocities in an elastic collision between identical particles. In a large sample of gas. v. we can alculatc the root-meansquare speed from measured values of the pressure and density of the /) I is the x component of the velocity of particle 1. assumin hydrogen to be an ideal gas. u find the pressure. The time required to cross the cube is Liv. Hence ~= 1. Equation 14 holds even Utile box contains a mixture of molecules of different masses. Also. The quantity in parentheses in Eq.. or F ••. (14) v v. Sample Problem For any panicle.) To obtain the total force on AI.•2mv .Section 23·3 Suppose that this panicle reaches Al without striking any other panicle on the way. v. Similarly. there will always be a molecule that collides with Al with momentum lnlJ ~ corresponding to the molecule that left A 1 with .) AtA1 it again has its x component of velocity reversed and turns to AI' Assuming no collisions with other molecules. Thus mlU •••• IN. when the number of particles in the system is large enough. Hence our neglect of collision) is merely a convenient device for calculation.\ container of any shape: the cube merely simplities the calculation. (We consid r this avera~e in mote detail i \Section 24~3. Then. however. we must sum the quantity mv. the result is true even when we consider collisions..01 Ie-Pal' Ii' """I 8. to propagate with a speed that is roughty the same . and so on.

where pVis the total mass ofgas.$ .we calculated v10n(hi" basis. The right side of Eq. we may consider Eq. the center of mass would be ill rest Thus.a (p V"" nRT).-It-~3~T. Solution The density of a gas is P- p "'" 3BnMi)2). the kinetic energy of a molecule._O_O_fv_1_T~1Pr:RATURE {30e K) Translational Kinetic Energy . (16) so that the speed of sound 1'( at a temperature 71 is related lO the speed of sound 1': In the same gas at a temperature Tl by '(7. in which n is the number of moles and M is the molar mass. Combining this with the equation of state of an Ideal g. The total mass of the gas can be written as mN ••• ntH. the large number of collisions restrains the advance of the ammonia molecules. That is. Combining this with the ideal gas law pVnRTyields p RT -. Making this or substitution yields pV.p being the density. us speed in arr at 30(1 K is •• Note .331 m/s) y[3OOl<. tha: the absolute (Kelvin) temperature Why?' This result connects the kinetic theory with the equation of state ofan ideal gas. I. or characteristic speed of molecular motion.-jJlM(. fir K 347 m/s. onl\ ~r\mI: 1 _~ SOME: MOLECULAR __ R.' 1'01 example. 17 is therefore two-thirds the total translational kinetic energy. We can also write the mass gas as IIA1. Although molecular speeds arc high. This explains why there is a time lag between opening an ammonia bottle at one end of a room and smelling it at the other end. to calculate V2. snow how the speed of sound for an ideal gas would depend on the temperature. 28. where Nis the total number of molecules.. In 'lli other frames the molecules each have velocities greater by u (the velocity of the center of mass in tha: frame) than 111 the . In ection 23-2 we assumed random motion as part of OUf statistical d 'bnitioll of an ideal gas and in Section 23. The temperature of a gas is related to the average translational kinetic energy measured with respect to the center of mass of the gas. and a microscopic property. In reality.• hal the speed of sound In a gas 1\ the same as the root-mean-square speed or the molecules. we gain some insight into the meaning of temperature for gases. temperature.514 Chapser 23 Kinetic Theory and the ideal Gas SPEEDS AT Our initial assumption .. do not move very far during a period-of the sound vibration.0 18. they are confined to a rather small space by the effects of a large number of collisions. (he speed of sound i~proport iona I 10 Ii"".t ••• IT. If the speed of sound at 273 K is 331 mls in air. which is in fact what we observe.0 . v. 1370 645 1920 517 3720 3750 3740 Nitrogen . 17 as or Sample J'roblcm3 Assuming that the speed cf'sccnd inages is the same as the root-rnean-square speed of the molecules. the average ttunslational mole of an ideal gas is proportional I (I ) V' nM 10 kinetic energy per the temperature in which M is the molar mass (the mass of I mole) and n is the number of moles. tll. For a distribution of molecular vclociucs having random directions. They diffuse through the air at speeds that are very much less than molecular speeds.")=lm(NVZ).t 342 3750 '1hc molar mass. E.• per Mole (g/mol) (m/s) (lImo!) crudely correct..we must use a reference frame 1[\ which the center of mass of the gas is at rest.0 32.'(orar mass A/Vrm . is given here for convenience in g/mnl: its S1unit is kg/mol.. .0 4. Oxygen Carbon dioxide Sulfur dioxide 3730 44 •• 0 412 3730 64. we obtain iMVl = iRT. The total translational kinetic energy of the gas is (17) !m(vf+vi+ . we obtain pV'= 1PVt)l. Either way..l. Hydrogen Helium Water VUI')()f 2. In spite of their high speeds. l8 as a connection between a macroscopic property. sometimes also known as the molecular weight. We can write Eq.0 3740 483 ---- 23-4 KINETIC INTERPRETATION OF THE TEl\tlPERA T RE If we multiply each side Eq. Equivalently. Th kinetic energy a~"()<:HII('d with the motion of the center of mass of the gas has no bearing on the gas temperature. (. The molecules themselves.> Does this change the conclusions of this sam plc problem regarding the dependence of'the speed of sound on the temperature? See Sample Problem 6 for a derivation of the speed of sound in a gas . is used here. 14 by the volt! me I'.p M' We obtain from Eq IS t'r •• .

then . which is the number of molecules per mole of a gU3. will escape faster than the heavier one The ratio of the number of molecules of the two gases that pass through the porous walls in a short time interval.' (19) 10v. indcr Crhl\\ slightly depleted OPHU) is returned to Iced the previous \()\'CI stage. 21 to the square root of the inverse ratio of their molecular masses or.349 hymo] and th. molecule is determined by the temperature. we can therefore write the work.Seclljm ] J·5 W(lrk Dtnu) Oil (111 Ith'{l/ (.). As Eq. given by Eq. 0.. the pressure would not be dearly defined during the process. After 11such paS!j. 21 to the diffusion of two different gases in a container with porous walls placed in an evacuated space. we obtain n w 350. anu we ha -e Solution The molar mass M er=ur.IAe~. out to be very useful. which dealt with molar quantities. this quantity (the tt anslational kinetic energy per mole) has nearly the same value for real gases at a given temperature (300 K in this caser From Eq. might require seve ul thousand }h:I)S Solving. Sample Problem 4 Natural uranium consists primarily of two isotopes. If we reduce the temperature of the gas.. .• . the work done on the gas in that case is positive. 23 could not easily be evaluated. The upward force exerted by the gas due to its pressure p is given by p. their molarmasses: ex'" Jm1/m1 - w- J F'dx= J (-pA)dA. it is desired to increase the abundance of . 20 we conclude that at a particular temperature Tthe ratio of the root-mean-square speeds of molecules of two different gases is equal to the square root of the inverse ratio of their masses. Only m is easIly fissionable. and thus according to Eq. Using EQ. whose molecules move more rapidly on the average. . 18. The ratio RjNA is. We can write Eq.\f/S = m.n 0. the relativeconcentralion oP}~U will increase by 0-". 22: ct _ Each successive y M7 n:r. Find dx. Here we see that the average translational kinetic energy of 3. the mass of a single molecule.3$2 kg/mol. In a sample of the gas UF 6 (uraruurn hexafluoride). 8.l{ passes most easily through a b mer (and thus h ~ltgh\l) ellridj~'J in lJ)U) advances \0 the ne: t stage.007) ••. m 2 3k we obtain 1 i1 (21) 2 3k 2 23~5 WORK DONE ON Al IDEAL GAS • If'we raise the temperature ofthe gas in the cylinder off l' 1. from 1$ accomplished through successive stages. this =u. hence the motions will no longer be random.)u1= !miJi-HR/NA)T. . characteristic of natural uranium.7%. where A is the area of the piston. vlule the TI!IH.. it contracts instead or expanding. To obtai n nearly pure such U~!~ requued IN nuc 1e. The lighter gas. (20) a "(0. m~ is the average translational kinetic energy per molecule. 1'=2. If the piston moves through tance <I dis- barrier. _ 0. To mrrease the concentration of mU from 0.7% to 3% by forcing the gas n ti rnesthrough a porous fl. 18 predicts for an ideal gas.993. Otherwise. from Eq. We then h ve relative fraction of Wu by a factor of o. Thus after passage through a POfIJUS barrier ihe gas will be en riched in m U by Ihe sepal a Iion ract or a. m. and we obtain different values fer Vi.weapons.oJ) .. . is equal to the ratio of their rms speeds.352 kg/mol _ \ GO. in which II portion 01 the g:J\ th.the volume of the gas changes by an . W done on the gas at. the gas expands and raise the weight against gravity. 23 is carried out slowly. iI passage through porous WJll mcreases the HM/N. the Boltzmann con rant k whi h plays the Tole of the gas constant per molecule.97 0. and the minus sign enters because the force exerted by the piston on the gas is in a direction opposite to the displacement or the piston.The temperawn: of'a gas in a ontainer does not increase when we put the container in a moving cart Let us now divide each side ofEq. mU (07% abundance) and =u (99.1! . and the mtegral in Eq. equivalently.3% abundance). We assume that the process described by Eq.. We an apply EQ. That is. Thus . (23) Here dx represents the displacement of the piston. the number determined from II of rous barners that must be pa cd l~ !mi)l. the gas does (positive) work on the •••• eight. Lquation 20 is the molecular analogue of Eq."u from 0. to 3%. . In the last column of Table 1 we list calculated values of !-\h~n. b 0. 7 of Chapter 7. 18 by the Avogadro constant N ".01 515 center-of-mass frame.V1 ••. which is called the separationfactor a. In ofl3'UF6 is 0. (o. the force exerted by the piston 011 the gas is equal and opposite to the force exerted by the gas Oft the piston. so {hot the gas can be considered to be in equilibrium at all intermediate stages.fkT. an enrichment commonly used III 1)(1\ er reactors. By Newton's third law. 23 in a more general form that turns -IM2/M1• (22) The diffusion process through porous walls is one method used to separate the atoms of an element by mass into its different isotopes.349 kg/mol .

). Figure 6 shows the similar situation for the work done on the gas. with P plotted on the vertical axis (like F) and V plotted on the horizontal axis (like x). A graph in the form of Fig.-PI . A. Let us suppose we wish to take our ideal gas om the initial conditions VI and PI (point A') to the final c nditions Vrand pr<poinfD). Conversely. and the final volume VI' v -----. (25) . as FIg. 7.<J'r- V. while along path 2 (ACD) the work is equal to the area of the rectangle ACFE amount aV .a( ------.•• can take between A and D. the work done on the gas is negative I th pr ss increa s the volume of the gas and positive the process reduces the volume of the gas. 24 that WAD ••••O. so that the pressure remains constant at the value Pc while the volume increases from Vi to Vr. or Vr < VI (in which case Wis positive).J P dV+ J:" dV- -p. so that the volume increases from Vi to Vr' We then increase the pressure from PI to Pr at the constant volume Vr by increasing tbe temperature and adding weight to the piston to keep it from moving. Along path 1 (ABD).taken from (lie pressure --. Once again.+\ - WAS + WaD J pdV--pt J:"dV=-pr(VrV. 24: if the gas expands. It make: no reference to the outside agent that d s the work. of which two are e own in Fig.. 6). V. 'otethat he algebraic sign of the work. There are many different paths •. the pressure is constant (at the valuep-) and comes out of the integral. P being a scalar quantity having only p sitive values. You will recall from Fig. Along BD. Thus the work done on the gas can be written W-- J pdV . as in Fig. (We might a plish this by turning up the control knob on the th • 1 I BD by increasing the temperature but adding no additional weight to the piston. The magnitude oithe work done on the gas is equal to the area WIder the pressure curve on a P V diagram. Work Done at Constant Volume The work is zero for any process in which the volume remains constant (as in segments AB and CD in Fig. It states simply that the work done on the en -an be calculated from the pre sure and volume of the ".). if the gas contracts. The work done in this entire procedure is the area of the rectangle BDrE (the area below the line BD). to Pr at constant volume.IE and BD: ~ WI = WAB+ WDD· Because the volume is constant along AB. We can compute this as W1- WAC + WeD 0 . 2 P. 7 d monstrates. The sign of Wis d terrnined according to whether Vr> Vi (in which case IV is ne ative. and the work depends on the path.ork I~ equal to the area of the rectangle BDFE. increasing the temperature of the gas.5 6 Chaptcr Li K!I1tilC Theon and the Ideal Gas p P 1 •• __ • __ -.) '~eri tollcw ~a. Along path 1 (ABD) the v.and volume Figure 7 A gas is point A to the pressure and volume at point D along two dlf· ferent paths. the vork done by F is just the area under the curve between XI and Xr.A ax. negative. we first increase the ure from p.. 7 of Chapter 7 that if we plot F'against x. '1 we sirnultar -ously add just the right amount of iuonal weight . ABD and A CD. ""0- To follow path 2 (ACD). dVis positive and HI i<.0 the piston to keep it from moving. dV is negative and the work done on the gas is positive. it follows from Eq.y a varir ble force F. 7): W"" 0 (constant V). 6 is called a pV diagram. adding no additional weight to tbe piston). The pre sure force i clearly nonconservative.. We can perform a variety of operations on the gas and evaluate the work done in each case.1 i elf. The work done in this case is the area under the line AC or the rectangle ACFE. E' C IF V Figur 6 The magnitude of the work IV done on a gas by a proce of rbitranlv varying pressure is equal to the area under the pressure curve on a p V diagram between the initial volume'P.. (24) The integral is carried out between the initial volume VI and the final volume Vr• • Equation 24 is the most general result for the work done o a g s. Equation 24 is analogous to the general result for the work done on a system l:.. is irnplicitly c nrained in EQ. The result is J. by considering the \ ork done along th two segments . We can find W" the work done on the gas along path 1. Clearly WI . we first increase the temperature while holding the pressure constant at PI (that is. W1..

and VI' Because t> 1. the relationship between p and V. Note that t the work done on the gas. Figure 9 An adiabatic process IS represented on u {II <. lt'we allow the gas to expand with no other constraint • the path it \\ ill follow is represented by the hyperbola-like . The work done in changlng the volume is equal to the area under the curve between Vj and VI' V. Note that It is not sufficient that the process start and end with the same volume.8.I'>C). Carrying out the integral.• We deduce directly from Eq.(11 -". The work is zero only for vertical paths such as AB. ~ "v1' •• (Qn~t. the volume must be constant throughout the process for the work to vanish. I --. (In Section ::~·4 We discuss the specific heals or g.-I ~ __~ __--------L--VI ------~----~--. 28 is determined trom the pressure I" p I~ 1 " pV I '" 1 " .in i othermal process. is pV = constant. 24 that W. 1 from contact with the thermal reservoir and rest it on a slab ot insulating material. For example. The volume starts and ends at V" but the work is certainly not zero.10 adiabutic process. 7. To find the work done on a gas during . 8.1 1. 7.. (26) Examples are the segments •.IMt! P. '24. its temperature will change. The gas will then be H\ complete thermal isolalion from its surroundings: if we do work on u. A process arried out in thermal isolation is called . in contrast to itsbehavior when il wa in contact with tbt~ thermal reservoir. 1 COIll. I'o do this we use the ideal gas equation of state to write p = uRT/ V.p (Vf Vi) (constant p). 9. represennng a process at constant volume. given by the ideal gas law.curve P !l1 "'" constant.->'''<". The parameter y. "tTdV -IIUl' J-" i . and we derive Eq. W=- I Vt v.. must be determined empirically Ior any particular gas. hen I' varies. Work Done at Constant Pressure I lere we can easily apply Eq. the curve p~/Y . On a pI' diagram. we use Fq. V.---~ constant. (28) f <IV - = . the adiabatrc curve has a Sleeper negative $Iupe than the isothermal curve pi' ••• .rau» (if specifu: heats. as can be seen from Fig.Iia gram by the hyperbola-like curve pVt •••constant '1 he "()r~ done in changIng the volume IS equal to the area under the curve between V.---I-------~ J w v Figure 8 A process do lie-at constant temperature (isothermal process) IS repr esemed by a hyperbola on a pV negative for both of these segments. consider process ACDB in Fig.0 if Vis CQnstant.constant is a bit steeper than tl e curve [1 !I ••• constant. I where the last step can be made because we are la\. 9. Work Done at Constant Temperature If the gas e pands or contracts at constant temperature. The con-stunt in Eq. I W . pdV=- II" nwr v. the plot of the equation pV"" constant is exactly like a plot of the equation xy'" constant on an Xl' . 24.. €IV -. v. because the volume increases in both processes. 2(}in Secuon 25·6. and thus ••s hewn in Fig. as shown in Fig.. Cand SD in Fig. but we must find a way of carrying out the integral v. because the constant p comes out of the integral: W=-p Note that this is also negative whenever Vr> I t (In . called the.. Its values arc tYPI(ally III the range 1. coord I nate system: it is a hyperbola. A process done at constant temperature is called an isothruua! process.) Because "I is greater than I. and the orresponding hyperbolic curve on the p V diagram is called an isotherm.\ is positive for x > I) and positive whenever VI < l'" Work Done in Thermal Isolation Let us remove 'the gas cyll nder in ria..e fwd H' "'" - nRT In Vr (constant 1').in' 7 to bea constant. and hence the work done In this process will be somewhat smaller in magnitude than the work done in expanding from Vi to VI at constant I..

and volume at any particular point on the curve. . Evaluate for air lit room temperature (20'0 Solution (a) In the differenual limit.. as we inferred in Sample Problem 3. in Fig.-I) =0. 27. then VdVr< 1. Thus Pi V. the bulk modulu (see leq 5 of Chapter 17) can be written 1J ••• _ I' tip ampl Problem 5 A sample or gas consisting of 0. Making this subsutution._l?L. 7).V.O mJ) In -4'0 . followed by a process at constant pressure. --.. P-~ p' (29) Path 2 represents an isothermal process. one at constant pressure followed by another at constant volume.. -III VI In V . = nRT.. (b) Use the adiabauc bulk modulus to Clod the speed of sound in the gas a a funcuon of temperature.}'. we determined that the speed of'sound In a gas can be written (V. and since a number less than I raised to any positiv power remains less than I. W1 - We can now find.) II' p(I'I.) 1 Note that the work is positive for all three processes. Thus B . PI) 40 3 30 v- fifiP.{Vr. 28 (pV' the derivative with respect to j'. which gives . 1 ..:. ~ •. we can write the adiabatic work as W..PrVl.VI)" -( 10 PaX 1. w- :~'l(~~y~' [ -I] V. r IVf V1 dv v. 26. .. -PiVt' VI-.0 - p. which can also be written 11M. Path 2 is an isotherm.--..-(40 Pa)(1. 9.-the work again is negative. the work done during the isothermal process can be found using Eq.11 mol is dV' For an adiabatic proce Eq. A gas V(m~ Thus the speed of sound in II gas depends on the SQuare roo! of the temperature.4.. dll or v---'1P dV dp . 25). (30) If the gas expands. ....!V I -(10 PaX4. "1'" p dV - Il"PJn dVi+ P. log the result of pan (o)and the ideal gas equati n of state( Eq. . and that the magnitudes increase according to the area under each path on the p V diagram. d(PV constant) compressed from a volume of 4:0 mJ to 1. . takin dV 1)_(d.0 m' .. ~y(nRTIV) ~ p p c::. elution Path I consists of two processes. for nRT. W . (b) In Section 20·1.518 Chatuer 23 Kinetic Theory and the Ideal Gas The work done at constant volume is zero (see Eq. 10m) m 1- 5S J.0 Inl) . give.p( ~ r.yp for an adiabatic process involving an ideal gas.4. V. and so the total work for path 3 is First by bringing a factor of V{-l inside the parentheses. 234 The Quantity p V is the total mass of the gas. we obtain v- '1P -.0 m' . for which the work is again zero. substituting p.30 J. alon whi h T constant.) .(Pr (~p }'.0 m')'" 120 J.). so the total work for path I is WI .". Let us choose the initial point PI. where /I is the number of mole and M I~the molar mass.L )1_ r I (V1-Y I - Path 3 consists of a process at constant volume. p~ where B is the bulk modulus andpis the densuy of the gas. Compare the work done along the three different paths hown in Fig.0 in) while its pressure increases from 10 to 40 Pa. and second by using PI V{ .---10 Sample Problem S. 10. and so P r_ J)IV/ or r 30 J + 0 •••30 J. 20 10 '----:-----~ (V.the adiabatic work: w. Sample Problem 6 (a) Find the bulk modulus B for an adl batic process involving an ideal gas.. The work done at constant pressure is found from Eq.PrV. we have ligure IS taken from initial point i to !lnnl point f along three different paths.I (adiabatic).

where 1 is the rotational inertia of the molecule for\otauons about a. The x'y'z' eoordinatesystern is fixed to the center of mass of the molecule. 33 the change in temperature is also negative. for example. there lS no other form for the internal energy Eint to take. w. and the parameter '1is about 1. There is no molecular potential then follows that t:.of two-atoms -. and thu!> there is 110 term in the kinetic energy corresponding to such rotations. «. One way to change the internal energy of an ideal gas is to do work on il (or to allow the gas to do work on its environment). If the piston moves upward. the internal energy can only be transla- tional kinetic energy. Eq. 32. Instead of considering a molecule to be represented as a point particle. as we have seen. depends on the translational kinetic energy of the molecules.consisting considered i' to be point particles. The total kinetic energy of the molecule is the sum of the translational and rotational parts: K . -------~----. (34) j f For all ideal gas. and thus there are kinetic energy terms for such rotaticns. Such a molecule can acquire kinetic energy by rotating about its center of mass. and by Eq. 28 of Chapter 8) then gives (32) Because kinetic energy is the only type of energy the molecule can have.4. so that Wis positive in Eq. + 11. 11)can be written KlOI = 11x-w. even if one has greater rotational energy and thus greater internal energy. A simpler way is to evaluate the average energy per molecule. 1 is isolated from the thermal reservoir.O. The interna] energy of aft ideal gas depends cnly on the temperature. 23-6 THE INTERNAL ENERGY OF AN IDEAL GAS OUf model of the ideal gas is based on molecules that are considered to be point particles.0290 kg/mol.31 . those with two atoms in each molecule.. . Thus for T.m = nUAJVl) "'" jnRT (31)- using Eq. let it be considered as two point particles separated by a given distance. Suppose the environment does work on the gas. If we' have n moles of an ideal gas at temperature T. For point particles. To determine the relative contributions of translational and rotational kinetic energy (and possibly other forms as because Internal energy is the only way the gas can store energy. Let the environment do work tV on the gas. . particular axis.Secuon 23·6 For air. For point masses. The generalized law of conservation of energy (see Eq.0290 kg/mol the internal energy the contributions of rotational krn uc energy as well as translational kinetic energy. Suppose we do work Won the gas. the envircnrnentdoes negative work on the gas. including such common gases as O2• N1• or CO (carbon monoxide). and using EQ. 0..4X8. To find the total internal energy of the gas. two gases with the same average translational kinetic energy have the same temperature.t/mol· KX293 K) ••• 343 The Internal Eller ')' ()j (111 Idea! {. How much of this increase appears as translationa! kinetic energy and how much as rotational kinetic energy? This determination is very important for understanding the macroscopic proQerties of the gas.lmv~ + mv. According to Bq. 18..(J5 519 I m s. is shown with its axis along the z! axis of a coordinate system. In this orientation. 34 over all N molecules. increasing its internalenergy. The rotational kinetic energy of a diatomic molecule. the average molar mass is about 0. Let us now modify one of the basic assumptions in our model of the ideal gas. 34 also represents the contribution of one molecule to the internal energy of the gas. on the pressure or the volume of the gas. then E. . That i . because only the average translational kinetic energy of a gas CIJI/tributes to its temperature. and it is therefore necessary to consider in )I' --·---. This . nor is-there any internal energy associated with the rotation or the vibration of'the molecule.20·C . Suppose the gas in the cylinder shown in Fig.--Figure 1) A diatomic molecule. + J)'ow.. 31 we can write (33) so that the temperature change is also positive.•.. The temperature. there is no kinetic energy associated with rotation about the :' axis. V . It does not depend. 32 the change in internal energy is negative.odel gives a better description of diatomic gases. and the work gives the only contribution to the change in internal energy of the gas. + 1m!}.w.L~x r. we must find the sum of expressions such as Eq. (1.293 K. N. the roo tat{onal inertia for rotations abour lhe z' axls is zero. The rotational inertias for rotations about the x' and y' axes are not Zero. illustrated in Fig.E101 must be positive. because J:. and then multiply by the number of molecules. + !I)-.

\ here the more violent collisions can cause the molecule I vibrate. Equation 35 is identical with EQ.() O1l h.'. as i'i\ CO2). the Iinal pomt reached in Ih~ adiabatic process lies vertically Iar above the final POlOt reached in the Isothermal process (40 Pal. we can how that. We also see that. Other kinds of energy may also contribute.inTI'.520 homer 21 Kineuc Theory and the Ideal Gas well) to th internal energy. urc can be found using the adiabatic relauonship of I'q. In Section 25-4. as the temperature of a gas is lowered. This theorem. In To find the change internal energy.31 J/mol· --I} o -lK • J K) £. d the ch II' 1)( 10 internal energy of the gas. a/energy. and vibrate would ha e 7 (.-IOP. The internal kinetic energy per molecule could then have a sixth term. <. For c ample. A monatomic gas has only three degrees of freedom r molecule. F L . depends only on the temperature and is 01. Vl'W~'. !mv. + ." by rr ·. This consisteut With the adiabatic curves being steeper than the rsotherrnat CIlf\C~.0 m1)' n ifwc (I. 34. rotate. a diatomic molecule that is free to vibr te (imagine the two atoms to be connected by a spring) has two additional comribuuons to the energy: the potential energy of the pring and the vibrational kinetic encrg of the atom. The vibrational modes in the internal energy arc usually apparent nly at high temperature. From classical statistical mechanics. So far we have considered only the contributions of the overall translational or rotauonal kinetic energy to the internal energy of a gas.llmol)( . such as the five terms in Eq.3nRT (polyatornic gas).Orn')'''' -1(lOP N(!kT} . when the number of particles is large and Newtc nian mechanic holds. and the total int mal energy of the N molecules is l:. 10. deduced by Maxwell.ftI '{ k'Tv= two." 0 that at a low enough temperature only the 3 translational degrees of freedom are present. p. For other gasc .11(100 PaX 1. 9. (lOPa)(4. We can thus say that the seeds of quantum theory lay in the kinetic theory of gases . and let \I omprcs the a adiabatically atomic Solution as until its olurnc IS I'. and for nonrigid molecules it 'is necessary to include terms in the energy corresponding to the Vibrational motion (se Section 15-10). 4 is called a degree of freedom. as. the five terms of Eq. 'IS shown in FiS. Thu a diatomic molecule free to translate. In other words.0 m nR 0101)( . 31. since it has only translational kinetic energy (H. (36) A polyatornic gas (more than two atoms per molecule) generally has three possible axes of rotation (unless the three atoms Ii in a straight line. 29: flrp V1 .". and 1.3 + 2 + 2) degrees of Irecdom.61\).\1' 110 \ III and we can find the final temperature If we now rh PI ure and volume of the final porru.I I t ihe cvlin crb removed from the thermal fee. is called the equipartition . the result is E'nl - know the change in temperature.6 and 8. the internal energy is On the pr' diagram of Fig. we can u •••.3IJ/mol· ')(IOQK- The change in internal nel'%Y i po IIi\('.11 mol)(8. tlR fI. For a diatomic gas. 1 ct us use the equipartition of energy theor m to write an cxpr Ion for the internal energy of a monatomic ideal gas. each o] these independent terms has the same average energy of !kT. rvorr. The 010$1 senous shortcoming of this ideal gas model is Its failure to account for (he quantum effects inherent In atomic and molecular structure.(10 Pa)(4. (37) --"'" . if the molecule IS rigid..t q nRT (monatomic gas). it i necessary to consider the avcrag valu of each different term in the expression for the internal energy of a gas. For polyatornic mole ules.1 -HO. See "On Teaching Quantum Phe-nomena.). c nsistcnt \ ith I q '2 for this adiabatic proccs . for example. For 6 degree of fseedorn. which we consider in Chapter 24.sumlllg it to t • helium (a n with r= 1. (35) where we have used Eq .\ hich the ~a begin at the initial pouu \ ith \olumc~'. because the wor done In cornnrcs In th gas is similarly posiuvc •. we how that the results defied in this section give a very good description of the relauonship between the internal energy and the temperature of real gases. ugust 1964.:-"1 0\\.inRT (diatomic gas).31 J/mol'K) I) -44 K . We an nnd the rru I 1 temperature USIng the ideal ga 1\\\\ ( ince p.0rn1) (0. We can now proceed to fin 1the initial and final temperature and then the change In Internal energy' I. which is based on the a urnption of a rigid diatomic molecule. Each independent form that a system's energy can take. T E'n! - i '( kT) . diatomic g ••hasfire degrees of freedom per molecule. Th final pres. \.ftI-~nRtJ..• 'ample Problem 7 cnsidcr once agam the situauon otSam- pic Probl m 5. with S degrees of freedom. we might need to include a third rotational term.-40m)andpf ssurcp. 401. tributed in equal shares to each of the independent ways that a molecule can store energy. I. the number of vibrational terms in the energy can be greater t ha n I T r Prl'( --= (0. III \.!. the vibrational and rotational m ti IlS can he "frozen. COrl/C'IIlP{)rtJr) Physln.(."t· !nll'. E pcrimcnts with ga collisions provided earl) evidence that the internal energy of an a (1111 I'> quantized. The average internal energy per molecule is lkT ( degre s of freedom X !k'f per degree of freedom). the available cnerg.

'111C potenual energy is u minimum at the equilibrium separation 'v. or course. :n~ 7 I~TEHMOL£ CLAR I·ORCc~ (Optional) }'OC\. It IS evident that either assumption will lead to the Slime results. the)' Are short-range forces. ln J sotid. that molecules do not interact electrically. 12(/. correspondmg to this potential energy. so that these forces act only over short distances. At '0 no force acts between the molecules. for example. The molecules repel each other because there is no way tor a molecule to rearrange itself internally to prevent repulsion of the adjacent external electrons. Hen e an attractive intermolecular force results. This does riot mean. However. because one molecule can very QUickly mO\1: out ot the ran~t' f influence of the other. Then the other molecule ISrepelled (rom 0 when the slope of Uis negative and is attracted 100 when the slope is positive. however. This internal rearrangement takes place only when molecules are fairly close R~ u!~.5 X 10-10 Attr(je\. These ac elerations may laM for only a very short ume. 12a represents the mechanical energy of'rhe colliding molecules. smaller than rhc imermolecolar force by a factor or lO. When it sudden! . is indllatrd by the horizontal hne. and clastic. of which the action I:' insensible except 31 a certain small distance. diarneter of the molecule.If'the molecules come very close together. In Fig.N! I his IS a t -pieal result flIHJ shows that gravnauon 1\ ncghgihle 10 iutermole ular forces. The mcchunical energy E. These molecules are electncally neutral in the sense that the negative charge ef the electrons is equal and opposite to the positive charge of the nuclei. as a function of distance r between the. so that their outer charges begin 10 overlap.\l) that these rorces 'In unpart instantaneous accelerations of the order of IO" mrs' ( 10'· Ri. Molecules have theirgre.1\ the mass 01 a mulecule is scsmall (about 10 ~o k. In a liquid the molecules have greater vibrational energy about centers that are free to move but that remain about the same distance from one another. The force F JCling on each molecule is related \0 the potential ene~~y U 'I F= -dV/dr. and the molecules move in straight lines between collisions.~f---'t-----~r -. or about <\ diameters. In Fig. appears it) a repulsive force of very great mlen"ily. Lei us assume that molecules are approximately spherically symmetrical. given b) (/(ildr. All molecules com In electric charges in motion. The molecular force thus has a very short range.!1 Jort'e between the molecules. and the force and potential energy approach zero as r Increases to about 10-" m. they alway show the qualitative behavior Indicated In Fig. Here we can imagine one molecule to be fixed at O. _ . In a gas the average cisranee between the molecules is onsiderably greater than the eflecuve range of intermolecular Iorces. we must remember Ih. at which POlO! the force IS zero. For example. 12a we plot a typical VCr). lib we plo: the mutual force F(r) corresponding to this potential energy function.5 X IO-H) m fot simple molecules.12 «(I) The mutual potential -~. when two moteeuleaapproach each other. est kinetic energy in the ~{)US state.0 molecules as a function of their separation distance r. 12. The distance '03t which the potential is a minimum (the equilibrium point) is about J. Maxwell discusses the relation between the kinetic theory model of a gas and the uuermolecular forces as follows: "Instead of~} 109 that the parucles arc hard. the ferce between tWO helium atom is about 6 X 10-'1 N. spherical. The lme Em Fi . the charges on each are disturbed and depart slightly from their usual positions in such a wny that the averagedistance between opposite charges in the two molecules is a little smaller than that between like charges.C$ between molecules are-of electromagnetic origin. The centers of vibration 0 are mote or less frxcd in a lid. the slope is zero there. -----. the intermolecular force becomes repulsive.lying below the horizontal axis in Fig.The separation of the centers of two molecules at the turning point is the distance of closest approach. from the attractive binding force). (/1) The raJI. C. differcillt molecules have different sizes and internal arrangement of charges so that intermolecular forces vary from one molecule to another. The separation distance ar which the mutual potential energy is zero may be taken as the approximate disranee of closest approach in a low-energy collision and hence as th. Fersimple molecules the diameter IS about 2. Although the miermolccular forces appear to be small h) ordrnary standards.j X 10 IU 10. gravitational force of attraction between molecutes. we may ir we please say th!ll the particles are centers of force." It is interesting to compare the measured intermolecular forces with the.r centers. If It were nor for this repulsion. The gravitational force III that separauon IS about 7 IO-~: N. molecules vibrate about the equilibrium position 'er Their total energy E is negative. If we choose a separailon distance of. The molecule do not have enough energy to escape from the potential valley (that is. The intersection of U(r} with this line is a "turn109 point" of the motion (see Section &-4). molecules would move right through each other instead of rebounding 00 collision. Then we can describe inrermclecutarforcesgraphic311yb) plotting the mutual potential energy of two molecules. that is. It is this repulsion on contact that accounts or the billiard-ball character of molecular collisions In gases.-Figure (b) energy U of \\'. of course.

This force.• . I mole of a gas has a volume of 22.-". 6p . the molecules exert forces on one another only during collisions: thus the only fore that acts on a molecule colliding with the wall is exerted by the wall.4 L. .I • C " . anot her so close that the distance between their centers woul~ than d(Fig. (The factor of comes about because. the impulsemomentum theorem. To account for the effect of tlie range of the force between molecules. we showed that n realistic way of'looking at the intermolecular force lead us 10 conclude that molecules have a small but certainly nonzero diameter(which may contradict assumption 4 of the ideal gas model) and that the range ofthe force may extend beyond the "collision diameter" (which contradicts assumption 5).~N .lib) .522 23-8 Chapter 23 Kinetic Theory and the Ideal Gas Solving for p.. Two molecules are not permitted to apprcacn 0WiC. which I rcsponsible for surface tension. . The "f e volume" available (or one n IS therefore decreased by the volu me of a hemisphere ot d centered on the other molecule. Here d is the diameter of a molecule. and thus the correction b is normally small (0... \ 1 II •I I I I I I' d ~ -II • I . unci we focus our attention on a particular molecule C that 1\ about to strike the wall. let us consider a region of the gas within a distance d of one of the walls of the container (Fig. we obtain nRT P-V-nb' Equation 39 indicates that the pressure of a real gas is incre d relative to that of an ideal gas under the same conduions. as we discussed in Section 2 .) Under normal conditions. A gas molecule C (here considered to he a point) near the wall of the container experiences a net force away from the wall due to the attraction pf the surrounding molecules within the range d of the force between molecules.1%). \ e choo d to correspond to the range of the force between molecules. the reduced volume available to the molecules mean that they make more collisions with the walls and thereby rncrca c the pressure. In the ideal gas mod I. I I. Fiaure 14 or .. If we take the estimate from the previou section of d .. The total volume available to the entire collection of molecules in /I moles is thus the volume V of the container less an amount nb that represents the volume occupied by the molecules.. The "free" volume available to the gas is thus V .2 X 10-) LImo!. by Newton's third Jaw. the sum of all the intermolecular orce give a resultant that acts away from the wall. ( 101ecules near the surface of a liquid experience a similar inward force... 14).. '...nb..010. In the previous section.. but it can become much more significant if we study a gas at high density. and we' can modify the equation of state accordingly: p(V .. In effect..". 13). The net pressure on the walls of the container is reduced by all such molecules within a distance d the walls.S EQ ATIO OF TATE (Optional) Kinetic theory provides the microscopic description of the behavior of an ideal gas.J F dt..s b . .nRT.C • 1 I 1-( .. as two molecules approach one another. The free volume available for molecule B is reduced by the volume of such a hemisphere centered on each molecule of the gas. can be used to relate the change in momentum of'the molecule to the impulse of the II t force F that acts on it during the collision. the range of the force) For a mol ule near the wall. Many modifications to the equation of tale oftbe ideal gas have been suggested to correct for these deficiencies..2 X 10-' m Imol . let us regard each molecule as a hard Qilere or diameter d. is equal to the force exerted on the wall by the molecule and thus is responsible for the pressure that the gas exerts on the wall of the container.5 X 10-10 m. In this section we devefOp a modified equation of state that takes these factors into c. . (38) -.' I I I I I --. Now suppose that molecule C also experien es force from the attraction of other nearb molecules (tho: 'I~\O within a hemisphere of radius d. the volume within which they interact is not a full sphere but the hemisphere facing the direction of approach. Let b represent the decrease in the available volume due to the molecules in I mole of a gas.) 1 nus during the collision the component of the force acting away from the \'"311 THE A DER \ AI.. . e Section \ 7-6.: I • . Ii Figure 13 If molecules of a ga arc considered to behave like hard spheres. then we estimate b as ro. but certain of the assumptions of our model of the ideal gas are not valid when applied to real gases... When it strikes th wall..t: To consider the effect of\ilae finite size of the molecules.•• H1tcf3) .. then the center of molecule B is not permitted to move within the hemisphere of radius d centered on molecule A..2.

as EQ. it suggests that some _he CO.. each suffering the same effect The overall effect thus Increases ninefold. OUf imaginary hemisphere will have three times as man). As the as is compressed along this isotherm.. The van der Waals model thus suggests the existence of mixtures of different phases. the reaction force exerted by the molecule is maller. so that the corrected pressure becomes p-----a V-nb where a is a proportionality state can be written The an der WUUI. J 3 I 4 (b) I 0 b 1 Vcr 2 V(lO-'m) • l 3 -. (b) Isotherms for I mole of eo. The net effect of the intermolecular force is to introduce a correction to the pressure..~) (V - 11b). proportional to (N/V)l.. If we were 10 compress a sample of CO:.I model with oversimplifying assumptions. Note that at large volume.leaving less of lt in the gascO\lS state. we write it in terms of the number of moles It. the volume approaches the value of b.. indiea ti ng that as we decrease the volume. but instead would follow the horizontal segment A1:J in Fig. 40 requires.!TRi. as the gas condenses into a liquid llt constant pressure. The dashed line 1/l shows a more re hsuc representation of the T. The van der Waal model gives an improvement over the ideal gas model. is condensing uuo allqllid. rather than the value of sere.:---. a the ideal gas equation of state would predict. No simple formula can be applied 10 all gases under all conditions. For a given change in momentum from a collision with the wall. The values.. we would find that tire actual T. the van del' Waals isotherms behave more like those of tbe-ideal a) IOle also thai. which I'> also proportional to the number of molecules. The towl reduction in pressure resuiting from the force between molecules is thus proportional to (N/I-y That is" if we triple the number of molecules but keep the volume of the container constant. of the onsiarus and b must be deiernuned by experiment. Note that Eq. d-et-e-rm-·.-. the molecules are very far apart and the gas density is small) .264 K isotherm would not dip downward as th van der Waals equation predicts.. molecules and hence molecule C will suffer three times the force pulling it away from the wall. . N/V.lIh the wall is proportional to the number of mole ules in the hemisphere of radius d surrounding molecule C and thus to the number f molecules per unit volume of the gas. which makes the equanon empirical in this respect.•..-in-ed-rrom- " the van der Waals equation. The modified equation of This expression. The uet effect due to all the molecules like C in the surface layer of Hue ness d I~ proporuonal to the number of molecules in that layvr . some of the gas ondenses into a liquid.. and the pressure remains constant .--. and only through exPerimenis can we learn w hether one equation rs supenor 10 another in its de ription of reality over a certam set of condmons. which the ideal gas model cannot do.. the pressure likewise decreases. the isotherms begin to co rve down ward. the force exerted by the wall during the collision is therefore smaller. D. is called the van der Wa«/Jl:q/IGIIOtl ofstate..:!6·1 K isotherm. 4 !I ! 3 2 --- . In the entire gas there will be three times as many of these molecules. 15. Since this behavior is contrary to expectauons for a gas. it IS also based on . gas with those calculated for CO2 USing the van der Waals equation or stale.. nRT (h)l V' (40) constant.Section 2]·8 has two corunburlons. van der Waals (18371923).---:--:--:-:--:-~:-:-:-------Figure 15 (0) Isotherms for I mole of an idea! gas. per unit volume of the s. tne ideal and van der Waals·isotherms behave sunilarly.I Equation t!rSIMI' (OptlOl/al) 523 (4 I) (I' a . Instead of wnring thi$ correction in rerms of the number of molecules N. Note that Ihe deviation from ideal behavior occurs primarily at h:igh pressure and at low temperature. 264 K ~ o I I ! I I I I I T 1 c I I I I -rf~-r--~~~ IB I _ o (oJ) I C V (10-4 ml. one from the wall and another from the surrounding molecules. Like the ideal gas equaticn of state. For CO) at temperatures below 304 K. 4! reduces to the ideal gas equation of state (Eq._T •• 304 K •. 7) when the gas occupies a large volume (t1l31 is. but no simple mode! is able: to account for the behavior ofthe gas under all possible cireurnstunces. Figure 15 compares isotherms for an ideal. and the pressure exerted by the gas is likewise smaller Tim reduction In pressure owing to the collision of molecule ". As the temperature is raised. as the pressure becomes very large. first deduced by J.

1Wlhk. as it does other movmg panicles? 8. The tn ! kinetic energy of the molecules' motion relative 10 the t('\' can be 'he same in the two cases. However.1 i molt at the critical pomr. on the temperature. Kinetic Theory and rhe Meal Gas \ e also find that om ether results for the ideal gas are only approximately correct in their application to real gases. In either case. 'd. Setting both derivatives equal to zero and SOh·1O these cquutions simultaneously for (1 nod b. WhatjllstifIC~Hio" is there In neglecti ng the changes rn gravrtational potential energy of mole ules in a gas'! 9.•• estimate the values of the van der Waals constants a and b for COl' Solution The minimum of a curve on a pI" diagram is determined by the point at which the lope dp/dV is zero." Hew does the densuy of humid air compare with tltat of dry cir at the same temperature and pressure? S. Where does the root-mean-square speed of molecules in still air at room temperature fit into this sequence: 0: 2 mts (wal 109speed). 13.1 X 10' mts (escape speed from Earth): 3 X 10' mts (speed of light)'! 6. If the state of the gas L sue. For example. 500 m/s (supersonic airplane). us I appropnate for an isotherm. th: I repulsive forces are more significant than attractive forces.96 X 10-' m '.28 x 10" m) for . sing this information along with the value of the critical pressure p. the disranee between the mole ulcs decreases the pctential energy. 111 till' 14. Actually. In taking both derivatives we assume constant 7.und that the weight of an empty Oat thin plastic hag not changed when the bag is filled with air. III internal energy is not simply a function of temperature but depends on the volume as well. 30 't(lts (fast car). yt:1 continue indefirutely with no sign of dimirustnug <pc•. ISh for CO2 at a temperature of T.1I1(£.1successful fIrst step III irnproving the ideal cas model in t::lSCS ill which the molecule arc sufficienti) close together that the ba ic assurnpuons of the ideal gas model do nOI hold.. Consider a hot. Arc these statements contradictory? If not. h 0. In which room is there more air? 7. [I is fo. For some gases (hydrogen and helium at ordinary temperatures. We can find the derivative when the van der Wallis equation of slate is written in the form of Eq. Explam how. howc 1:1. cornpletely unable to do.ative IS zero. aptt II"" RT. and thi expectation IS consrstcnt with experiment in most gases. We have assumed that the force exerted by molecules on the wall of a container i~steady in time.524 Chapter ']J .. We have assumed that the walls of the container arc clastic for molecular colli ions. the fact that the number of atoms is large) is the secret of its rolution:' Discuss this sentence. How is tbis JU~lIficd? 10. J Sb. Mayer and Mayer state: "The very complexity of the problem (that is. Nevcrthele s. and in calculu: we learn that at a point of inflection the second deri •. • QUESTIONS 1.15 X 10' Pa from Fig. On a humid day. We therefore expect the Internal energy ofa gas to increase slightly with volume.Jt is distinguished by having a minimum and a point of inflection (the point where the curvature changes from downward to upward) that coincide at a single point. stationarygol ball silting on a tee and a cold golf ball just moving off the tee alter being hi. a 5t ne Will Iall t the ground If we release It. Why docs this make no diff~"'encc as long as the walls are at the same temperature 3\ the !'\s? 4. '1wo equal-size rooms communicate through-an open door. the walls may be. it still represents only an approximation or the actual behavior.. the average temperatures in the two rooms are maintained at different values. 2..304 K is called the critical isotherrn. Reading PH Sample Problem 8 The isotherm drawn in Fig. In the case of CO~. If tbcre are attractive forces between the molecules. for 1OSI. the above calculation gi . . flow IS the peed ot'sound rc!atl'd kinetic theory model'! 10 the g<l~ . then increasing. for instance) the internal energy i observed to decrease as the volume increases. \vh> nOI" I~ 11: We know tha. What is the ni!Tcrence between the two cases'! . and it even suggests condensation due to the force between I'" = 311/1 ••• 1. Molecular motions nrc maintained by no outvide Iorrc. then the internal potential energy increases as we increase the average distance between the molecules. Justify the fact that the pressure of a gas depends on the square of the speed of its parucles by explairung the dependence of pressure on the collision frequency and the momentum transfer of the particles. we fino (J ~ 27R2T2 Ct 64p. it is . some say that the air is "heavy. what conclusion can you draw from them? 3.wav. We put no constraint on molecules of the air. In discussing the fact that it is impossible to llpply the laws of rncchamcs individually to atoms in a macroscopic system. 1.inelastic. 1 he measured value. yet Ihe~ don't all' fall to the ground. the internal energy ofa real gas depends on the volume as well 3<._7XlO~$lU}/mol. 40: = 0. a-OJ64J'm)/moI2 Although the van der Waals model gives a much more r'::III.: description than me ideal gas model of (he bchav ior of a real gas such as CO2. we then calculate and h"'4. What is the reason that friction does nOl bring these 1lI1] particles to rest. which the ideal gas model i. Why not? 12.ti. Real gases behave like an ideal gas at low densities. In kinetic theory we assume that there is a lar&c number of molecules in a gas.hc volume .

. that is. a person placed in such an envir nment would freeze to death rather than vaporize. 11. \lands until its volume i 1530 em) and its pressure is 106 -Pa. Iso't it just a matter c of time? . internal energy. then. Comment on tlu taterneru: "There are two W:lY to carry out an adiabatic proce s. Of the 101l0w lng quantities. 16. 120 change? 32. What is ibe gas volume now? 6. \\'hy must the lime allowed for diffusion separation be relall\d. the van der W als equation tends to the equation of state of an ideal gas. How. ( ) Calculate the volume occupied by 1. 20.1) How many moles of the gas are plesenl?(b) If the pressure is now raised to 316 kPa and the temperature is r ised to 31. What is the explanation? 18. extensive quantities arc necessarily defined for a ." 35. for a gas to consist of molecules th I all have tl e me speed? 22. assumed to be at a uniform temperature.00 mol of an ideal gas t standard COI dition .00 aim (. However. Do the pressure and volume of air in a house change when the furnace raises the temper ture si nificantly? If'not. PROBLEMS Section 13-) Macroscopic Properties of a Gas and the Ideal Gas Law 1. 38. S. mass.>. being under no restraint from the confining bag. The Nost vacuum thai can be attained in the laboratory corresponds to II pressure of about 10-1$ arm. lfhot air rises. 33. rather than fall. Titan. 4. the atmcspheric pressure is down to 36. density. 0 ygen gas having a volume of 1130 ern! at 42. if'at all. from a lighted candle? 2.lbof. We OHCH )' tha: we see the steam em rgin from the SPOUI ola ' eule in w hi h Wilier is boiling. holt' system.0·C. F r bove the Earth's surfa e 'he gas kinetic temperature is reponed to be on the order of 1000 K. Would we use the same pro- 525 cess'? If not. short? 27. volume.t. but our own Moon does nor. Why doe n't the Earth's atmo phere leak away'? At the lOP of the atmosphere toms will occasionally be he ded out with speed e.0cm Hg and the helium has expanded. (.0 em Hg) and a temperature of 22. (b) Show that the number of molecules per cubic centimeter (the Loschrnidt number) at stan tard conditions is 2.0·C nd a pressure of 10I kP e. whereas intensi ·c quanuues apply uruforrnly t uny small part of the system.01 X ]0-1) Pa. Would you expect real mole utes 10 be spherical! '~ymmel· rieal? If not.0·C and a pressure of 108 kPa oc upies a. Explain why the temperature of a gas drops in an adiabatic expansion. Considering the diffusion of gases into each other. At thi elev titian the gas temperature IS -48. 37. Would a gas v-hose molecules were true geometric points obey the ideal gas law? 25. A s led rubber balloon contams d very light gas The balloon IS released and it rises high into the atmosphere. md (a) the number 0 milks of oxygen in (he: syste ::! (b) its nnal temperature. tion? Is a entrifuge better than a diffusion chamber for separation of gases? 30. At an elevation of 6. eeding the e pe speed. Explain. Show that as the volume: per mole of a t' ~increases. A weather balloon is loosely inO led with helium at a pressure of 1. Wh} docs smoke rise.00 atm (-7'. e plain how the separation pr e s waul have to be modified 28. or 1.••.Problems . easily observable in the l. i$ the ideal gas law violated'! 31. an ideal as cannot be. temperature. How many molecule are there per cubic centimeter in such a vacuum at 22"0 3. One is to do it quickly and the other is to do it In an Insulated box. is given by . A quantity of ideal gas at 12. steam itself is a c lorless What is it that you really see? 2).0·C. 36. In large-scale inel stic colli ions mechanical energy is lost through internal friction resulting in a rise of temperature OWlOg to increased internal molecular agitation. Sup ose we want to obtain mU instead oflUU as the end product of a diffusion process. Is there a ] s of mechanical energy to heat in an inelastic collision between molecules? . determine which are extensive an which are intensive: pressure. pressure of 1. Although real gases can hquified.values that depend on what the system's boundaries are.•.0·C.1. The gas volume is 3. By c nsidcrina quantities that rnu t be conserved in an el tic colli ion. can you draw an an logy to a large jostling crowd with many "collisions" on a large Inclined plane WIth a stope of a fewdegree ? 29. show th tin general molecule of a gas cannot have (he same speeds alter colli ion a they had befor . whereas intensive quantities are independent of the choice of boundaries. one of'Sarurn's many moons. Can you describe a cenuifu al de 'ice for gaseous separ .68 X 1019• 2. has an atmosphere. The variation in pressure m the Earth's atmosphere.50 krn. However. how would the potential energy function of Fig. would you expect the composition ofthe air to change with altitude? 19 Expl ••in why the temperature decreases with height in th tower atmosphere. v lurne of2.ttof) occurs . Extensive quantities have.Is It sible. Wh} do molecules not travel in perfectly straight line between collisions and what effect.47 m-. how much volume will the gas now occupy? Assume no leaks.47 ml. Explain. That is.01 X 10i P ) and temperature of O·C ("" 273 K). DeS ribe and explain the thermal nu mechanical beh vior of the b lloon.IS a result? 'lb. why is It cooler at the lOP of mountain than near sea level? 34.

1. _ " • . •• • A • •.22 atrn pressure.0 X !OJ Pa and at a temperature or 400 K.1 when the temperature is . part evenly spaced at the centers of identical cubes. Using Avogadro' constant and taking the dlarnctcr-of'a molecule to be 3..44atm.J . PrIl-Mtyll!. Imagine that the molecules are for the most. Suppose that the radius ora (spherical) argon atom is 0.:~". find the length of an edge of such a cube and calculate the ratio of this length to the diameter a molecule. or I J. ~ • • •.) IS. and (c) a VTdiagrnm.22 Land 3. . where n" is the number of molecules per unit volume. (d) How do these curves depend on the mass of gas chosen? 8. • • •• 4t • •• -----. ----figure 17 Problem 13.. as 5110wn in Fig. Again imagine the molecules to be evenly spaced at the centers of identical cubes and repeat the calculation in (a) 11.'.• it :. Express your estimate as a fraction of the mass of the Earth.2. The temperature in interstellar space IS 2..'igurc 16 Problem I::.1. Calculate the root-mean-square peed or ammUOI:I (1'< ..5 m deep where the temperature is 3.'m . The larger vessel is then healed to 108'(' while the smaller one remains at 16. (lJ) a pTdiagrllm. and isothcnnal (constant temperature) processes on (a) apV diagram.! and contains air at a gauge pressure or24.'" ·41·· . The onne ling valve l~ opened.4 em) volume is at the bottom or a lake 41.) 10.60'C. ~ •. where J\{ is the molar mass 01 the air. Whatis the depth h of the lower end of the pipe? Assume that the t .71b/in. An open -closcd pipe of length L •. as in Fig.the vessels arc at the same temperature. Calculate the fmal pressure (flint: There (Ire 1'10 leaks. J..• •• • •. 16. Calculate the fraction of the container volume actually occupied by atoms.-:~ • • • ••••4Ir '~:i:!:(5~. .0"('. (11InI: It is not necessary to convert from British to S1 units..0 em I of mcrcur '1\ admitted through the stopcock at the bouorn The level on lht' Itlt increases 600 em and thai on the nghl increases 4 ()Oem Find the pressure Pn Figure 18 Problem 16.00 X 10-scm. 7..•• • • • .2 Ib/in.. The edge length is an estimate of the distance between molecules in the gas. 16. Recall that atmospheric pressure equals 101 kPa.liv>II<'. Container A contains an ideal gas at a pressure of 5.. (See Table I.6·C and its volume increases to 1020 in. (0) Consider J.00 atrn pressure.• . or tube to container B witl: four time the volume of /v. (b) Now consider a mole of water ha ing a volume of I8 cm1..Jmually.n v(Je-. Section 23-3 Kinetic Calculation ollht Pressure 17..0·C and 1. J 6.RO·C: The bubble rises to the surface.. which is at a temperature of 22. Find the gauge pressure or the air in the tire when its temperature rises to 2S.. Estimate the mass of the Earth's atmosphere. •. (See Section 17-3.i II molecules at 56.710 X 10-10 m. ..526 fJ - Chapter 2J Kinetic Theory and tile Ideal Gas .-::-::0-:-....) Show that II" . 9. . An atom or nitrogen has a mas. and the same pre sure..•• '?. .14. Take the temperature of the bubble to be the same as that of .0 X IO~ Pa and at a temperature or 300 K. Two vessels of volumes 1. B ..:. U is thrust vertically into II freshwater lake until the water rises h~lrway up in the pipe.18 LCQnt(l1O krypton gas and are connected by a thin tube. Consider a sample of argon gas at 35. B contains the same ideal gas at a pressure of 1." . see Fig 17. and equilibrium is achieved at a common pressure while the temperature of each container is kepI constant :lI its initial value.7 K Find the root-mean-square spec of h -drogcn molecules at this ternperature. An air bubble of 19.OO mol of an ideal gas at 285 K and 1. constant volume.:-.• .• .. Whal is the final pressure in the system? 14. Why? Use P.pc::!:~ • • • ••••••• . llt WIth the temperature constaru.•• 25.0-C.0 m contains air at atmospheric pressure. A rnercury-fllled manometer with two unequal-length arms of the same cross-sectional area is scaled off with the same pressure Pn in the two arms. Consider a given mass of ideal gas.the surrounding w':ltcr and find its volume just before It reaches the surface.6"C. .) 18.••.0'C.rnperaturc is the same everywhere and docs not change .--------. It is connected hy II thin r .an additional 10.7'. An automobile tire has a VOlume 0['188 in. 12.. Compare curves representing constant pressure.

nRmcly.cubical box 25 em on a.68 X IO! Pa. Cb) What is the mass of this volum e of air'? Assume that 75% of the molecules llre nitrogen (Nt) and 25% tire oxygen (01). 28. (c)1ne temperature lugh in the Earth's upper atmosphere is aboui !000 K.0 cm2 of wall at an angle of 55" with the normal when moving with a speed of 1.Problems 2. :':.50. Ceuslder a gas at temperature T occupying a volume V to consist O!a mixture of atoms. 30.000 atm pressure the densitiesofair. is present. 25. What fraction of the total pressure 011 the coruumer W. assuming only these two gases 10 be present 20.'.. oxygen.0 to 8. i9 is the corona- Find the average translatlena! kinetic energy orindiv!dua.0 ml alQng either path 1 Of r .250 kg{m'. of . (oJ Do the same for the Moon. ((1) Co temperatures at which the tHIS speed is equal to of escape from the surface ofthe Earth for molecular ltydtogen and f¢f meleenlar oxygen. Tbeglewsurrounding me !'HlH in the x-ruy photo shown in Fig.. Hs temperature and pressure are P:L Calculate the rms speed of free absoll.0 X IOs cmrs. for the gas molecules.S)1. wn mu. At what iemperature do the atoms of helium gas h::vc the same nus speoo as the molecules ofhydtogcn gas n 26. and at IOO·C. (a) Find p. It 1. side. (b) Suppose now that N. und the envelope has a capacity of 2180 ml. and t . (0) Calculate-the nurnbet of moles of gold present.rttrn in Fig. what Should be the temperatute uftht enclosed air to give the balloon a lifting CUPllcity.0·C? 35.JI! is attributable to the second gas? (Hint: See Problem 22. Two motes of the first molar mass M\.. what would be the ratio of the pressure after combination to the pressure before? 31. Calculate the ratio of the change in gravitational potential energy ofa mole of oxygen molecules falling the hei&ht of the box. what pressure do they exert on the wall? 21. lull' stares that when mixtures of gases having no Chemical interaction are present together in a vessel. (Ii) Find the molar mass of the gas and identify it 22. 26. with twO ideal gases. Derive this law from kinetic u.nssofnltrogen in the air from these data. U5! ng (.) Section 23-4 Kinetic lnterpretatio» cfth~ Tempitrtlttlrc 2.'tS at 1S' C and 1. Duiron'.23 X 10"'" atm the density of a gas is t n 10' &/<:m'.22 kgfm'. How m uch work is done Oil : he gas if its pressure changes with volume according to each of th e three processes shown in t. the atmosphere of'tne SUIl.:) X Hr14 g.number of molecules in 1. respectively.0 'X 10· K and 0. to the total tr'lnsla· tionalldm:tic eners}' of the molecules. How many grams orgas leaked out of the tank'l 3:. (0) Find the.OFa. atoms ofma$~ m• • each having an rms speed v. (a) What is the volume utthe tank? (Ii) The tank is cheeked later when the tempc1"dture has dropped to 22. at liJ)'C. + Once the temperature retums to its original value. assuming the grttvhationai uecelcration -on itsslltfacc to bell! 6g._and 0. PI. Calculate the fraction by m. Consider a 2. 23-5 Work Don« an tIn laMl (J(JJ Flgur': 19 Problem 24.H! .he pI! diug.0·C. The mass of the H2 molecule is ~.33 X lO-J6 kg and an atom of hydrogen has 1. At 44. has a denr:lty 011.61 x lO-H kg. At O'C and 1. (b) How many atoms of gold are presenfl 29.429 kg/m". It is then compressed back to 2.& sample of pure goW vapor. Oxygen (01) g.HI1C tJ~~lhe d surrounding air. Suppose that a sample of gas expands frorn 2. 20'? 37. Would you expect to find much hydrogen there? Mueh ox)'gen'l 34. 2:.N.0·C and the absolute pressure has fallen to 8.0 ml while:its pfC$$ure . Gold has II raolsr (atomic) mass of t 97 S/rool. temperatures. and that the total pressure is equal to the SUm of the partial pressures of each gas.3M .. decreases from 15 to S. (0) latlOnal C a teulare Ihe a verage value in electron-volts of'the transkinetic cnergy of the particles of'an ideal gas atO'C 36. 1.35 X l06Paandtempenlture77.m. A steel tank CMlains315 g of ammonia g.0·C and 1. 31.0 !T\ l alotlg the diagonal path in the pI! diagram . Molecules oflhe second gas ha vc a molar mass .0 atm pressure is confined to a. (b) Find the traMlalional kinetic energy per mole otan ideal gas at these.1 f he Sun is a huge ball of hot ideal (NH) tit an m". • 13 527 mass of 19. When fully inflated. dition to its 0. . A sample ofgllscxpands from tOto 5.030 electrons in the corona. the pressure exerted by each constituent at a given temperature t'.A$S1. and nitrogen are.! nitrogen molecules at 1600 K (a) in joules and (b) in electron-volts. "'" N~ and that the diiferent atoms combine at constnnt volume to form molecules t1f mass nI.5 mol of this g:t:. At what temperature is the average translational kinetic energy ofa molecule in an ideal gas equal to LOO eV? 27.. :no A oruainer encloses gas are present. The envelope and basket of a hor-eir balloon hll'"~ a cornbined mass 01' 249 kg. zn ~ Seetion.i the same as It would exert ifi! alone filled the whole vessel.293 ks/ml 1.0·C and at a pressure of tOO atm. in joules.00 m) ofnital 20. and N"atoms of'rnass m" each having an rms speeo VI>' (0) Give an expression for lhe total pressure exerted by the gas.lteprcssureofl.6 X 1011 hydrogen molecules per second strike 2.hown in Fig.

Calculate the mtcrnal .) Which assumption is more reasonable? Section 23·6 Tit" Internal Enug)' of an Idea! Ga 48.0'( and I e){) nun pre•• ure s and delivers compressed air al 2 30 aim pressure I'hc cornpressor operates a12_ 0 W of useful PC>W\)I. 54.142 m1 at 103 kPa gauge pressure is expanded isothermally to zero gauge Pl'(:!>SUfC and then c ooled at constant prccsure until it reaches its initial volume. Show that t'l/!'.00 ntrn pressure has a dcnsirv of : . An air compressor takes air at 1 . and dcr Waals C'QU:lhOn rn. It lies honzontal!y.0' C. Show. Find ItS final pres urc and temperature. The "!X'eOof <ound in different gases at the same temperatuft' depend •• Oil the molar mass of the gas. - . 42.4 6 \ (Ill)) 8 1 mole r In Id I. k) How man moles of gas ~Il' P:'.! I' = I 36 rn I. T=-2JO ClOP"'" 1. Determine (0) the final pressure-and (tJ) the fmal temperature.:.. If the tube is now turned to a vertical position.. assuming the gas to be an ideal gas for which r . (b) The gas if.\!S ~q\JMI(1n art' substances. . \<1 l'r 55. gas occuo mg a volume of 14."<!'11 'S lC!cnll' at 56. o . A thin tube. the middle 10. is 1. Calculate the work done on» rnoles o a van der Waalvgas In an isothermal expansion from volume V.'I.\ ir • t O'(X)'C and 1.:nc1t:' .40 and the volume expansion entia is 1.::1t' (d) What IS or the total translational kinetic coer!')' per mote before and after the compression? (e} Calculate the rauo "f the rms speed befere to that after the eompressk 11. 53. calculate the final temperature if j' "" 1. 10 5 '2 . 3 0 2 J V(m~ 4 5 6 Figure 20 Problem 36. 39. Compute (El) the value of y of air and (b) the effective molar mass air. (c) How much work was done on the p? 44. sealed at both ends. An ideal gas experiences an adiabatic comprcssi '0 I:. Calculate the total rotational (II' Hi g: <:I.1I the mercury be displaced? Assume that the process is (a) isothermal and (In adiabatic (For . Show that V CI"'" 3ltb. Compute 'I\. 50. Compute the work done on the gas. (a) Calculate the value Ill' 'j (i'l Find the: In I .2 L. 41.00 m tong.32 aim pressure to 15. 40.' path 2. where is the speed of sound m the gas of molar mas M 1 and Ii) is the speed of v.\ tH!'. Assuming the process i~adl:lbauc. (oj Frnd lllc temperature of the compressed air. t\ cosmic-ray particle with enctg\ I . Gas occupies a volume of 4. '. now cooled hack to 273 Kat constant pressure Find the final volume.33 L at 1 pressure of I. hv what amount w. Assume (a) that the \ an der Waals equation is correct.~·!·).1. Section 23-8 Th« Van der Waal5 Equatlo« of Sla(1' 52. 4. calculate tbe pressure at 16.0·C.06 L. 45. and the speed or sound is 33 l mts at that temperature. 5 49.1 • cutes in [ mote of air at 25."1.1.\ detecting tube that contains 0. the van for all substances. JR. (eI) One liter (If gas with f'" 1. It is compressed adiabatically to a volume of 1.:H d\l~ (constant T). u p-122kPa.IO. The constants a and different for different toke V.•. lern 8.40.0·C of 2. }'= I AO. I? aun and a temperature or.. pressure.4 Land 1. Calculate th work done by an external agent in compressing I 12 mol of ox w~n from a volume of 22.32 is at 27) K and 1.3 L at the same temperature.·.111:11<' ~\hH!1'.0 em containing mercury and the two equal ends containing air al standard atmospheric pressure. (b) How much cornprc sed arr In liters. '\S ume that the compressor operate adiabati ally.59 mls for each Celsius degree nse In temperature near 20·C.528 Chapte) 23 20 Kinetic Theory and the Ideal Gas original volume. ~ und in the gas 0 molal mass /If .29 t '/ 10 ' >rJc·m) occupies 0.1::'0 mol of II (In /::ts ()n'" this energy Isdl~tributl'J among .In 'Ih: t\. is delivered each second? 47.JH) K. (c) Find the (0l31 "url. Van der Waals b for oxygen is J~ em 1/r~()1.l. T'..urc l~ IS suddenly (adiabatically) compressed \0 halfits kmcti(' cncrzv .00 31m pres .5) mol ot O. then (b) that COl behaves a~ an ideal gas.28.n Pc<' and Tn temperature. that If W{' as the umts ol volume. Compute the net work done on the gas for the complete cycle in each cas::.7m'. U~ the result of Sample Problcm S tc show that the speed of sound in lllr increases about 0.! diameter of an 0) molecule.'\ IS stoPl'l'J Ifl. Using the values of a and h for co) found In amnlc Ph I. bv 1\0\\ mu : IS the temperature of the neon mrrcase-I? S1. . Air Ih. The gas in a cloud chamber at n temperature of 292 K undergoes a rapid expansion. however. h in the van dcr W. cone nil (he gas. 46.