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Mathematical Methods



Often, important laws are reformulated to change variables in order to simplify the analysis of a system. For example, Newton's laws of motion can be rewritten in completely equivalent Lagrange's equations for appropriate coordinate systems in classical mechanics ..The Lagrange's equations, in turn, can undergo a change of variable to produce the related Hamilton's equations that are fundamentally important in quantum mechanics. Changes of variables, known as Legendre differential transformations, yield functions that are fundamentally important in thermodynamics, If the state of a system is described by a function of two variablesf(x,y), which satisfies the equation df


u dx

+ v dy



and we wish to change the description to one involving a new function g(u,y), satisfying a similar equation in terms of du and dy, then it is necessary to define the Legendre transform g(u,y) as


=1 -



It is readily verified that g satisfies the equation

dg = -xdu

+ vdy.


Let us use Eq. (10..2) to define new thermodynamic state functions. Consider the first law of thermodynamics for a hydrostatic system with heat expressed in terms of temperature and entropy, namely,

dU- -PdV+TdS,





Fundamental Concepts

where U is a function characterized by V and S. Therefore, U is convenient for situations involving changes in volume and entropy. For other situations, it is easier to work with different variables involving different functions. Define a new characteristic function H, called enthalpy, using Eq. (10.2) to obtain

= U +Pv.


Since U, P, and V are all state functions, H is also a state function. In differential form,


V dP+ TdS,


where H is a function characterized by P and S. Enthalpy is a convenient function for problems involving heat quantities, such as heat capacities, latent heats, and heats of reaction, when pressure is the variable being controlled. Equation (l0.4) may be rewritten as
dU = TdS - PdV,

in order to generate a characteristic function other than enthalpy, namely, the Helmholtz function A, given by the Legendre transform



(10.7) (10.8)

which is also a state function. In differential form,
dA = -SdT - PdV,

where A is a function of T and V. This function is appropriate for problems in which temperature and volume are the convenient independent variables, such as the partition function in statistical mechanics. The last characteristic function, known as the Gibbs function G, is generated by a Legendre transformation of



+ V dP,

that is,


(10.9) (10.10)

which is also a state function. In differential form,
dG = V dP - S dT,

where G is a function characterized by P and T. The Gibbs function is designed for problems in which pressure and temperature are the convenient independent variables, namely, phase transitions and most chemical reactions. It is important to realize that no information is lost in the transformation from one characteristic function to another. The gain is a new function expressed in thermodynamic coordinates amenable to the experimental situation at hand. This remarkable formalism and procedure was introduced into thermodynamics during the 1870s by J. Willard Gibbs, Professor of Mathematical Physics at Yale for his entire career, but the names of the functions and their symbols were chosen by other scientists.

such as wires. electrets. For example. are conserved. namely. and no new constants or functions appear in the calculation. But. S). V. The characteristic functions U( V. and dG These differential equations expressing U in terms of V and S. or paramagnets.1 (p. 3. from which it follows. and G(P. T) are known as thermodynamic potential functions. dU dH dA = = = = -PdV -PdV + TdS. V dP+ TdS. we could not obtain the rest of the thermodynamic properties of the system without performing integrations. the thermodynamic coordinates of pressure and volume are replaced by appropriate conjugate variables.13. U). (10. whereas intensive quantities replace negative pressure. as given in Table 3. batteries. then all the thermodynamic properties of a system can be calculated by differentiation only. which. it must be given as a function characterized by V and S. T. that (au) s av =_P and (au) as v = T. The choice of U. S) could be solved to give S(V. . For other simple systems. H. form a complete set of functions. 66). and so forth.S dT. and G as the fundamental set of functions has the advantage that all four functions are energies. Any of the four differential equations could be rearranged to produce another function. if the internal-energy function U were chosen to be a function of V and T. and S for a hydrostatic system. For U to be classified as a thermodynamic potential function.4). from comparison with Eq. and we could then say that S is the characteristic function for volume and internal energy. surfaces. (l0. which introduce unknown constants of integration. just as U is the characteristic function for volume and entropy. we have written four differential equations that are formulations of the first law. T).SdT. notice that the extensive quantities simply replace volume. H in terms of P and S. if the internal-energy function U is known as a function of V and S for a system. There can be characteristic functions calculated for hydrostatic systems other than the four functions just mentioned. of course. A(V. For instance. A.11) However. in Sec.CHAPTER 10: Mathematical Methods 251 In terms of the state functions so far defined. U(V. then we can calculate all the other thermodynamic properties of the system by differentiation. H(P. based on successive Legendre transformations of the four thermodynamic variables P. For example. V dP . We may write dU=(~~)/V+ (~~tdS. S). a compo- . because they have the property that if the functions are expressed in terms of the appropriate thermodynamic variables.

the terms involving the Obviously. In other words. solid. or a series of small holes. the initial state of the gas is an equilibrium state contained between the faces of the two pistons.S dT. due to friction between the gas and the walls of the pores in the plug. A throttling process is also known as a porous plug process or a Joule. (10. imagine a cylinder. In order to investigate this sum. since the right-hand piston against the wall prevents any gas from seeping through the porous plug. lO-l(a). The wall. shown ruled in horizontal lines. The importance of the porous wall is to permit mass to flow from one chamber to another while controlling the pressure.){' .2 ENTHALPY In discussing some of the properties of gases in Chap. These intermediate nonequilibrium states cannot be described by thermodynamic coordinates. Its four characteristic functions are: dU = -PdV dH = V dP dA = -PdV and + /-Lo'?ldm + T dS. the sum of U and PV appeared several times (see Probs. Between the left-hand piston and the wall there is a gas at a pressure Pi and a volume Vi. + J-Lo'?ldm . .252 PART I: Fundamental Concepts site system of an ideal paramagnetic gas was considered.S dT.Thomson expansion.7 and 4. After all the gas has flowed through the porous plug. t A throttling process exhibits internal mechanical irreversibility. m/-LOd'?l + T dS. Now. but an interesting conclusion can be drawn about the initial and final t Also known as a louie-Kelvin expansion: in the middle of the nineteenth century. unlike a free expansion. the gas passes through dissipative nonequilibrium states on its way from the initial equilibrium state to the final equilibrium state. lO-l(b). a narrow constriction. 4. the final equilibrium state of the system is shown in Fig. who did not become known as Lord Kelvin until the end of the nineteenth century. imagine that both pistons move simultaneously at different speeds to the right such that a constant higher pressure Pi is maintained on the left-hand side of the porous plug and a constant lower pressure Pf is maintained on the right-hand side. in a simple system of a paramagnetic hydrostatic variables would not be present. can be a porous plug. thermally insulated and equipped with two adiabatic pistons on opposite sides of a porous wall that is also adiabatic.9).12) dG = V dP . 4. There is no knowledge of the temperature of the gas in either the initial state or the final state.m/-LOd. as shown in Fig. 10. James Prescott Joule collaborated on this experiment with William Thomson.

and (10. The throttling process occurs in an adiabatic enclosure. r. so The net work done by the pistons on the gas causes the gas to flow across the boundary of the system enclosing the porous plug. (10.15) are combined to obtain (Uf .15) with Eq. that is. (l0.a: 0 Since both pressures remain constant on either side of the porous plug.14) + Q. coordinates.Uj) then Of course. (10. A state function can be devised for which there is no difference in the end-states.13) shows that the internal energy U is different for the two equilibrium end-states of the Joule-Thomson expansion. the sums in Eq.16) function H=U + PV. that is. From (10.Vi) = W Q=O.13) (10. If Eqs. which are described by thermodynamic the first law. = -(PfVf .5).14).13).16) are simply the characteristic enthalpy introduced in Eq. (10. (10. (10. (Vf . (10.15) Comparison of Eq.5) . the net work is (10.CHAPTER 10: Mathematical Methods 253 (0) Initial state (b) Final state FIGURE 10-1 Throttling process (J0 ule.Thomson expansion). W =- JO Vf PfdV - JV. equilibrium states.PjVj)l (10.

dU + P dV. the initial and final equilibrium states may be represented by points. Therefore. however. __. and a constant lower pressure on the other side. VdP. we may write hi = hI.18) dH=dQ+ (10. as shown in Fig. We have. since one cannot speak of the enthalpy of a system while it is passing through nonequilibrium states during this irreversible process. For every kilogram of fluid that undergoes the throttling process.5)..16) becomes Hi = HI (throttling process) [property (1)]. dH -' dU but. The continuous Joule-Thomson expansion. dQ + PdV + V dP. Notice that in a throttling process the initial and final enthalpies are equal. is also used in mechanical refrigerators for attaining low temperatures in situations where liquids are unavailable or undesirable. Eq. (10. cannot be plotted.254 PART I: Fundamental Concepts So.17) which is the first of several experimental properties of enthalpy.19) High pressure Pump Low pressure 1 Constant high Constant low 'f FIGURE 10-2 Apparatus for performing a continuous throttling process . (10. 10-2. where h = Him indicates specific enthalpy. In plotting a throttling process on any diagram. which is essential in the production of liquid nitrogen and other cryogenic liquids. . One is not entitled to say that the enthalpy remains constant. The intermediate nonequilibrium states. A continuous throttling process may be achieved by a pump that maintains a constant high pressure on one side of a porous wall or expansion valve. consider the change in enthalpy that occurs when an arbitrary system undergoes any infinitesimal quasi-static process from an initial equilibrium state to a final equilibrium state. from Eq. In order to determine other properties of enthalpy. (10. (10.

the characteristic function enthalpy H(P. Thus. (isobaric) [property (3)]. at constant P. dH=ctQ+ VdP. (10. whereas for an isobaric (constant pressure) process in a hydrostatic system. If H were a function of other variables. are calculated using Eq. (10. boiling. heat is the flow of enthalpy. Eq. as shown in Eq.22) completes the explanation of the concept of heat begun in Sec.21) and the results are expressed as specific enthalpy or molar enthalpy as a function of temperature. Enthalpy values for real vapors and gases at low pressures. or sublimation)." but the phrase enthalpy of reaction is more informative. melting. then the partial derivative would be complicated with terms in addition to the isobaric heat capacity. the isobaric heat capacity is constant and Hj . in theory. -H. For an isochoric (constant volume) process in a hydrostatic system. (10. 4. heat is the flow of internal energy.22) Equation (10.Ti). If heat is added to the system during a first-order phase transition (e. with empirical temperature dependence of Cr.20) shows that the state function enthalpy H is related to an experimental quantity. then the change of enthalpy of the system is called "latent heat. The enthalpy is related to heat.20) provides a means of calculating the enthalpy from isobaric heat capacity data. ~ r c-at (all processes).20) Equation (10. S) is not expressly a function of temperature. namely. Notice that H must be a function of T and P in order to perform the partial differentiation in Eq.4. (10.g. u.CHAPTER 10: MathematicalMethods 255 Dividing both sides by dT. Such data are extremely useful in experimental or practical work. the isobaric heat capacity. Furthermore. which is also a state function. (10." The word "latent" acknowledges that there is no change in temperature of the system when heating the system during a phase transi- . where the mathematical formulation of the first law was introduced and heat was explained as heat in transit due to a difference in temperature between the system and surroundings. we obtain dH ctQ dT = dT+ dP V dT' and. The change of enthalpy of a system during an isobaric chemical process is commonly called the "heat of reaction. [property (2)].21) For an ideal gas..20). the change in enthalpy during an isobaric process is equal to the heat that is transferred between the system and the surroundings. even though.l9). (10. (10.Hi = Cp(Tj .

Partial differentiation yields (8H) 8S PressureP = p T and (8H) 8P = s V. The integral S V dP. From the expression dH=dQ+ VdP.S P dV is represented by the area under an adiabatic curve on a PV diagram. unlike heating without a phase transition. known as (negative) flow-work in engineering practice. whereas the integral . and then carried to a region of lower pressure. is energy that is received by a flowing gas in a region of higher pressure.23) The integral in Eq. (10. perhaps from a pump or piston.256 PART I: Fundamental Concepts tion. (10. Again. is the same as Eq. (10. such as Fig. which. If a pure substance undergoes an infinitesimal reversible process. . such as in the continuous JouleThomson expansion. The integral . There is a thermodynamic difference between the two integrals. the change of enthalpy for an adiabatic process is Hf-Hi= VdP r (adiabatic) [property (4)].S P dV is adiabatic work. then Eq.23) is represented by the area to the left of a curve for an isentropic process on a PV diagram. which changes the configuration of a system with constant mass by changing the volume. (10. it is more informative to use the phrase latent enthalpy.24) Isentropic curve Volume V FIGURE 10-3 PV diagram illustrating the difference between work and flow-work.6). The change in enthalpy of a system undergoing a reversible adiabatic process has an interesting graphical interpretation. 10-3. (10. of course.19) may be written dH = T dS + V dP.

(10.1 for comparison of the two functions. only at the initial and final equilibrium states. the gas expands irreversibly. S) and the enthalpy H(P. S) Throttling process (irreversible) Hi=Hf In general dV=dQ-PdV dE =dQ+ VdP (~~) p= (~~v= Cv Isochoric process Cp Isobaric process H. Consequently. (10. The properties of internal energy U( V. including the chamber that was initially empty of gas.Vi = P av r Adiabatic process Hf-Hi= VdP r r e-st Nearby equilibrium states dU= TdS-PdV (~~) v= T Nearby equilibrium states dH= TdS+ VdP (~~)p= T (~~) s= V (~~) s=-p . which prevents work and heat from entering or leaving the system. S) are given in Table 10. TABLE 10.= Qp For an ideal gas V. Furthermore. S) Free expansion (irreversible) Vi"" Vf In general Enthalpy H (P.-H. . = Ufo Notice that the system is the entire interior volume. that is. The free expansion of a gas occurs in a rigid adiabatic container. U. so no statement can be made about U during the process. the internal energy U is unchanged.CHAPTER 10: Mathematical Methods 257 The relations given in Eq.24) are analogous to similar relations for internal energy given in Eq.1 Comparison of properties of U and H for a hydrostatic system Internal energy U ( V.Vi = r For an ideal gas cvsr Hf -Hi = Adiabatic process Vf .11).

. that is.ST. dA =0.D.7). For a reversible isothermal and isochoric process. For a reversible isothermal process. in a reversible isothermal process.7) as another Legendre transformation of the internal-energy function U( V.QT = D. . but are irreversible in any real. T) was introduced in Eq. In fact. and A = const.3 PART I: Fundamental Concepts HELMHOLTZ AND GIBBS FUNCTIONS The Helmholtz function A(V. from Eq. natural process. the Helmholtz function is given by Eq. WT. Alternatively. we may write. it follows: 1. as in the case of purely mechanical systems.AT = D. (10. For an infinitesimal reversible process. 2. The decrease of the Helmholtz energy D. So.AT = D. From the differential of the Helmholtz function. (10.A. whereas thermodynamic systems are only reversible in idealized cases needed for simple calculations. W T that is performed by the system.8).. UT does not equal the work that the system can perform..UT .25) Hence..UT . dA = -PdV .258 10. S)..26) In other words.SdT. A is sometimes called the Helmholtz free energy. dA = -PdV. A = U. (10.T D.. depending on Thermodynamic work is significantly different from mechanical work.. the decrease in the Helmholtz function is the maximum amount of work done by the system. Mechanical systems are usually considered to be reversible. For any finite isothermal process. the Helmholtz function has the same initial and final values when the initial and final temperatures and volumes are unchanged. or D. (10.~. the increase of the Helmholtz function during a reversible isothermal process equals the work done on the system.)y =- 1: (P dV)y.AT of a system equals the maximum amount of isothermal work D.. hence. The internal energy UT also decreases..TS. or (Af .. (10. but the decrease D.

This is a particularly important result in connection with processes involving a change of phase. and vaporization take place isothermally and isobarically. g". so the volume and the entropy may then be calculated by the partial differentiations: (8G) T= V 8P and G and (10. At the triple point. .CHAPTER 10: Mathematical Methods 259 dA = -PdV . = const. fusion. respectively. the equation of the vaporization curve is e" = «".9) as the last Legendre transformation. the Gibbs function of the system remains constant. dG=O. the pressure and the entropy may be calculated by performing the partial differentiations: (8A) =_P 8V T and (10.27) All the other thermodynamic variables can be calculated by differentiating the Helmholtz function.SdT. T) was introduced in Eq. dG = V dP . and saturated vapor. For an infinitesimal reversible process. the molar Gibbs functions of a saturated solid.TS.S dT. two equations hold simultaneously. namely. (10. that is.29) All the g's can be regarded as functions of P and T only.29) serves to determine the P and T of the triple point uniquely. and the equation of the sublimation curve is g'=g"'. during such processes. (10. saturated liquid. (10. If we denote by the symbols s'. Hence. g' = s" = g"'. and s". then the equation of the fusion curve is g'=g". Sublimation. as shown in one of the problems at the end of the chapter.28) In the case of a reversible isothemal and isobaric process. G=H . and hence Eq. The Gibbs function G(P.

) Considering y to be a function off y df + (~. Thus. since chemical reactions begin and end at the same equilibrium atmospheric pressure and ambient temperature. and N with respect to x. thenf may be regarded as a function of any two of x. and z. we get and Since the two second derivatives of the right-hand terms are equal. and z. Substituting this expression for dy in the preceding equation. y. and N are all functions of x and y. and z may be considered to be a function off and one other of x. and z. If a quantity f is a function of x.260 PART I: Fundamental Concepts The Gibbs function is extremely important in chemistry. y. and z. and z. y. and it applies to all four characteristic functions.ox (oz) y and then dz = Mdx+Ndy. regarding x to be a function off and y. dy = (~. M. dz = (~:) If we let M_ y dx + (~. y.) f dy. Partially differentiating M with respect to y. If a relation exists among x.30) This is known as the condition for an exact differential. and a relation exists among x. THEOREM 2. . dx = (~. whence. then we may imagine z expressed as a function of x and y. Similarly. y. we get .) z df + (:) f dz. where z. 10.) x dy.4 TWO MATHEMATICAL THEOREMS THEOREM 1. y. and z. anyone of x. it follows that (10.

31) is not the same as Eq.32) 10. (10. we obtain (10. Since U. Equate the dz terms of the last two equations to obtain (~. (10.6).CHAPTER 10: Mathematical Methods 261 But. and N are all functions of x and y.31) Notice that Eq. where z.5 MAXWELL'S RELATIONS We have seen that the hydrostatic properties of a pure substance are conveniently represented in terms of the differentials of any of these four functions: dU = -PdV + TdS. H.30). and G are actual functions. which is an expression involving three variables instead of four variables. their differentials are exact differentials of the type dz = M dx + N dy.S dT. (10. dG = V dP . dA. to the four exact differentials dU. and dG to obtain: . Equating the df terms. (2. Apply Eq. dH.SdT. the condition for an exact differential. dH= VdP+TdS. (ox) f (Oy) f (OZ) f _ oy OZ ox - 1 . M. A.) f (iz) = (~~) / f that is. dA and = -PdV .

Konig who first published it. 4. hence. The differential of the characteristic function for a simple system always equals the sum of two terms that include the differential of . Of course. is called a Konig-Born diagram. volume. dA=-SdT-PdV. one can determine changes of entropy by quantities that can be measured. The four characteristic functions and associated Maxwell relations need to be remembered. O. because they provide relationships between measurable quantities and those which either cannot be measured or are difficult to measure. it should be noted that pressure. For example. A characteristic function is indicated at the midpoint of each side and its thermodynamic coordinates at the ends:'of the side. named after Max Born whose students popularized it and F. Maxwell's relations are enormously useful. namely. then (aV /aT)p is positive and the derivative (as/ aph is negative. By using the Maxwell relations. If the pressure on a substance is increased isothermally and if no unusual molecular rearrangements take place (such as association or dissociation). (~~)T= -(~~t (:~t (10. 10-4. A useful mnemonic device for this purpose. the Helmholtz function A is a function of thermodynamic coordinates V and T. and temperature can be measured by experimental techniques. hence. 3. our knowledge about these molecules is increased. according to microscopic theory. therefore. (~~) s = -(~~t 2. in a more orderly state. The square is also referred to as a VAT. may be combined with the volume expansivity (3 of a pure substance in order to provide information concerning the statistical interpretation of entropy in the following way. V. These equations do not refer to a process but express relations that hold at any equilibrium state of a hydrostatic system. So. and T in a hydrostatic system.262 PART I: Fundamental Concepts 1. and the internal-energy function U is a function of thermodynamic coordinates V and S. for example. the molecules experience a decrease in entropy and are. dU = TdS . P. (~~).33) The four equations on the right are known as Maxwell's relations. dH = T dS+ V dP. (:~)T= VdP. In other words. dG= -SdT+ = (~~t hence. which is shown in Fig. In particular.PdV.VUS diagram because of the labels on the top and left side. hence. whereas entropy cannot be determined experimentally. If a substance has a positive expansivity. the fourth Maxwell relation. the reciprocals of Maxwell's relations are also valid equations.

it follows that T(~:) v = Cv. thus.VUS diagram is modified for other simple systems by replacing P and V by the appropriate intensive and extensive variables in the new system. . The differential dU equals the sum of terms including dV and dS.30) to each of the four thermodynamic potential functions. 10. a mnemonic device for s H P writing the differential forms of the four thermodynamic potentials. except that P is replaced by the negative of the intensive variable. the thermodynamic coordinates. (10. The coefficient of dV is found by the arrow that connects V to P. the coefficient of dS is found by going in the direction of the arrow that connects S to T. The coefficient of the differential in each term is found by connecting the arrow from the thermodynamic coordinate of the differential to its conjugate coordinate across the VAT. Consider.VUS diagram. for example. And. Notice that the connection goes against the arrow. dS and Since T dS = = (as) dT aT v aT v + (as) av + T(as) dV T ' dV.CHAPTER 10: Mathematical Methods 263 v A T u G FIGURE 10-4 The VAT. S). from Maxwell's third relation. T dS = T(as) dT av T dQ for a reversible isochoric process.6 T dS EQUATIONS The entropy of a pure substance can be considered as a function of any two variables. The VAT. The Maxwell relations are obtained by applying Eq.VUS diagram. but =P. so the coefficient of dV is not P. Similarly. the internal-energy function U( V. such as T and V.

T dS = T(8S) 8T p dT p + T(8S) 8P T dP. Using the molar van der Waals equation of state. (10.. .) /v. Imol of a van der Waals gas undergoes a reversible isothermal expansion from an initial molar volume Vi to a final molar volume How much heat has been transferred? For 1 mol. and Cv indicate molar quantities. (10.34) vi- We shall call Eq. Therefore. finally. = where s. then. Cv Tds = cvdT + RT --b. And. r dS=(.~)/P. Since T is constant. and.:)/T+ (. dv v- dT = 0. A second dS equation can be derived if the entropy of a pure substance is regarded as a function of T and P. and hence. It is useful in a variety of ways. q = IT ds. Tds cvdT + T(. q = RT and.34) the first TdS equation. q I v! Vi ---=-b ' V dv = RTln Vf Vi _ b b. For example. from Maxwell's fourth relation. and But. T(!:) = c-. V. since the process is reversible.264 PART I: Fundamental Concepts therefore.

as the pressure is increased from zero to a thousand times atmospheric pressure at room temperature. V=2 xI0-sm3. Reversible isothermal change of pressure.andPj = 1. and the volume expansivity changes about 4 percent. In the case of a solid or liquid.t. We then have ! Q or = -TV{3 P! J Pi dP.01 x 1Q8Pa. for a substance with a negative expansivity (such as water between 0 and 4°C. If the pressure on 15 cm ' of mercury at 20°C is increased reversibly and isothermally from 0 to 1000 atm. V and {3 are assumed to be constant and are brought in front of the integral sign. we obtain Q = -T which can be integrated when the dependence of V and {3 on the pressure is known. Two important applications of the second T dS equation follow. which is more useful than the first T dS equation because the partial derivative holds pressure constant rather than volume constant. Q = -T J(~. and TdS=-T(~. neither V nor {3 is very sensitive to a change in pressure. therefore. in the case of mercury. J V{3dP.35) is the second TdS equation.tdP. Q = -TV{3(Pj - PJ It is seen from this result that.{3= 1. For example. the volume of 1 mol of mercury changes only percent. When T is constant. Hence. heat will flow out if {3 is positive but that. whereT=293K. .81 x 10-4K-1. as the pressure is increased isothermally. the heat transferred will be approximately Q ~ -TV{3Pj. 1.CHAPTER 10: Mathematical Methods 265 thus. (10. The volume and the expansivity of most solids and liquids behave similarly.) /P (i= Remembering that the volume expansivity is ~(~.35) Equation (10. or a rubber band). an isothermal increase of pressure causes an absorption of heat. A third T dS equation for hydrostatic systems will be found among the problems at the end of the chapter.

3J.07J.3J of heat flows from the system but only 3.PdP. Therefore. The isothermal compressibility is also fairly insensitive sure. In the foregoing example.p2 r: rv pf) For example. Therefore. K.01 = -80. at constant temperature. which has changed by an amount b.p} X 10-11 Pa-I for mercury. In other words. The isothermal compressibility of mercury at room about 2 percent as the pressure is increased from zero atmospheric pressure.2 K. + 3. 80. taking K.3J of heat leaves the system in order to hold the temperature constant as the pressure is increased by an enormous amount.07J of work is performed on the system! The extra amount of energy in the form of heat comes. by constant w = ~VK. of course. we get = ~(1.(p} IV .01 x 108 Pa)2 = 3. = -(ljV)(8V W= we get J P! Pi VK. = 4.01 W = ~VK. we may again replace values and obtain to a change of prestemperature changes to a thousand times V and K.3N·m = 108 Pa) -80. if the pressure is increased from 0 to 1000atm during a compression of 15cm' of mercury maintained at 20oe.U= Q+ W = -80. Recalling the isothermal compressibility.5 X 10-5 m') (4.2J. w~ - J(~~)/dP j8Ph. from the store of internal energy.266 PART I: Fundamental Concepts X Q = -(293 K)(1.3J = -77.5 x 10-5 m3)(1. It is interesting to compare the heat liberated by the system with the work done on the system during the compression. is always a positive quantity.01 x 10-11 Pa-1) (1.1J Whereas isothermal compressibility K. then 80. w=and.81 x 10-4 K-I )(1. j3 is . it is seen that. JPdV. volume expansivity j3 may be positive or negative.

T = C (Pf .T(~~) pdf. 2. be written TV{3 D. then the adiabatic increase of pressure would have produced a decrease in temperature. even for an increase of 10.4.7 INTERNAL-ENERGY EQUATIONS If a pure substance undergoes an infinitesimal reversible process between two equilibrium states. 0 10.81 139J/kg·K 2. Cp In the case of a solid or liquid. an increase of pressure of as much as 1000 atm produces only a small temperature change. may. The equation above. p It is clear from the discussion above that a reversible adiabatic increase of pressure will produce an increase of temperature in any substance with a positive expansivity.Pi). thereby eliminating the effect of work being performed. TdS or dT =0 = c-ur .000 atm. the change of internal energy is . dP p = _!__ c.38 x 10-5 m3/kg)(1.38 X 10-5 m3/kg) at 20°C is increased isentropically from 0 to 1000 atm. Since the entropy remains constant in this process. 2. Reversible adiabatic change of pressure. when applied to a solid or a liquid.CHAPTER 10: Mathematical Methods 267 positive and heat flows out of the system during compression.01 X 108 Pa) In Sec. If the system were a substance with negative {3. heat is absorbed by the system and the internal energy is increased. Also. the temperature change will be approximately Tv{3 D. x 10-4 K- 1 ) (1. The discrepancy in results arises because the earlier calculation was done at constant volume.84K. if the pressure on 15 em:' of mercury (specific heat Cp = 139 J/kg· K and specific volume v = 7.T~-Pf Cp = = (293 K)(7. therefore. For a substance with a negative expansivity (3. For example. experiment shows that Cp hardly changes. the inverse of this example found that a 10 e change in the temperature of mercury requires approximately 450 atm of pressure. and a decrease in temperature in a substance with a negative expansivity. or (av) = TV{3 dP.

. and u = J Cv dT . 2.~) P. but is a function of only T in an ideal gas. U does not depend on V.~ + const. If T is held constant. Two examples of its usefulness follow. T T- Using Maxwell's third relation. Although holding the volume constant is difficult in an experiment. (8Sj8Vh = (8Pj8T)v.2 v-b v' and Consequently. we get = TdS . S. with the temperature remaining constant. It follows. therefore. and (=~)= T(. Van der Waals gas (1 mol): RT 1 P=---. that the internal energy of a van der Waals gas increases as the volume increases.PdV. we get (10. Ideal gas: . 1.36) We shall call this equation the first internal-energy equation. Therefore. dU = T dS_p dV dV ' where U. it is straightforward in an equation of state. then the derivatives become partial derivatives.:«: V' =T nR V' and (8U) 8V nR V T -p=o. and P are regarded as functions of T and V.268 PART r: Fundamental Concepts dU Dividing by dV.

(l0. We start with Eq.4).37) which is the second internal-energy equation. 10. If T is held constant. dU = TdS . c-ur - T(~~)/P Cp - = c. dT = T(~. S. Therefore.)/V. dU _ T dS dP dP-P dV dP' of internal where U.) v dV + T(~~) PdP. then the derivatives become partial derivatives. and V are regarded as functions of T and P.8 HEAT-CAPACITY EQUATIONS Equating the first and second T dS equations.C ' v and fJT) = ( fJP v T(~~)r c--:c.PdV.CHAPTER 10: Mathematical Methods 269 The second internal-energy equation shows the dependence energy on pressure. Cv and solving for dT. and Using Maxwell's fourth relation. and divide by dP. we obtain But. dT=(~~tdV+(~~tdP T(~.at + T(~.)v Cv Cp - fJT) _ ( fJV p. (fJS/fJPh = -(fJV/fJT)p. Both of the foregoing equations yield the result that . Then.Cp . we get (10.

39) .It would be extremely difficult to measure. that (8P) p aT v . and. C» ---+ Cv. Cp-Cv=-T 8V)2 (8P) ( aT p 8V T· (10. T (10. 2. (10. The equation for the difference in the specific heats is very useful in calculating Cv in terms of Cp and other measurable quantities. Remembering that volume expansivity is I (8V) (3 = V 8T and isothermal compressibility is K p' = _2_ V (av) ap T . the two heat capacities are equal. or.38) in the form TV[~(~)J Cp . 1. the temperature at which the density of water is a maximum. at 4°C. Values of cv.38) and it shows Equation (10. or Cp can never be less than C v . we may write Eq. therefore. with any degree of accuracy. Since (8P/8V)T is always negative for all known substances and (8V /8T)~ must be positive.Cv = _2_ (8V) 8P Tv(32 K V or cp-cv=P--. Laboratory measurements of the heat capacity of solids and liquids usually take place at constant pressure and for unit mass. must be known for purposes of comparison with theory. by Eq. therefore. however. Cp = Cv. Cp = Cv when (8V /8T)p = O. and. Cv of a solid or liquid. data are reported in terms of specific heat cr. For example. at absolute zero.Cv can never be negative. because of thermal expansion. then Cp .6). (2.38) is an important that: equation in thermodynamics. As T ---+ 0. 3.270 PART r: Fundamental Concepts C» _ Cv = T(8V) 8T It was shown.

3 J /kg K.CHAPTER 10: Mathematical Methods 271 where v is the specific volume.7 J/kg·K. let us calculate the specific heat at constant volume of mercury at 20 e and atmospheric pressure.40) But. we obtain cpdTs = T(~~) /Ps. the quantity in brackets is equal to -(oV /OP)T.01 X 10-11 Pa-1.) /Vs.38 X 10-5 m3/kg. . K . Cv = cr - [(OV /OT)p] (OP) (oP/oT)v oV s Therefore. we have cr = 139J/kg· K. Finally. f3 = 1. (10. ds and At constant S.Cv = = k (293K)(7. D 139 J / g. cvdTs = -T(~. As another example. T = 293 K.15.T(~~t dP.41) and. the ratio of specific heats 'Y is 'Y =Cv Cp = 121 .39) was used in Sec. From experiment. The two T dS equations for specific heats are T = cpdT. as usual. Equation (10. Cp Cv (oP/oV)s (oP/oVh· The isentropic compressibility is defined as KS = . x lO-sm3/kg)(1.8 to calculate Cv of crystalline solids. 9. K = 1. and /'i.81 X 10-4 K-1.81 4. Hence. = 4.01 X 10-11 Pa-1 x 10-4K-1)2 and Cv = 121.~ (~~) ~ s' (10. and Dividing. the isothermal compressibility is given by K= (~~t We have.3 J /k 139J/kg·K g. therefore. v = 7.38 17.

for an ideal gas: (a) (b) (c) A = J Cv dT .T J G = i dT . in contrast to equilibrium thermodynamics presented in this book.2.T J i dT + nRTlnP - const. 10. 10. S). entropy S. Another set of characteristic functions for a single-substance system can be defined by performing the Legendre transformations on the entropy S(U. oT v oT v Cv = -T(:T~) v· H = G _ T(OG) = _T2 [O(G/T)] oT oT C = -T(:T~) U= p p p.42) /'i. derive the remaining three by using only the relations: and (ox) (OY) (oz) =-1 oY OZ ox (ox) f (OY) f (Oz) f = + 1. internal energy U. Derive the following equations: (a) (b) (c) (d) A(T. volume expansivity (3. V) rather than on the internal energy U(V. heat capacity at constant pressure Cp.4.=-=-. Show that. _T(OA) = _T2 [O(A/T)] . .nRTln V J c-ar . as was done for NaCl in Table 9.272 PART I: Fundamental Concepts .s from which values of ss may be calculated. The thermodynamic potentials turn out to be particularly useful in statistical mechanics and the theory of irreversible thermodynamics. PROBLEMS 10. heat capacity at constant volume Cv. 10. Starting with the first Maxwell relation. 10..5. oy OZ ox z x y . (10.5. T + const. derive expressions for pressure P. and isothermal compressibility /'1.3. Apply the above equations to 1mol of an ideal gas. p (Gibbs-Helmholtz equation). Cv Cp /'i. const. T + const.1. From the differential equation for the thermodynamic potential V).

PIT). 10. V) that produces the thermodynamic potential Y(lIT.7. demonstrate reversible heat QR is not a thermodynamic property. dP (3 K.) (a) How much heat is transferred during the compression? (b) How much work is done during the compression? (c) Determine the change of internal energy. (Take the density p = 8. 10. is given by the transform U J=-T+S=-T' and dJ A P = U T2 dT + TdV. Derive the third T dS equation. (10.10. (Numerical values are given in Table 9. From the fact that dV I V is an exact differential. V) that produces the characteristic function J(lIT. By invoking the condition for an exact differential. 10.5 X 10-6 K-1.9.2 kg of water is increased reversibly and isothermally from atmospheric pressure to 3 x 108 Pa at 20°C. and specific heat cr = 385 J/kg· K to be constant.) (a) How much heat is transferred? . T2 V T derive the relation G 10.CHAPTER 10: Mathematical Methods 273 (a) Show that Legendre transformation of S(U. = 6.96 X 103 kg/m". Eq. V). TdS = Cv(~~) vdP+ Cp(~~) pdV. known as the Planck junction. is defined by the transform H Y=-T+S=-T' and H dY=-dT--dP. p C + (3V dV . The pressure on 0.sr : = CvK. The pressure on 500 g of copper is increased reversibly and isothermally from 0 to 5000 atm at 298 K.18 X 10-12 Pa-1. that the and show that the three T dS equations may be written as follows: (a) (b) (c) TdS=CvdT+(3Tdv. TdS= T dS c. known as the Massieu function. V(3TdP. (b) Show that Legendre transformation of J(lIT.6. volume expansivity (3 = 49. (d) What would have been the rise of temperature if the copper had been subjected to a reversible adiabatic compression? 10.6. isothermal compressibility K.30).8.

(c) A relation that holds during an adiabatic process is P(v . (a) Using the virial expansion Pv = RT(l + BP+ Cp2 + . and A may be written dU = (Cp .0000 1.PV(3)dT + V(KP .16. 10.217 4. an equation for an adiabatic process is T(v .181 Cp. 10. calculate (8u/8vh and its limit as P -t O. (c) In the case of a gas obeying the equation of state .0121 p. 5.b) = RT. dH = CpdT and 10. (c) Using parts (a) and (b). The pressure on 1g of water is increased from 0 to 108 Pa reversibly and adiabati- cally.. 10. Show that: (a) u is a function of T only.b)R/CV = const.15.2.11.) 10. °C 0 5 50 Specific volume v.12. 10. H. Derive the equation (8CV) 8V = T(82~) T 8T v . A gas obeys the equation P(v .f3T)dP.b) = RT.14.274 PART I: Fundamental Concepts (b) (c) How much work is done? Calculate the change in internal energy.. with Cv a function of T only.) calculate (8u/ 8Ph and its limit as P -t O.f3T)dP. calculate (8P/8vh and its limit as P -t o.202 4.13 Show that for a gas obeying the van der Waals equation (P + a/v2) (v . (b) Using the same expansion. (a) dA = -(PVf3 + V(l.0002 1. to-3m3/kg 1.b)'Y = const. where b is constant and Cv is constant. Calculate the temperature change when the initial temperature and other variables have the different values given in the three cases below: ~F-lJlffia~~"fMt i flU! &iWJG$iilWiI Temperature. (b) 'Y is constant. 10-6 K-1 -68 +16 +458 103 J/kg·K 4. (Compare the solution with the results of Rossini and Frandsen given in Sec. Show that the differentials of the three thermodynamic potentials U. + S)dT + PVKdP. (b) Prove that Cv of an ideal gas is a function of T only.

Derive the following equations: (a) (b) (e) ell -. compiled by Gladun."y .1S.14 1. kg/m' 1240 1206 1170 lO-2K-1 1.9 II 3. (0) Derive the equation (aa~)T=-T(~. d2B dT2P+(cP)o.24 6.12 2. is a function of T only.8 10 3.06 4.40 37 39 41 42 2.17. Calculate the plot against temperature: (0) ev. In the accompanying table are listed the thermal properties of liquid neon. 10. 25 27 29 1.33 P.) (b) p' (e) prove that C» of an ideal gas is a function of T only. In the case of a gas obeying the equation of state Pv = RT+BP. K p.79 31 33 35 1131 1089 1042 992 1.86 1. show that ev = RT --v dT2 (BT) + (cv)o.63 1.04 2.4 6.18 2. 111:.19.62 0. where (cv)o is the value at very large volumes.43 ur J/kg· K L81 Cp.36 2.63 4.94 2.96 7.03 1.84 0. T. 10. 10-8 Pa-I 0.07 43 18 26 10.50 0._r(ap) (av) er sr (~~)s=-d. (b) «s. show that cp=-T where (ep)o is the value at very low pressures.46 1. where B is a function of T only.93 932 754 859 813 4.52 3.04 2. and (e) "y.' v s' (8Vj8T)s (BV j8T)p I 1 .CHAPTER 10: Mathematical Methods 275 PV_t where B ur : d2 + v' f!.

(ap/aT)s (ap/aT)v 10.1). How much heating is required? (Take the volume expansivity f3 = 1.) 0 . = ap) ( aT T(av) aT Cp p (ap) aT s .20.22. = 3. The temperature of 1kg of mercury at 20 e is increased by soe under conditions of constant volume. specific heat at constant pressure Cp = 139Jjkg· K.276 PART I: Fundamental Concepts 10. Show that TJ = __ 1 (f3T _ '" (b) A measure of the result of the Joule-Thomson expansion (adiabatic throttling process or isenthalpic expansion) is provided by the Joule. = C (f3T .81 X 10-4 K-1. (a) A measure of the result of an adiabatic Joule free expansion is provided by the Joule coefficient TJ = (aT /av)u.Thomson coefficient /-l = (aT /ap)H.94 X 10-11 Pa-I to be constant. Show that /-l Cv p) . s = Vf3T· .21. "t>: 1 . isothermal compressibility". Derive the following equations: (a) (b) (c) c. p V 10.

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