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    Chapter 3 Termo

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    Maman Gocek

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    Chapter 3 Volumetric Properties of Pure Fluids ‘The equations of the preceding chapter provide the means for calculation of the heat and work quantities associated with various processes, but they are useless without knowledge of property values for internal energy or enthalpy. Such properties differ from one substance to ‘another, and the laws of thermodynamics themselves do not provide any description or model ‘of material behavior, Property values come from experiment, or from the correlated results of experiment, or from models grounded in and validated by experiment. Because there are no internal-energy or enthalpy meters, indirect measurement is the rule. For fluids, the most com- prehensive procedure requires measurements of molar volume in relation to temperature and pressure. The resulting pressure/volume/temperature (PVT) data are most usefully correlated by equations of state, through which molar volume (or density), temperature, and pressure are functionally related, In this chapter we: + Present the phase rule, which relates the number of independent variables required to fix the thermodynamic state of a system tothe number of chemical species and phases present + Describe qualitatively the general nature of PVT behavior of pure substances + Provide a detailed treatment of the ideal-gas state + Treat equations of state, which are mathematical formulations ofthe PVT behavior of fluids + Introduce generalized correlations that allow prediction of the PVT behavior of fluids for which experimental data are lacking 3.1 THE PHASE RULE As indicated in Section 2.5, the state of a pure homogeneous fluid is fixed whenever two intensive thermodynamic properties are set at specific values. In contrast, when wo phases of the same pure species are in equilibrium, the state of the system is fixed when only a sin tele property is specified, For example, a system of steam and liquid water in equilibrium at 68 3.1. The Phase Rule 6 101.33 kPa can exist only at 100°C. It is impossible to change the temperature without also changing the pressure, if equilibrium between vapor and liquid phases is to be maintained. ‘There is a single independent variable For @ multiphase system at equilibrium, the number of independent variables that must be arbitrarily fixed to establish its intensive state is called the number of degrees of freedom of the system. This number is given by the phase rule of J. Willard Gibbs." It is presented here ‘without proof in the form applicable to nonreacting systems:? Fal-atN B.) ‘where F is the number of degrees of freedom, a is the number of phases, and Nis the number of chemical species present in the system. ‘The intensive state ofa system at equilibrium is established when its temperature, pressure, and the compositions of all phases are fixed, These are the variables of the phase rule, but they ‘are nol all independent, The phase rule gives the number of variables from this set that must be specified to fix all remaining intensive variables, and thus the intensive state of the system. ‘A phase is a homogeneous region of matter, A gas or a mixture of gases, a liquid or a liquid solution, and a crystalline solid are examples of phases, An abrupt change in properties always occurs at the boundary between phases. Various phases can coexist, but they must bbe in equilibrium for the phase rule to apply. A phase need not be continuous; examples of discontinuous phases are & gas dispersed as bubbles in a liquid, a liquid dispersed as droplets, in another liquid with which itis immiscible, and solid crystals dispersed in either a gas or a liquid. In each case a dispersed phase is distributed throughout a continuous phase, ‘As an example, the phase rule may be applied to an aqueous solution of ethanol in equi- librium with its vapor. Here = 2, # = 2, and —84N=2-24 2 ‘This is a system in vaporfiquid equilibrium, and it has two degrees of freedom, Ifthe system cexists at specified T and P (assuming this is possible), its liquid- and vapor phase composi: tions are fixed by these conditions. A more common specification is of T and the liquid-phase ‘composition, in which case P and the vapor-phase composition are fixed Intensive variables are independent of the size of the system and of the individual phases. Tus, the phase rule gives the same information for a large system as for a small one ‘and for different relative amounts of the phases. Moreover, the phase rule applies only to individual-phase compositions, and not to the overall composition of a multiphase system, Note also that for a phase only N~ 1 compositions are independent, because the mole or mass fractions of a phase must sum to unity ‘The minimum number of degrees of freedom for any system is zero, When F = 0, the system is invariant; Eq. (3.1) becomes « = 2 +N, This value of zis the maximum number of phases that can coexist at equilibrium for a system containing N chemical species. When 1, this limit is reached for # = 3, characteristic ofa triple point (Sec. 3.2). For example, the ‘Yosah Willard Gibbs (1839-190), American mathematical physics, who deduced iin 1975, See pen. wiki pediaorgwiki Willard Gibbs he theortcal justification ofthe phase reacting ystems is considered in See. 148, for nonreacting systems is given in Sec. 12.2, nd the phase rule for 70. CHAPTER 3. Volumetric Properties of Pure Fluids triple point of HO, where liquid, vapor, and the common form of ice exist together in equilib rium, occurs at 0.01°C and 0.0061 bar. Any change from these conditions causes at least one phase to disappear. Example 3.1 How many phase-rule variables must be specified to fix the thermodynamic state of each of te following systems? (0) Liquid water in equilibrium with its vapor (6) Liquid water in equilibrium with a mixture of water vapor and nitrogen (c) A three-phase system of a saturated aqueous salt solution at its boiling point with excess salt crystals present. Solution 3.1 (@ The system contains a single chemical species existing as two phases (one liquid and one vapor), and Fo2-a+N -241=1 ‘This result is in agreement with the fact that for a given pressure water has but one boiling point. Temperature or pressure, but not both, may be specified fora system comprised of water in equilibrium with its vapor. (b) Two chemical species are present. Again there are two phases, and F satN=2-242=2 ‘The addition of an inert gas to a system of water in equilibrium with its vapor changes the characteristics of the system, Now temperature and pressure may be independently varied, but once they are fixed the system described can exist in equilibrium only at a particular composition of the vapor phase. (If nitrogen is considered negligibly soluble in water, the liquid phase is pure water.) (©) The three phases (jr = 3) are crystalline salt, the saturated aqueous solution, and vapor generated at the boiling point. The two chemical species (= 2) are water and salt, For this system, F=2-3 425 3.2 PVT BEHAVIOR OF PURE SUBSTANCES Figure 3.1 displays the equilibrium conditions of P and T’at which solid, liquid, and gas phases of a pure substance exist, Lines 1-2 and 2-C represent the conditions at which solid and lig uid phases exist in equilibrium with a vapor phase. These vapor pressure versus temperature 3.2. PVT Behavior of Pure Substances n lines describe states of solid/vapor (line 1-2) and liquid/vapor (line 2-C) equilibrium. As indicated in Ex. 3.1(@), such systems have but a single degree of freedom. Similarly, solid/liquid equilibrium is represented by line 2-3. The three lines display conditions of P and T at which two phases may coexist, and they divide the diagram into single-phase regions, Line 1-2, the sublimation curve, separates the solid and gas regions; line 2-3, the fusion curve, separates the solid and liquid regions; line 2-C, the vaporization curve, separates the liquid and gas Tegions. Point Cis known as the critical point; its coordinates P, and T. are the highest pressure and highest temperature at which a pure chemical species is observed to exist in vapotfiquid equilibrium. The positive slope of the fusion line 2-3) represents the behavior of the vast majority of substances. Water, a very common substance, has some very uncommon properties, and exhibits a fusion line with negative slope. The three lines meet at the triple point, where the three phases coexist in equilibrium. ‘According tothe phase rule the tiple point is invariant (F = 0). Ifthe system exists along any of the two-phase lines of Fig. 3.1, itis univariant (F = 1), whereas in the single-phase regions it is divariant (F = 2). Invariant, univariant, and divariant states appear as points, curves, and areas, respectively, on a PT diagram. Changes of state can be represented by lines on the PT diagram: a constant-T change by a vertical line, and a constant-P change by a horizontal line. When such a line crosses phase boundary, an abrupt change in properties of the fluid occurs at constant T and P; for example, vaporization for the transition from liquid to vapor, resoneme) Uieson Pressure Figure 31: PT diagram for a pure substance. sora tesion 2° pot egion Ssuntmaton Temperature ‘Water in an open flask is obviously a liquid in contact with ait. Ifthe flask is sealed and the air is pumped out, water vaporizes to replace the air, and HzO fills the flask. Though the pressure in the flask is much reduced, everything appears unchanged. The liquid water resides at the bottom of the flask because its density is much greater than that of water vapor (steam), and the two phases are in equilibrium at conditions represented by a point on curve 2-C of Fig. 3.1, Far from point C, the properties of liquid and vapor are very different. However, if n CHAPTER 3. Volumetric Properties of Pure Fluids the temperature is raised so that the equilibrium state progresses upward along curve 2-C, the properties of the two phases become more and more nearly alike; at point C they become identical, and the meniscus disappears. One consequence is that transitions from liquid to ‘vapor may occur along paths that do not cross the vaporization curve 2-C, ic., from A to B. The transition from liquid to gas is gradual and does not include the usual vaporization step. ‘The region existing at temperatures and pressures greater than T, and P. is marked off by dashed lines in Fig. 3.1; these do not represent phase boundaries, but rather are limits fixed by the meanings accorded the words liquid and gas. A phase is generally considered a liquid if vaporization results from pressure reduction at constant temperature. A phase is considered 4 gas if condensation results from temperature reduction at constant pressure. Since neither process can be initiated in the region beyond the dashed lines, i is called the fluid region. ‘The gas region is sometimes divided into two parts, as indicated by the dotted vertical line of Fig. 3.1. A gas to the left of this line, which can be condensed cither by compression at ‘constant temperature or by cooling at constant pressure, is called a vapor. A fluid existing at a temperature greater than 7, is said to be supercritical, An example is atmospheric ai. PV Diagram Figure 3.1 docs not provide any information about volume; it merely displays the bounds- ries between single-phase regions. On a PV diagram (Fig. 3.2(a)] these boundaries in turn become regions where two phases—solidiiquid, solid/vapor, and liquid/vapor—coexist in equilibrium, The curves that outline these two-phase regions represent single phases that are in equilibrium. Their relative amounts determine the molar (or specific) volumes within the two-phase regions. The triple point of Fig. 3.1 here becomes a triple line, where the three phases with different values of V coexist ata single temperature and pressure. Figure 3.2(a), like Fig. 3.1, represents the behavior of the vast majority of substances, Wherein the transition from liquid to solid (freezing) is accompanied by a decrease in specific ‘volume (increase in density), and the solid phase sinks in the liquid. Here again water dis- plays unusual behavior in that freezing results in an inerease in specific volume (decrease in density), and on Fig. 3.2(a) the lines labeled solid and liquid are interchanged for water. Tee therefore floats on liquid water. Were it not so, the conditions on the earths surface would be vastly different Figure 3.2(b) is an expanded view of the liquid, iquid/vapor, and vapor regions of the ‘PV diagram, with four isotherms (paths of constant 7) superimposed, Isotherms on Fig. 3.1 ‘are vertical lines, and at temperatures greater than T do not cross a phase boundary. On Fig. 3.2(b) the isotherm labeled T > T, is therefore smooth, The lines labeled 7; and T; are for subcritical temperatures and consist of three seg ments. The horizontal segment of each isotherm represents all possible mixtures of liquid and vapor in equilibrium, ranging from 100% liquid atthe left end to 100% vapor atthe right end, ‘The locus of these end points is the dome-shaped curve labeled BCD, the left half of which (from B to C) represents single-phase liquids at their vaporization (boiling) temperatures and ‘the right half (from C to D) single-phase vapors at their condensation temperatures. Liquids ‘and vapors represented by BCD are said to be saturated, and cocxisting phases are connected by the horizontal segment ofthe isotherm at the saturation pressure specific to the isotherm, Aso called the vapor pressure, itis given by a point on Fig, 3.1 where an isotherm (vertical Tine) crosses the vaporization curve. 3.2. PVT Behavior of Pure Substances B v v @ ® Figure 3.2: PV diagrams fora pure substance. (a) Showing solid, liquid, and gas regions (6) Showing liquid, liquidivapor, and vapor regions with isotherms. ‘The two-phase liquid/vapor region lies under dome BCD; the subcooled-liquid region lies to the left of the saturated-liquid curve BC, and the superheated-vapor region lies to the right of the saturated-vapor curve CD. Subcooled liquid exists at temperatures below, and superheated vapor, at temperatures above the boiling point for the given pressure. Isotherms in the subcooled-liquid region are very steep because liquid volumes change little with large c’changes in pressure. ‘The horizontal segments of the isotherms in the two-phase region become progressively shorter at higher temperatures, being ultimately reduced to a point at C. Thus, the critical iso therm, labeled 7, exhibits a horizontal inflection atthe critical point C at the top of the dome, where the liquid and vapor phases become indistinguishable. Critical Behavior Insight into the nature of the critical point is gained from a description of the changes that ‘occur when a pure substance is heated in a scaled upright tube of constant volume. The dotted vertical lines of Fig. 32(b) indicate such processes. They may also be traced on the PT diagram of Fig. 3.3, where the solid line is the vaporization curve (Fig. 3.1), and the dashed lines are constant-volume paths in the single-phase regions. If the tube is filled with either liquid or ‘vapor, the heating process produces changes that lie along the dashed lines of Fig. 3.3, for ‘example, by the change from E to F (subcooled-liquid) and by the change from G to Hf (super- heated-vapor). The corresponding vertical lines on Fig. 3,2(b) are not shown, but they lie to the left and right of BCD respectively. Ifthe tube is only partially filled with liquid (the remainder being vapor in equilibrium with the liquid), heating at first causes changes described by the vapor-pressure curve (solid 14 CHAPTER 3. Volumetric Properties of Pure Fluids guia Figure 3.3: PT diagram for a pure fluid showing the vapor pressure curve and constant-volume lines in the single-phase regions. line of Fig. 3.3). For the process indicated by line JQ on Fig. 3.2(6), the meniscus is intially near the top ofthe tube (point J), and the liquid expands sufficiently upon heating to fill the tube (point Q). On Fig. 3.3 the process traces a path from (J, K) to Q, and with further heating

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