81 picking up an additional 40 ppm of dissolved solids during passage through the equipment and return lines. The total solids concentration in the boiler must not exceed 3000 ppm. Therefore water of this concentration is continuously withdrawn, or “blown down.” The solids content of the liquid in the steam is the same as that of the liquid in the boiler. Compute the ratio of blowdown to treated-water feed required. 2.65. In the operation of a synthetic ammonia plant, an excess of hydrogen is burned with air so that the burner gas contains nitrogen and hydrogen in a 1:3 mole ratio and no oxygen. Argon is also present in the burner gas since it accounts for 0.94 percent of air. The burner gas is fed to a converter where a 25 percent con- version of the N2-H2 mixture to ammonia is produced. The ammonia formed is separated by condensation and the unconverted gases are recycled to the con- verter. To prevent accumulation of argon in the system, some of the unconverted gases are vented before being recycled to the converter. The upper limit of argon in the converter is to be 4.5 percent of the entering gases. What percentage of the original hydrogen is converted into ammonia? 2.66. A 50 percent NaCl solution is to be concentrated in a triple-effect evaporator as shown in Fig. P2.66. (Each individual evaporator is termed an effect.) An equal [7 Pe Condenser { 50,000 Ibs/hr 50% NaCl soln. 35,000 Ibs per hour product Steam Condensate Fig. P2.66. amount of water is evaporated in each effect. Determine the composition of the outlet stream from effect 2 if the internal contents of effect 2 are uniformly mixed so that the outlet stream has the same composition as the internal contents of effect 2. The steam lines in each effect are completely separate from the evaporator contents so that no mixing of the steam with the contents occurs. 2.67. In the extraction process shown in Fig. P2.67, a feed stream, designated A, containing 70 percent by weight of unwanted material, U, is extracted in a coun- tercurrent extraction system with the solvent, chlorex, C. One thousand pounds of A and 3000 lb of C are charged per hour. The paraffin oil, P, exits at one end of the system and the undesirable material exits from the other end. Associated with the paraffin oil, P, is 0.1 Ib of chlorex per pound of paraffin oil inthe product. The undesired material, U, at the other end of the apparatus will retain the remainder of the chlorex and in addition will retain 0.2 Ib of paraffin oil per pound of U (this paraffin oil is not recovered). (a) What weight of paraffin oil is recovered per hour?82 Exit Gos Lean Oil Scrubber Overhead Natural Gosaine Gos from wells Strigper eae [8 Cooter Bottoms, Fig. P2.63. 2.64, Raw water for use in a boiler has the following analysis in ppm (pounds per million pounds of pure water): Catt 90 Mg?* 60 Nat* and K* 40 HCO; 210 sO} and Cl- 160 Total solids 620 ppm Na3PO, is added in 10 percent excess above that required to form insoluble Ca3(PO.)2 and Mgs(PO.)2, which are allowed to settle out before the treated water is fed to the boiler. See Fig. P2.64. The reactions are complete, and no other reactions occur. The steam produced entrains 4 Ib of liquid per 1001b of dry steam. Sixty percent of this wet steam returns to the boiler as condensate after Non-returned Steam Row Water Process ising Equipment Treater mt Condensate Return Ca3(POale Blowdown Mg3(POa)2 Fig. P2.64.83 CHAPTER 3 In this chapter we shall first discuss ideal and real gas relationships includ- ing some of the gas laws for pure components and mixtures of ideal gases. You will learn about methods of expressing the p-V-T properties of real gases by means of equations of state and, alternatively, by compressibility factors. Next we shall introduce the concepts of vaporization, condensation, and vapor pres- sure and illustrate how material balances are made. 3.7 Ideal gas laws In 1787, Jacques Charles, a French chemist and physicist, published his conclu- sions about the relationship between the volume of gases and temperature. He demonstrated that the volume of a dry gas varies directly with temperature if the pressure remains constant. Charles, Boyle, Gay-Lussac, Dalton, and Amagat, the investigators who originally developed correlating relations among gas temperature, pressure, and volume, worked at temperatures and pressures such that the average distance between the molecules was great enough to neglect the effect of the intermolecular forces and the volume of the molecules them- selves. Under these conditions a gas came to be termed an ideal gas. More prop- erly, an ideal gas is an imaginary gas which obeys exactly certain simple laws such as the laws of Boyle, Charles, Dalton, and Amagat. No real gas obeys these laws exactly over all ranges of temperature and pressure, although the “lighter” gases (hydrogen, oxygen, air, etc.) under ordinary circumstances obey the ideal gas laws with but negligible deviations. The “heavier” gases such as sulfur dioxide and hydrocarbons, particularly at high pressures and low tem- peratures, deviate considerably from the ideal gas laws. Vapors, under conditions near the boiling point, deviate markedly from the ideal gas laws. However, at low pressures and high temperatures, the behavior of a vapor approaches that of an ideal gas. Thus for many engineering purposes, the ideal gas laws, if prop- erly applied, will give answers that are correct within a few percent or less. But for liquids and solids with the molecules compacted relatively close together, we do not have such general laws.84 The fact that a substance cannot exist as a gas at 32°F and 29.92 in. Hg is immaterial. Thus, as we shall see later, water vapor at 32°F cannot exist at a pressure greater than its saturation pressure of 0.18 in. Hg without condensation occurring. However, the imaginary volume at standard conditions can be cal- culated and is just as useful a quantity in the calculation of volume-mole rela~ tionships as though it could exist. In the following, the symbol V will stand for total volume, and the symbol for volume per mole, or per unit mass. EXAMPLE 3.1 Use of standard conditions Calculate the volume, in cubic feet, occupied by 88 1b of CO; at standard condi- tions. Solution: Basis: 88 1b CO; 88 Ib CO, | 1 1b mole CO,| 359 ft? CO, 441b CO, |i 1b mole CO; Notice how in this problem the information that 359 ft? at S.C. = 1 1b mole is applied to transform a known number of moles into an equivalent number of cubic feet. Incidentally, whenever you use cubic feet, you must establish the conditions of temperature and pressure at which the cubic feet are measured, since the term “it?,” standing alone, is really not any particular quantity of material. 718 ft CO, at S.C 3.1.1 Perfect Gas Law. Boyle found that the volume of a gas is in- versely proportional to the absolute pressure at constant temperature. Charles showed that, at constant pressure, the volume of a given mass of gas varies directly with the absolute temperature. From the work of Boyle and Charles scientists developed the relationship now called the perfect gas law (or sometimes the ideal gas law): pV =nRT .1) In applying this equation to a process going from an initial set of conditions to a final set of conditions, you can set up ratios of similar terms which are dimen- sionless as follows: (Er) - Ge) 02) Here the subscripts 1 and 2’refer to the initial and final conditions. This ar- rangement of the perfect gas law has the convenient feature that the pressures may be expressed in any system of units you choose, such as in. Hg, mm Hg, N/m?, atm, etc., so long as the same units are used for both conditions of pres- sure (do not forget that the pressure must be absolute pressure in*both cases). Similarly, the grouping together of the absolute temperature and the volume terms gives ratios that are dimensionless. '85 Let us see how we can use the perfect gas law both in the form of Eq. (3.2) and Eq. (3.1) EXAMPLE 3.2 Perfect gas law An oxygen cylinder used as a standby source of oxygen contains 1.000 ft? of O; at 70°F and 200 psig. What will be the volume of this O, ina dry-gas holder at 90°F and 4.00 in. HzO above atmospheric? The barometer reads 29.92 in. Hg. See Fig. in HO gouge | bias 70°F 215 psio Solution: You must first convert the temperatures and pressures into absolute units: 460 + 70 = 530°R 460 + 90 = 550°R atmospheric pressure = 29.92 in. Hg = std atm = 14.7 psia sae _ 200 psig + 14.7 psia | 29.92 in. Hg initial pressure = TET psi 4 in, H,0 | 29.92 in. Hg T2in, HO ]33.91 ft H,0 ft H,0 | = 29.92 + 0.29 = 30.21 in. Hg = 437 in. Hg final pressure = 29.92 in. Hg + The simplest way to proceed, now that the data are in good order, is to apply the laws of Charles and Boyle, and, in effect, to apply the perfect gas law. From Charles’ law, since the temperature increases, the volume increases; hence the ratio of the temperatures must be greater than 1. The pressure decreases; therefore from Boyle's law, the volume will increase; hence the ratio of pressures will be greater than 1. Basis: 1 ft? of oxygen at 70°F and 200 psig final volume = 1004? |550°R | 437 in. He na’ volume = 1530°R 130.21 in. He Sat 90°F and 4 in. H,O gauge = 15.086 Formally, the same calculation can be made using Eq. (3.2), v,(2)(B) since n, = m EXAMPLE 3.3 Perfect gas law Probably the most important constituent of the atmosphere that fluctuates is the water. Rainfall, evaporation, fog, and even lightning are associated with water as a vapor or a liquid in air. To obtain some feeling for how little water vapor there is at higher altitudes, calculate the mass of 1.00 m3 of water vapor at 15.5 mm Hg and 23°C. Assume that water vapor is an ideal gas under these conditions. Solution: First visualize the information available to you, and then decide how to convert it into the desired mass. If you can convert the original amount of water vapor to S.C. by use of the ideal gas law and then make use of the fact that 22.4 m? = 1 kg mole, you can easily get the desired mass of water vapor. See Fig. 4.00 m3 2 m3 65mm -—> 23°C kg moles, Basis: 1.00 m? H2O vapor at 15.5 mm Hg and 23°C 00 m? [15.5 mm | (273 1 kg mole |18 kg H,O _ 7" 0mm [273 + 23"K] 224m? | Tkg mole ~ '5! x 10°? kg H.0 Notice how the entire calculation can be carried out in a single dimensional equation. EXAMPLE 3.4 Perfect gas law You have 101b of CO, in a 20-ft? fire extinguisher tank at 30°C. Assuming that the ideal gas laws hold, what will the pressure gauge on the tank read in a test to see if the extinguisher is full? See Fig.87 Solution: Employing Eq. (3.2), we can write (the subscript I stands for standard conditions, 2 for the conditions in the tank) Pr —— 14.7 psia {10 1b COz|1 1b mole CO, | 359 ft} [303°K | | 4416 CO, [1 lb mole) 20F 373K etn a a Ca T; yy, vy ge 1 2 F Hence the gauge on the tank will read (assuming that it reads gauge pressure and that the barometer reads 14.7 psia) 66 — 14.7 = 51.3 psig. We have not used the gas constant R in the solution of any of the example problems so far, but you can use Eg. (3.1) to solve for one unknown as long as all the other variables in the equation are known. However, such a calculation requires that the units of R be expressed in units corresponding to those used for the quantities p-V-T. There are so many possible units you can use for each variable that a very large table of R values will be required. But, if you want to use R, you can always determine R from the p-V-T data at standard conditions which you have already memorized and used; R merely represents a pV/T relation at some fixed condition of temperature and pressure. EXAMPLE 3.5 Calculation of R Find the value for the universal gas constant R for the following combinations of units: (a) For 1 Ib mole of ideal gas when the pressure is expressed in psia, the volume is in ft3/Ib mole, and the temperature is in °R. (b) For 1g mole of ideal gas when the pressure is in atm, the volume in cm, and the temperature in °K. (©) For 1 kg mole of ideal gas when the pressure is in N/m?, the volume is in m}/kg mole, and the temperature is in °K. Solution: (a) At standard conditions = 14.7 psia P = 359 ft3/Ib mole T = 492°R Then 14.7 psia| 359? _ 19. 73_(psiaXft?) 492°R_ [1 1b mole CR) mole}88 (b) Similarly, at standard conditions, p=latm % = 22,400 em3/g mole T= 273K R= EE = rae remale ~ 206g tay (c) In the SI system of units standard conditions are p = 1.013 x 105 N/m? P = 22.4 m3/kg mole T=273K _ ph _ 1.013 x 108 Nim? | 2.4m _ R= p= SK Tkgmore = 8:30 x 10 We want to emphasize that R does not have a universal value even though it is called the universal gas constant. The value of R depends on the units of p, V, and T, Similarly, you should realize that R is not a dimensionless quantity; i.e., there is no value of R = 21.9, but there is 2 value of = (in. Hg)(ft*) R= 21.9 aE mole\CR) (ma) CK)kg mole) EXAMPLE 3.6 Perfect gas law Calculate the volume occupied by 88 Ib of CO, at a pressure of 32.2 ft of water and at 15°C. Solution: See Fig. E3.6. gs |_| trot #° at 32.2 ft H20 Ib SC. and 15°C Fig. £3.6. Solution No. 1 (using Boyle’s and Charles’ laws) AtS.C.: p = 3391 ft HO ; fe V = 359 ipmole +7 = 223K Basis: 88 1b of COz 88 Ib CO, GeO 359 ft?_ | 288 | 33.91 798 ft? CO, ee 5 Tb mole CO; | 11b mole |273| 32.2 at 32.2 ft H,O and 15°C89 Solution No. 2 (using gas constant R): . First, the value of R must be obtained in the same units as the variable p, 7, and T. For 1 Ib mole, and at S.C, D = 359 ft3/Ib mole T = 273°K _ 33.91 | 359 ie 273 Now, using Eq. (3.1), inserting the given values, and performing the necessary cal- culations, we get ft HO) ft b mole)@K) Basis: 88 ib CO; nRT 88 Ib CO, | (44.6 ft H,O)(ft?)| 288°K a (lb mole)(°K) [32.2 H.0 = 798 ft? CO, at 32.2 ft H,O and 15°C If you will ins; ect both solutions closely, you will observe that in both cases the same numbers appear and that both are identical except that in the second solution using R two steps are required to obtain the solution. EXAMPLE 3.7 Perfect gas law One important source of emissions from gasoline-powered automobile engines that causes smog is the nitrogen oxides NO and NO;. They are formed whether com- bustion is complete or not as follows: At the high temperatures which occur in an internal combustion engine during the burning process, oxygen and nitrogen combine to form nitric oxide (NO). The higher the peak temperatures and the more oxygen available, the more NO is formed. There is insufficient time for the NO to decompose back to O, and N; because the burned gases cool too rapidly during the expansion and exhaust cycles in the engine. Although both NO and nitrogen dioxide (NO) are signi- ficant air pollutants (together termed NO,), the NO; is formed in the atmosphere as NO is oxidized, Suppose that you collect a sample of a NO-NO; mixture (after having removed the other combustion gas products by various separations procedures) in a 100-cm? standard cell at 30°C. Certainly some of the NO will have been oxidized to NO; 2NO + 0, —> 2NO, during the collection, storage, and processing of the combustion gases so that measure- ment of NO alone will be misleading. If the standard cell contains 0.291 g of NO, plus NO and the pressure measured in the cell is 1265 mm Hg, what percent of the NO + NO, is in the form of NO? See Fig.90 V=100 om p=1265 mm Hg Solution: The gas in the cell is composed partly of NO and partly of NO. We can use the ideal gas law to calculate the total gram moles present in the cell and then, by using the chemical equation and the principles of stoichiometry, compute the composition in the cell. Basis: 100 cm? gas at 1265 mm Hg and 30°C _ 160. mm Hg | 22.41 | 1000.em? _ ._ (rm He)(cm?) R=—aeK [Temoley] 11 = ©24 * 10* “exe mole) 1265mmHg __| 100 cm? (mm Hg)(em3) 0 6.24 x 100 303°K If the mixture is composed of NO (MW = 30) and NO; (MW = 46), because we know the total mass in the cell we can compute the fraction of, say, NO. Let x = grams of NO; then (0.291 — x) = g NO). Basis: 0.291 g total gas a= a = = 0.00670 g mole The sum of the moles is xgNO|I gmole NO , (0.291 ~ x) 8NO,|1 gol NOs _ 9.09670 30g NO og NO; 0.0333x + (0.291 — x)(0.0217) = 0.00670 x = 0.033 g The weight percent NO is 0.033 ° 77 100) & 11% and the mole percent NO is Oe C.00) = 171% 3.1.2 Gas Density and Specific Gravity. The density of a gas_is defined as the mass per unit volume and can be expressed in pounds per cubic foot, grams per liter, or other units. Inasmuch as the mass contained in a unit volume varies with the temperature and pressure, as we have previously men- tioned, you should always be careful to specify these two conditions. Unless otherwise specified, the volumes are presumed to be at S.C Density can be calculated by selecting a unit volume as the basis and calculating the mass of the contained gas.91 EXAMPLE 3.8. Gas density What is the density of N; at 80°F and 745 mm Hg expressed in (a) American engineering units? (b) cgs units? (c) SI units? Solution (ay Nz at 80°F and 745 mm He 1 745 mm Hg| 1 |b mole 28ib oy ~TS40R 170mm Hel 359A TTT mole ~ 9:0696 10 density = 0.0696 Ib/ft? of N, at 80°F and 745 mm He = 111Sg density = 1.115 g/l of N, at 80°F (27°C) and Smm Hg (e) Basis: | m? N; at 80°F and 745 mm Hg 492°R | 745mm Hg|1kgmole| 28 kg 40°R | 760mm Hel 22.4m> Trkemole |! !5ks density = 1.115 kg/m? of Nz at 80°F (300°K) and 745 mm Hg (9.94 7 10! N, m?*) The specific gravity of a gas is usually defined as the ratio of the density of the gas at a desired temperature and pressure to that of air (or any specified reference gas) at a certain temperature and pressure. The use of specific gravity occasionally may be confusing because of the manner in which the values of specific gravity are reported in the literature. You must be very careful in using literature values of specific gravity. Be particularly careful to ascertain that the conditions of temperature and pressure are known both for the gas in question and for the reference gas. Among the examples below, several represent inade- quate methods of expressing specific gravity. (a) Whar is the specific gravity of methane? Actually this question may have the same answer as the question, How many grapes are in a bunch? Unfortunately, occasionally one may see this question and the best y possible answer is density of methane at S.C. SP 8 = —“Gensity of air at SC (b) Whar is the specific gravity of methane (H, = 1.00)? Again a poor question. The notation of (H, = 1.00) means that H, at S.C. is used as©) (d) (e & 92 the reference gas, but the question does not even give a hint regarding the conditions of temperature and pressure of the methane. Therefore the best interpretation is _ density of methane at S.C. SP Br = ~~Gensity of H, at S.C. What is the specific gravity of ethane (air = 1.00)? Same as question (b) except that in the petroleum industry the following is used: sp gr — density of ethane at 60°F and 760 mm Hg density of air at S.C. (60°F, 760 mm Hg) What is the specific gravity of butane at 80°F and 740 mm Hg? No reference gas nor state of reference gas is mentioned. However, when no reference gas is mentioned, it is taken for granted that air is the reference gas. In the case at hand the best thing to do is to assume that the reference gas and the desired gas are under the same conditions of temperature and pressure: density of butane at 80°F and 740 mm Hg SP 8 = ~“Gensity of air at 80°F and 740 nim Hg What is the specific gravity of CO, at 60°F and 740 mm Hg (air = 1.00)? density of CO, at 60°F and 740 mm Hg density of airat S.C. What is the specific gravity of CO, at 60°F and 740 mm Hg (ref. air at $.C.)? spgr= sp gr = same as question (e) EXAMPLE 3.9 Specific gravity of a gas What is the specific gravity of N, at 80°F and 745 mm Hg compared to (a) Air at S.C. (32°F and 760 mm Hg)? (b) Air at 80°F and 745 mm Hg? Solution: First you must obtain the density of the N, and the air at their respective con- ditions of temperature and pressure, and then calculate the specific gravity by taking a ratio of their densities. Example 3.8 covers the calculation of the density of a gas, and therefore, to save space, no units will appear in the following calculations fa) Basis: 1 ft? N? at 80°F and 745 mm Hg u a Le | = = = 0.0696 Ib N,/ft? at 80°F, 745 mm Hg Basis: | ft? of air at 32°F and 760 mm Hg a eo 7 | +09 29 — 0.0808 Ib air/ft? at 32°F, 760 mm HgTherefore 0.0696 _ Ib Na/ft? Nz at 80°F, 745 mm He SP at = gogog = 0-863 Te airfft? air at S.C, Note: specific gravity is not a dimensionless number (b) Basis: | ft? air at 80°F and 745 mm Hg \ 4s a 29 _ 0.0721 Ibjft? at 80°F and 745 mm He 0.0696 _ 9 o¢e Ib Nal (SP 80m, = QaaT = 0-965 pair air = 0.965 Ib N3/Ib air Note: You can work part (b) by dividing the unit equations instead of dividing the resulting densities 1 | 492 | 745 [28 dy, [5407760 [3ST] 28 bp spar = SS = Daas 55 = 55 = 0.965 1b Nz/lb air 340) 760 | 359 The latter calculation shows that the specific gravity is equal to the ratio of the molecular weights of the gases when the densities of both the desired gas and the refer- ence gas are at the same temperature and pressure. This, of course, is true only for ideal gases and should be no surprise to you, since Avogadro's law in effect states that at the same temperature and pressure 1 mole of any ideal gas is contained in identical volumes. 3.1.3 Ideal Gaseous Mixtures, In the majority of cases, as an engineer you will deal with mixtures of gases instead of individual gases. There are three ideal gas laws which can be applied successfully to gaseous mixtures: (a) Dalton’s law of partial pressures. (b) Amagat’s law of partial volumes (c) Dalton’s law of the summation of partial pressures. (a) Dalton’s laws. Dalton postulated that the total pressure of a gas is equal to the sum of the pressures exerted by the individual molecules of each compo- nent gas. He went one step further to state that each individual gas of a gaseous mixture can hypothetically be considered to exert a partial pressure. A partial pressure is the pressure that would be obtained if this same mass of individual gas were alone in the same total volume at the same temperature. The sum of these partial pressures for each component in the gaseous mixture would be equal to the total pressure, or Prt Prt Prt +P, =P 3.3) Equation (3.3) is Dalton’s law of the summation of the partial pressures.To illustrate the significance of Eq. (3.3) and the meaning of partial pressure, Suppose that you carried out the following experiment with ideal gases. Two tanks of, 150 ft? volume, one containing gas A at 300 mm Hg and the other gas B at 400 mm of Hg (both gases being at the same temperature of 70°F), are connected together. All the gas in B is forced into tank A isothermally. Now you have a 150-ft? tank of A + B at 700 mm of Hg. For this mixture (in the 150-ft? tank at 70°F and a total Pressure of 700 mm Hg) you could say that gas A exerts a partial pressure of 300 mm and gas B exerts a partial pressure of 400 mm. Of course you cannot put a pressure gauge on the tank and check this conclusion because the pressure gauge will read only the total pressure. These partial pressures are hypothetical pressures that the individual gases would exert and are equivalent to the pressures they actually would have if they were put into the same volume at the same temperature all by themselves. You can surmise that, at constant volume and at constant temperature, the pressure is a function only of the number of molecules of gas present. If you divide the perfect gas law for component I p,V, =2,RT,, by that for compo- nent 2, p,V; = n,RT,, at constant temperature and volume, you can obtain Bam (3.4) Pr ny which shows that the ratio of the partial pressures is exactly the same numeri- cally as the ratio of the moles of components | and 2. Similarly, dividing the ideal gas law for component | by the gas law for alll the molecules, p,V, = n, RT, you will get Dalton’s law of partial pressures: 21 = 4 = mole fraction = y, (3.5) Pom Equation (3.5) shows that the ratio of the partial pressure of an individual com- ponent to the total pressure is exactly the same numerically as the ratio of the moles of the individual component to the total moles. With this principle under your belt, if the mole fraction of an individual gaseous component in a gaseous mixture is known and the total pressure is known, then you are able to calculate the partial pressure of this component gas by generalizing Eq. (3.5): Pi =ViPo (3.5a) where i stands for any component. (b) Amagat’s law. Amagat’s law of additive volumes is analogous to Dalton’s law of additive pressures. Amagat stated that the total volume of a gaseous mixture is equal to the sum of the volumes of the individual gas components if they were to be measured at the same temperature and at the total pressure of all the molecules. The individual volumes of these individual components at the same temperature and pressure are called the partial volumes (or sometimes pure component volumes) of the individual components: VitV,+Vi4+--4V,=%, , 69)