80 CHEMICAL ENGINEERING 3.12. HEATS OF COMBUSTION The heat of combustion of a compound —AH? is the standard heat of reaction for complete combustion of the compound with oxygen. Heats of combustion are relatively easy to determine experimentally. The heats of other reactions can be easily calculated from the heats of combustion of the reactants and products. The general expression for the calculation of heats of reaction from heats of combustion is AH; = > AH?, reactants — )> AH?, products G21) Note: the product and reactant terms are the opposite way round to that in the expression for the calculation from heats of formation (equation 3.26). For compounds containing nitrogen, the nitrogen will not be oxidised to any significant extent in combustion and is taken to be unchanged in determining the heat of combustion. Caution. Heats of combustion are large compared with heats of reaction. Do not round off the numbers before subtraction; round off the difference. ‘Two methods of calculating heats of reaction from heats of combustion are illustrated. in Example 3.9. Example 3.9 Calculate the standard heat of reaction for the following reaction: the hydrogenation of benzene to cyclohexane. (1) CoHe(g) + 3Ho(g) > CoMia(g) (2) CoHe(g) + 7302(g) > 6CO2(g) + 3H200) AH? 3287.4 kJ (3) CoHi2(g) + 902 > 6CO2(g) + 6H20(1) AH? 3949.2 kJ (4) CUS) + On(@) > COLL) AH? = ~393.12 kT (5) Ha(g) + 10,(¢) + F200) AH? = ~285.58 kd Note: unlike heats of formation, the standard state of water for heats of combustion is liquid. Standard pressure and temperature are the same 25°C, 1 atm. Solution Method 1 Using the more general equation 3.26 AH? = > AH;, products — )7 AH; reactants the enthalpy of formation of CsHs and CsHj2 can be calculated, and from these values the heat of reaction (1), From reaction (2) AH®(CsHs) = 6 x AH2(COp) +3 x AH(H20) — AH5 (CoH) 3287.4 = 6(—393.12) + 3(—285.58) — AH} (CsHs) AHj (CoH) = —3287.4 — 3215.52 = 71.88 ki/molFUNDAMENTALS OF ENERGY BALANCES. 81 From reaction (3) AH CoH) = AH}(CoHi2) = 3949.2 — 4072.28 = 123.06 KI/mol 3949.2 = 6(—393.12) + 6(-285.58) — AH (CoB) AH} = AH} (CoHi2) — AHG (Cols) AH? = (123.06) — (71.88) = =195 ki/mol Note: enthalpy of formation of Hp is zero. Method 2 Using equation 3.27 AH? = (AH! (CoHe) +3 x AH2(H2)) — AH2 (CoH) (—3287.4 + 3(—285.88)) — (—3949,2) = — 196 kJ/mol Heat of reaction AH? = 196 ki/mol 3.13. COMPRESSION AND EXPANSION OF GASES The work term in an energy balance is unlikely to be significant unless a gas is expanded or compressed as part of the process. To compute the pressure work term: 2 -we Pdv (equation 3.5) 1 a relationship between pressure and volume during the expansion is needed. If the compression or expansion is isothermal (at constant temperature) then for unit mass of an ideal gas: Py = constant (3.28) Py, RT. Po and the work done, —W=P\y ln =—— In (3.29) WePoang =p, 6) where P; = initial pressure, P) = final pressure, v; = initial volume. In industrial compressors or expanders the compression or expansion path will be “polytropic”, approximated by the expression: Pv" = constant 3.30)82 CHEMICAL ENGINEERING The work produced (or required) is given by the general expression (see Volume 1, Chapter 8) P,\o-bin RT; \e—bin Pa a1) =z85 - 3 (2) 1) =ZF ) 1] G31 where Z = compressibility factor (1 for an ideal gas), R = universal gas constant, 8.314 JK! mol7!, T, = inlet temperature, K, M = molecular mass (weight) of gas, W = work done, Jkg The value of n will depend on the design and operation of the machine. The energy required to compress a gas, or the energy obtained from expansion, can be estimated by calculating the ideal work and applying a suitable efficiency value. For recip- rocating compressors the isentropic work is normally used ( = y) (see Figure 3.7); and for centrifugal or axial machines the polytropic work (see Figure 3.6 and Section 3.13.2). 3.13.1. Mollier diagrams If a Moltier diagram (enthalpy-pressure-temperature-entropy) is available for the working fluid the isentropic work can be easily calculated. W=H\-Hy (3.32) where H is the specific enthalpy at the pressure and temperature corresponding to point 1, the initial gas conditions, H, is the specific enthalpy corresponding to point 2, the final gas condition. Point 2 is found from point 1 by tracing a path (line) of constant entropy on the diagram, ‘The method is illustrated in Example 3.10. Example 3.10 Methane is compressed from 1 bar and 290 K to 10 bar. If the isentropic efficiency is 0.85, calculate the energy required to compress 10,000 kg/h, Estimate the exit gas temperature, Solution From the Mollier diagram, shown diagrammatically in Figure 3.5, Hy = 4500 cal/mol, Hz, = 6200 cal/mol (isentropic path), Isentropic work = 6200 — 4500 700 cal/molFUNDAMENTALS OF ENERGY BALANCES. 83 p=10 ‘Actual path Enthalpy Isentropic path Entropy —> Figure 3.5. Mollier diagram, methane « _ re ton 5 Centrifugal G 70 Volumetric flow rate (suction conaitions), mis Figure 3.6. Approximate polytropic efficiencies centrifugal and axial-flow compressors For an isentropic efficiency of 0.85: Actual work done on gas pa 2000 cal/mol So, actual final enthalpy Hi, = Hy + 2000 = 6500 cal/mol84 CHEMICAL ENGINEERING 100 90 0 Isontropic efficiency 70 60 1 15 20 2530350 Compression ratio Figue 3.7. Typical efficiencies for reciprocating compressors From Mollier diagram, if all the extra work is taken as irreversible work done on the gas, the exit gas temperature Molecular weight methane = 16 Energy required = (mols per hour) x (specific enthalpy change) 10,000 x 2000 x 103 = 1.25 x 10° cal/h = 1.25 x 10° x 4.187 5.23 x 10° Ih ° Power = 222°" _ 45 mw 3600 3.13.2. Polytropic compression and expansion If no Mollier diagram is available, it is more difficult to estimate the ideal work in compression or expansion processes. Schultz (1962) gives a method for the calculation of the polytropic work, based on two generalised compressibility functions, X and Y; which supplement the familiar compressibility factor Z. r(x v \ar)» Pa v (F), 3.34) His charts for X and Y as functions of reduced temperature and pressure are reproduced as Figures 3.9 and 3.10. The functions are used to determine the polytropic exponent n 3.33) y=FUNDAMENTALS OF ENERGY BALANCES. 85 for use in equation 3.31; and a polytropic temperature exponent m for use in the following equation: Tr 835) Zh MA yx) & 6.36) where mae (Ee ‘or compression, 3 ZR m= © (Ep + X) for expansion 6.37) E, is the polytropic efficiency, defined by: yt rk for compression Ey = POPS NO wl work Fequ 7 for expansion £, = Sl work obtained P » = ~Solytropie work An estimate of E,, can be obtained from Figure 3.6. 1 —— 3.38) Y—ma +X) CS) At conditions well removed from the critical conditions equations 3.36, 3.37 and 3.38 reduce to: (3.36a) (3.37a) (3.384) I-m ‘These expressions can be used to calculate the polytropic work and outlet temperature by substitution in equations 3.31 and 3.35. They can also be used to make a first estimate of T> in order to estimate the mean reduced temperature for use with Figures 3.9 and 3.10. ‘The use of Schultz’s method is illustrated in Examples 3.11 and 3.16. Example 3.11 Estimate the power required to compress 5000 kmol/h of HCI at 5 bar, 15°C, to 15 bar. Solution For HCI, P, = 82 bar, T, = 324.6 K C5, = 30.30 - 0.72 x 10°F + 12.5 x 107%; and 3.36a. 3.9 x 10°7° ki/kmol K Estimate 7 from equations For diatomic gases y = 1.4. ¢, Note: y could be estimated from the relationship y = —"86 CHEMICAL ENGINEERING At the inlet conditions, the flow rate in m*/s = 5g 3600 273 From Figure 3.6 E, = 0.73 14-1 From equations 3.360 and 3.35, m= ATT ass ram (8) aan 4424-228 T, won = Te a5gg = 108 S415 P, nm) = 2 > = 0.12 2x82 At T pean) C9, = 29.14 ki/kmol K Correction for pressure from Figure 3.2, 2 kJ/kmol K Cp = 29.14 +2 ~ 31 ki/kmol K From Figures 3.8, 3.9 and 3.10 at mean conditions: X=018, ¥=104, Z=097 98 Z at inlet conditions = From equations 3.36 and 3.38 0.97 x 8.314 ( 1 31 antes) 1 1.04 — 0.41 + 0.18) From equation 3.31 1.76 W polytropic = 0.98 x 288 x 8.314 x = W polytropic = 0.98 x 288 x 8. ae (8) 299 kI/kmol Actual work required = P&'Y*tePic work Ep = 2222 _ 4520 ky/kmol 0.73 4520 =— x 5000 = Ww 3a00 * 5000 = 6275 ki Say, 6.3 MW Power ry ass ('5)"" saeconpresitiy fee,» Reduce ampere, T,= 10. Reducodterpersr,T, Pigue 38 Reduced pressure, P, > Compress facta of ete and vapore Tw pressure range P, STONVIVa ADKINS JO SWINSON aFigue 3.9. Geatalisedcompersiy fseon X ‘oN3BMIONS TWOINIHOpee83 2 18. Seas omoresaiy Rtn, ¥ > STONVIVa ADKINS JO SWINSON cy