574 ‘Chapter 7 Fundamentals of Biological Trectment used fo develop energy balances in bioenergetic analyses. Determination of the free energy change resulting from the oxidation of hydrogen by oxygen is illustrated in Example 7-2 Free Energy Change from Hydrogen Oxidation by Molecular Oxygen Determine the free energy change resulting from the oxidation of hydrogen by malec- ular oxygen. 1. Identify the electron donor and acceptor Electron donor; —_faydrogen Electron acceptor; oxygen 2, Determine the change in free enespy, From Tuble 7-7, the free energy change val- ues for the half reections ate: 6’, kJ/mole o- No, 28 Hy 2H +260 ~40.46 No. 4 ©, + 2H! + 2e HO -78.14 Overall H, +10, HO AG - -118.60 Because the AG vaiue is negative for this oxidation reduction reaction, energy is released and the overall reaction will proceed as written Fxergonic resetiony are catalyzed by enzymes within the microbial cell, making energy available to support cell zrowth. Only « portion (40 to 80 percent) of the energy produced is captured by the bacteria, while the rest escapes as heat. McCarty (1971) assumed 60 percent energy capture otiieiency, but the exact amount varies. The energy that is not captured or releused can result in aa elevated temperature in the surrounding liquid, where high biomass concentrations exist and high reaction rates are occurring. ‘An example is autothermal aerobic digestion in which liquid temperatures are increased feom 20°C t0 as high as 60°C due to biological oxidation and energy release. The volatile solids concentration in wutothermal aerobie digesters may be in the range of 20 1040 gL. “The key steps in bioenergeties analysis are o (1) identity the electron donor (sub- strate oxidized) and efectson zeceptor, (2) determine the energy produced from the bac- tetia oxidation reduction reaction, (3) determine the amount of energy nevded for con- verting the growth carbon source into cell matte, and (4) calculate the cell yield based on a balance between energy produced and energy needed for cell yield. The energy production step Was iDustiaied above for oxidation of hydrogen with oxygen as the electron acceptor. “The amount of energy required for cell synthesis depends on the specific carbon and nitrogen compounds used for growth. The bioenergetics analysis discussed here is for heterotrophic bacteria. A different procedure is used for the case of autotrophic bac- spa sri7-4 Boctorial Growth and Energetics | 575 teria, and additional detaily can be found in MeCarty (L971, 1975) and Rittman, and MoCarty (2001). For hetemtraphic bacteria, many carbor sources tay be used for growth with different energetic effects. The analysis assumes pyruvate as an internedi- aie organic compound in cell synthesis, and energy will be either produced or consumed depending on the free energy of the organic compound relative to pyruvate, Pyruvate ‘was selected by McCarty (1071) because if is at the end of the glycolysis pathway and just ahead of the Rreb cycle. When CO, is useé for the carbon soure, as for autotrophic bacteria, « considerable amount of encrgy is needed to incorporate CO, into cell mass. Ti nitrogen is not zvailabe inthe form of smmonia, additional energy is needed to con- vert the nitrogen source to ammonia, The energy required for cell synthesis is estimated as follows, with pyruvate as the organic imermediate for cellular carbon constituents: AG; AG, 4G, = 274 = AG, + z 1a AG EY 7-8) where AG, = free energy to convert | electron equivalent (e~ eq) of the carbon source to cel! materia} AG, ~ free energy te convert 1 e ¢q of the carbon source to the pyruvate imermediate action of energy transfer captured m= +1 if AG, is positive and | if energy is produced AGg = fice energy to convert I 2 eq of pyruvate intermediate 10 1 e° eq of cells AGyy = free energy per e” eq of cells to reduce nitrogen to ammonia “The value for AG, is ~31.41 klfe eq of cells (MeCarty, 1971) and the AG, for the fol- Towing nitrogen sources are +1746, + 13.61, +15.85, and 0.00 kife~ eq of cells for NO;, NOs, Ny. and NH7, respectively. The value for AG, is estimated by using the free energy fia reactions to convert the varbon source to the pyruvate intermediate, ‘The electron donor used for heterotrophic seactions is divided between portions oxidized to produce energy or used in cell synthesis. The energy balance relative to the substrate used is illustrated in the following equation in which the energy made avail- able (on the ‘eft side of the equation) equals the energy used for cell growth (right side of the equation) aa) =~ AG, {7-9} Lthalo {7-10} fraction of encrgy captured energy released from oxidation reduction rezctions, kimole e (cansfered 4, =e mole of substrate oxidized per e~ mole of substrute used if =e mole of substrate used for cell synthesis per e~ mole of substrate used AG, = cnergy used for cell growth, kY/mole e~ transfer for cell growth Equations (7-9) and (710) are used with half reuctions and their free energy val- vues to estimate cell yield by solving fer f, and f.. The terms f, and / represent the frac- tion of substrate oxidized or used in cell synthesis, respectively. The substrate is576 | Chopler 7 Fundamentols of Biclolcal reahront expressed as COD hecause a mete of COD contains a set quantity of clectron moles of oxygen transfer. Thus. the values for and f, can also be expressed as COD tractions The oxidation of acetate by heterotrophic bacteria with different acceptors is used in Example 7-3 to illustrate the bivenergeties analy EXAMPLE 7-3. Estimate Biomass Yield Using Energetics Compare the cell yield in g celis as COD/g COD used and g cells as VSS/g COD used for acetate utilization by het- erotrophic bacteria with oxygen and then carbon dioxide as the electron acceptor, and ammonia as the nitrogen source. Assume 60 pescent energy capture efficiency. Solution Part A~-Oxygen as the Electron Acceptor L. Solve for the energy produced and captured (KAG,) using reaction No, 18 for ‘ucetate oxidation and reaction No, 4 for oxygen reduction from Table 7-7. ka/mole e~ No. 18 }CH,COO + PHO }CO, + HCOZ HH +e - 7.88 No. 4 10, +H +27 JHO -78.14 JCHjCOO +10, + 10, + {COZ + 1H,0 AG, = -105.82 Energy captured by cell: K(AG,) = 0.60(— 105 82) = ~63.42 kimole &° 2. Solve for the energy needed per electron moie of cell growth (AG). AG, = 31-41 ki/mole &~ cells AGy = 0 AGp [acetate (reaction No, 18} to pyruvate (reaction No. 15)] AG ki/mole eo No. 18 ACH COO + 3H, 2€0, + gHCO, + ~27 66 No.15 $CO, + GHCO; + HE + ev > GCHCOCOO™ + $H,O 435.78 JCHsCOO + FCO, -» 7yCH:COCOO™ + GHCO, + gpHjO = AG = +812 Because AGy is positive, energy is required and m = +1 8.12 = | + 31.41 + 0} = 44.94 k1/mole & AGs~ Hea) ‘ me 3, Determine f, and f, using Eg. (7-9). fi -AGy __— 44:94 kT/mole e° f, KAG, ~ 63.42 ki/mole e~