9 Kinetics Fermentation N Thermodynamic

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TEKNIK FERMENTASI

ELEMENTAL AND REDOX BALANCES


Pillars of Reactor Design
Yield Coefficients
𝑞𝑖
 𝑌𝑗𝑖 = 𝑞𝑗

 Yield coefficients are measured in many consistent set of units, g g -1 or


mol mol-1, or for carbon-containing compounds C-moles (C-mole) -1.
Blackbox stoichiometric equation (C-mole basis)
 −CH2O − 𝑌𝑆𝑂 O2 − 𝑌𝑆𝑁 NH3- 𝑌𝑆𝑆1 S1-…+ 𝑌𝑆𝑋 X + 𝑌𝑆𝐶 CO2+ 𝑌𝑆𝑃1 P1+… 𝑌𝑆𝑊 H2O = 0

Glucose Oxygen N-source Secondary Biomass Carbon Product Water


Substrate Dioxide

 Rate of consumption of glucose in units of 1 C-mole = 30 g.


 Thus, if YSN = 0.05
 then 0.05 moles of NH3 is consumed every time 30 g = 1 C-mole glucose is
consumed by the chemical reaction
Blackbox stoichiometric equation (C-mole basis)
products synthesized per hour in the reactor
 Type equation here.
Blackbox stoichiometric equation (1 mole of carbohydrate
basis)
Respiratory quotient (RQ)
𝑞𝑐 𝑌𝑆𝐶
 𝑅𝑄 = = =𝑌𝑂𝐶
𝑞𝑂 𝑌𝑆𝑂

 Implications ??

 Correlation with kLa?


Degree of Reduction
 The degree of reduction, g, for organic compounds may be defined as
the number of equivalents of available electrons per gram atom C.
The available electrons are those that would be transferred to oxygen
upon oxidation of a compound to CO , H O, and NH .
2 2 3

 The degrees of reduction for some key elements are C = 4, H = 1,


N = -3, O = -2, P = 5, and S = 6.
Degree of Reduction
 Methane (CH4): 1(4) + 4(1) = 8, g = 8/1 = 8
 Glucose (C6H12O6): 6(4) + 12(1) + 6(-2) = 24, g = 24/6 = 4
 Ethanol (C2H5OH): 2(4) + 6(1) + 1(-2) = 12, g = 12/2 = 6

 A high degree of reduction indicates a low degree of oxidation. That


is, g CH4 > g EtOH > g glucose.
Degree of Reduction

 The degrees of reduction of substrate, biomass, and product are


g = 4 + m − 2n
s

C = 4, H = 1, N = -3, O = -2, P = 5, and S = 6.


Note that for CO2, H2O, and NH3 the degree of reduction is zero.
Degree of Reduction
 elemental balances on C, H, O, and N, an available electron balance, an
energy balance, and a total mass balance
 For such a data set, we would typically choose a carbon, a nitrogen, and
an available-electron balance, thus:

g = 4 + m − 2n
s
c+d+f =1
cδ + dz = b
cg + dg = g − 4 a
b p s
Degree of Reduction
 Assume that experimental measurements for a certain organism have
shown that cells can convert two-thirds (wt/wt) of the substrate carbon
(alkane or glucose) to biomass.
 Calculate the stoichiometric coefficients for the following biological
reactions:

 Calculate the yield coefficients YX/S (g dw cell/g substrate), YX/O2 (g


dw cell/g O2) for both reactions.
Degree of Reduction
 a. For hexadecane,
 amount of carbon in 1 mole of substrate = 16(12) = 192 g
 amount of carbon converted to biomass = 192(2/3) = 128 g

 Then, 128 = c(4.4)(12); c = 2.42.


 amount of carbon converted to CO2 = 192 - 128 = 64 g
 64 = e (12), e = 5.33
Degree of Reduction
 The nitrogen balance yields
14b = c(0.86)(14)

 b = (2.42)(0.86) = 2.085

 The hydrogen balance is


 34(1) + 3b = 7.3c + 2d
 d = 12.43

 The oxygen balance yields


 2a(16) = 1.2c(16) + 2e(16) + d(16)
 a = 12.427
Degree of Reduction
 For glucose, amount of carbon in 1 mole of substrate = 72 g
 amount of carbon converted to biomass = 72(2/3) = 48 g
 Then, 48 = 4.4c(12); c = 0.909.
 amount of carbon converted to CO2 = 72 - 48 = 24 g
 24 = 12e; e = 2
 The nitrogen balance yields
 14b = 0.86c(14)
 b = 0.782
 The hydrogen balance is
 12 + 3b = 7.3c + 2d
 d = 3.854
 The oxygen balance yields
 6(16) + 2(16)a = 1.2(16)c + 2(16)e + 16d
 a = 1.473
Degree of Reduction
TEKNIK FERMENTASI
Bioenergetics of Microbial growth : in relation to black box
stoichiometric model
 Heijnen, J.J., and Kleerebezem, R., Delft University of Technology
System definition of Microbial Growth
 Try to solve the stoichiometric reaction with only γ!
Overall growth reaction = Anabolism + f · Catabolism
cat
Thermodynamics

 Calculation of the Gibbs energy change of a catabolic reaction (∆𝑮𝟎𝟏


𝑪𝒂𝒕)

 The superscript ‘‘0’’ corresponds to standard conditions; 298 K, 1 bar for


gaseous species, and 1 mol/L for aqueous species. The superscript ‘‘1’’
identifies a correction for the biological reference proton concentration of 10 −7
mol/L.

 Standard conditions imply that the temperature equals 25◦C, that the
concentrations of all dissolved reactants are 1 mol/L, the partial pressure of all
gaseous reactants (e.g. O2) equals 1 bar, and that the H+ concentration equals
10−7 mol/L (pH= 7). A standard pH = 7 is based on the knowledge that the
intracellular pH (where the biochemical many reactions occur) is close to 7.
Thermodynamics

 Calculation of the Gibbs energy change of a catabolic reaction


(∆𝑮𝟎𝟏
𝑪𝒂𝒕 )
Thermodynamics

 Calculation of the actual Gibbs energy of a reaction under


nonstandard condition(𝑮𝒇𝟎 )
Thermodynamics

 Calculation of the actual Gibbs energy of a reaction under


nonstandard condition(𝑮𝒇𝟎 )
Thermodynamics

 Gibbs Energy Change of the Overall Growth Reaction


Thermodynamics

 Calculation of the overall growth reaction using Gibbs Energy


Change

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