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Stoichiometry of Bioprocesses
• Outline:
– Stoichiometry and energetics of chemical reactions
ChEn 5751 – Stoichiometry and energetics of biochemical reactions
– Reactions, coupled reactions, reaction networks,
Stoichiometry and Energetics of biopolymer synthesis, biomass synthesis
Biochemical Reactions – Biomass and product composition
– Stoichiometryy of biomass and product
p synthesis
y
– Yield coefficient
– Theoretical maximum
Prof. Wei-Shou Hu
– Anaerobic processor
Prof. Wei-Shou Hu 1
ChEn 5751 -Fall 2008
Whatt should
Wh h ld bbe b
balanced?
l d? • Macroscopically,
M i ll one mole l off glucose
l entering
t i
• Elements (C, N, O, H, P, S, etc.) the cell, may give rise to two moles of ethanol
and two moles of CO2
• Charge (if charges are not balanced, this will
• Macroscopic balance is thus:
create electropotential)
c6H12O6 → 2 C2H5OH + 2 CO2
The reactions are “physiologically feasible, i.e. the
enzyme system exists to carry the reaction out • Biochemically the result is the net reactions in
• Example: Production of ethanol glycolysis, converting glucose to pyruvate, and
in ethanol fermentation reaction
Prof. Wei-Shou Hu 2
ChEn 5751 -Fall 2008
CH2OH pyruvate
Prof. Wei-Shou Hu 3
ChEn 5751 -Fall 2008
Cell Composition
Elemental Composition of Bacterial Chemical composition of cells
Cell and Yeast % of Dry Mass
• Most abundant component is water, often not
Average
g Composition
p of a Cell included in biomass formulation
Mass (pg/cell) % of Dry Mass • Consisted of carbon compounds, proteins,
Animal Cell Bacterium Animal Cell Bacterium carbohydrates, lipids, nucleic acids, and non-
Wet Weight 3500 1.5
carbon compounds, electrolytes,
Dry Weight 600 0.3 100 100 • major elemental components: C, N, H, O, P, S
Protein 250 0.17 41 55
yp
• Typical cellular formula:
Carbohydrate 150 0.015 20 5
Lipid 120 0.015 1.5 5
– Bacterium CH1.6N0.20O0.27 to CH2N0.26O0.45
DNA 10 0.015 1.5 5 – Yeast CH1.64N0.16O0.52P0.01S0.005
RNA 25 0.075 2.5 25 – Animal cells CH1.98N0.26O0.49
Water 1.2 500 400
Volume 4 X 10-9 cm3 1.5 X 10-12 cm3
Prof. Wei-Shou Hu 4
ChEn 5751 -Fall 2008
slope = yield
Substrate consumed
Substrate consumed
Inputs Outputs
Subsrates consumed → biomass produced+ (CO2 + water) produced
Prof. Wei-Shou Hu 5
ChEn 5751 -Fall 2008
Prof. Wei-Shou Hu 6
ChEn 5751 -Fall 2008
Products that are converted directly from the Consider carbon utilization (carbon source is the substrate)
raw materials in an energetically favorable Aerobic Process
(i) Without product (other than CO2, H2O) formation
fashion
ΔX
The producer confers a biochemical pathway to convert the raw materials to the product with a ΔS = ΔSx energy
net generation of chemical energy.
O2 Δ CO2 + Δ H2O
Example: Ethanol production by yeast yeast, one mole glucose can be converted to two moles of
ethanol, and generates two moles of ATP. The reaction in thus energetically feasible,
and the theoretical maximum is (2x46/180=) 0.51 Kg ethanol/Kg glucose. The true (ii) With product formation partition ΔS into ΔSx and ΔSp,
yield in process is lower because some glucose will be diverted to make biomass. The estimate ΔSp from the theoretical maximum
basic way of calculating the theoretical yield of such products is to tabulate the pathway
and examine its energetic conversion.
e.g. production of 20g glutamate and 10 g cells
Example #2: Production of glutamic acid from glucose and ammonia in corynebacterium
glutamican encompasses the following pathways. from 100 g glucose. Y p/s, max = 0.8
Glucose + 2ADP + 2Pi → 2 Pyruvate + 2 ATP
Pyruvate + NAD + → acetylCoA + CO2+NADH
Pyruvate + CO2 + ATP + H2Ooxaliacetate +ADP + Pi
ΔSp= 20/0.8 =25 (theoretical yield 0.8 g glutamate/g glucose)
Acetyl CoA + oxaliacetate + NAD+ → α-ketoglutarate + CO2 + NADH 100g
α-ketoglutarate + NADPH + NH3 →glutamate +NADP + + H2O ΔSx= 100-25=75g, Δχ=10
Net reaction is:
Glucose + NH3 + ADP + Pi+ NADPH + 2NAD + → glutamate +CO2 + ATP + 2NADH + NADP + so Yx/s= 10g cell/ 75 g glucose
Overall, it is energetically feasible since a net production of 1 ATP and 1 NADH. So, the
theoretical maximum conversion based on carbon is
5/6 (mole carbon in glutamate/mole carbon in glucose), or on a mass basis (143/180=) 0.79
Prof. Wei-Shou Hu 7