Stoichiometry: Che 3Bk3 October 12, 2004 Chapter 7, Shuler & Kargi

Stoichiometry
ChE 3BK3
October 12, 2004
Chapter 7, Shuler & Kargi
Outline
z Yield coefficients
z Stoichiometric calculations
• Elemental balances
• Degree of reduction
z Theoretical predictions of yield
coefficients
z Sample calculations
Yield Coefficients Revisited
M
z Y
Recall that X S is the maximum yield of cell
mass per unit mass of substrate consumed
when no maintenance is considered
z There are other important yield coefficients:
• YX ATP , the ATP yield coefficient, represents the amount
of biomass synthesized per mole of ATP generated
M
• X ATP is nearly constant at 10-11 g dry weight/mol ATP
Y
for heterotrophic growth under anaerobic conditions
• The ATP yield for many autotrophic organisms is
~6.5g/mol ATP
• Under aerobic conditions, the values for X ATP are
Y M
usually much greater than 10.5 g/mol ATP

ATP Maintenance Coefficient
z A maintenance coefficient, mATP, can also be
estimated using an equation analogous to the
one developed for the substrate yield coefficient
in a chemostat:
1 1 m ATP
= + (7.1)
YXAPATP YXM ATP D
AP
z Y
Where X ATP is the apparent yield of biomass,
and mATP is the rate of ATP consumption for
maintenance energy
Growth Parameters of Organisms
Growing Anaerobically in a Chemostat
ATP Yields in Various Growth
Media
Yield and Maintenance Coefficients
for Oxygen Consumption
z Yields based on oxygen consumption can be defined
using an equation similar to eq. 7.1:
1 1 mO2
AP
= M
+ (7.2)
Y X O2 Y X O2 D
z Values of YX/O can vary from 0.17 to 1.5 g biomass/g O2,
2
depending on substrate and organism
z Respiratory quotient (RQ): CO2 produced per mole of
oxygen consumed
• Provides an indication of metabolic state (e.g. aerobic growth
vs ethanol fermentation in baker’s yeast)
Elemental Balances
z A typical cellular composition can be represented
as CH1.8O0.5N0.2
z One mole of biological material is defined as the
amount containing one gram atom of carbon, e.g.
CHαOβNδ
z Consider the following simplified biological
conversion, in which no extracellular products other
than H2O and CO2 are produced:
CH mOn + aO2 + bNH 3 → cCH α Oβ N δ + dH 2O + eCO2
• Where CHmOn represents 1 mole of carbohydrate
Elemental Balances
z Simple elemental balances on C, H, O, and N yield the
following equations: C : 1 = c + e
H : m + 3b = cα + 2d
O : n + 2a = cβ + d + 2e
N : b = cδ (7.4)
e
z The respiratory quotient is: RQ = (7.5)
a
z Equations 7.4 and 7.5 constitute five equations for five
unknowns (a, b, c, d, and e)
• With a measured value of RQ, these equations can be solved
to determine the stoichiometric coefficients
Data on Elemental Composition
of Several Microorganisms
Degree of Reduction
z In more complex reactions, as in the formation of
extracellular products, an additional stoichiometric
coefficient is added, requiring more information
z Also, elemental balances provide no insight into the
energetics of a reaction
z The concept of degree of reduction has been developed
and used for proton-electron balances in bioreactions
z The degree of reduction, γ, for organic compounds is
defined as the number of equivalents of electrons per
gram atom of carbon
z The available electrons are those that would be
transferred to oxygen upon oxidation of a compound to
CO2, H2O and NH3
Degree of Reduction
z The degrees of reduction for some key elements
are C= 4, H= 1, N= -3, O= -2, P= 5 and S= 6
z The following are examples of how to calculate
the degree of reduction for substrates:
• Methane (CH4): 1(4) + 4(1) = 8, γ = 8/1 = 8
• Glucose (C6H12O6): 6(4) + 12(1) + 6(-2) = 24, γ = 24/6 = 4
• Ethanol (C2H5OH): 2(4) + 6(1) + 1(-2) = 12, γ = 12/2 = 6
z A high degree of reduction indicates a low degree
of oxidation, so γCH >γEtOH>γglucose
4
Degree of Reduction and Weight of
One Carbon Equivalent of One Mole
of Some Substrates and Biomass
Example 7.1
Solution
Solution
Solution
Solution
Solution
z The growth yield on more reduced
substrate (hexadecane) is higher than
that on partially oxidized substrate
(glucose), assuming that two-thirds of all
the entering carbon is incorporated in
cellular structures
z However, the oxygen yield on glucose is
higher than that on hexadecane, since
glucose is partially oxidized
Theoretical Predictions of Yield
Coefficients
z In aerobic fermentations, the growth yield
per available electron in oxygen
molecules is ~3.14 ± 0.11g CDW/electron,
when ammonia is used as the nitrogen
source
• The number of available electrons per oxygen
molecule (O2) is four
• When the number of oxygen molecules per
mole of substrate consumed is known, the
growth yield coefficient, YX/S can easily be
calculated
Coefficients
z Consider the aerobic catabolism of glucose:
C6 H12O6 + 6O2 → 6CO2 + 6 H 2O

z The total number of available electrons in 1
mole of glucose is 24
z The cellular yield per available electron is YX/S =
24*(3.14) = 76/180 = 0.4 g CDW/g glucose
z Most measured values of YX/S for aerobic growth
on glucose are within the range 0.38 – 0.51 g/g
Coefficients
z The ATP yield (YX/ATP) in many anaerobic
fermentations is ~10.5 ± 2 g CDW/mol ATP
z In aerobic fermentations, this yield varies
between 6 and 29 g CDW/mol ATP
z When the energy yield of a metabolic pathway
is known (N moles of ATP produced per gram
of substrate consumed), the growth yield can
be calculated using the following equation:
YX/S = YX/ATP N
Example 7.2
Example 7.2

Stoichiometry: Che 3Bk3 October 12, 2004 Chapter 7, Shuler & Kargi

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Stoichiometry

usually much greater than 10.5 g/mol ATP

C6 H12O6 + 6O2 → 6CO2 + 6 H 2O

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