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Reaction Occurs
Mass Balance in Cases
Assistant Professor Betül Gürünlü
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ÿ In continuous reactions , new substances are


constantly entering the reactor, and the products
obtained are constantly thrown out.

ÿ Such a reaction is not initially stable. Temperature,


pressure, and concentration inside the reactor change
Mass Balance with time.
in Continous ÿ If the reaction conditions can be kept constant, it is observed that

Reactions the flow, temperature, pressure, flow rate, concentration,


percentage composition and other properties of the system
entering and leaving the system do not change over time after a
certain period of time after the reaction has started. This state is
called the 'rested state' .
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ÿ Continuous reactions in industry are used to save time.

ÿ It can provide a great advantage in terms of


increasing the efficiency, especially in reactions with
a low conversion rate in a single pass from the
reactor . In this type of reactions, very little of the
Reversible reactants can turn into products.
• These substances, which are mixed with the
reactions product, are separated from the product by some
physical methods and mixed with the new feed
stream entering the reactor by 'recycling' to be
used again . Thus, the amount of substance
entering the reactor and the rate of conversion to
product are increased. These types of reactions
are called reversible
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ÿ In reversible reactions, the mixture leaving the reactor is


separated as product and residue by a separation process.

reversible
reaction
flow chart Feed
Flow Product
Reactor Separator

Reflux waste
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ÿ In some reactions, all substances at once


It is not required to enter the reactor.

ÿ The temperature, pressure or amount of product formed in the reactor


'side' to some of the input current in order to control
transition (bypass) is done.

Flow ÿ The bypass current is passed outside the reactor and regenerated.
mixed into the mainstream.
chart for side- ÿ By adjusting the flow rate of the bypassing current, the desired

pass reactions amount of substance is allowed to react.

Side Pass
Feed
flow
Reactor Product
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ÿ Not all continuous reactions may have reversal or by-


pass processes.
ÿ In a normal, steady state reaction, on the one hand,
new substances enter the reactor, on the other hand,
products and residues are thrown out.

ÿ Since the flow rates and compositions of the inlet and outlet
streams to the system do not change over time, the resulting
product mass only depends on the conversion rate in a single
pass through the reactor.
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ÿ Methyl alcohol is obtained according to the following reaction by passing a 2/1


molar mixture of Hydrogen and Carbon Monoxide gases over a catalyst . The
degree of completion of this reaction is 20%. The gases coming out of the
reactor are cooled and most of the methyl alcohol formed is separated in
liquid form.

A small amount of methyl alcohol remains in the residual gases.


The gas mixture containing 2% methyl alcohol by volume is recycled. If 100
Example 1
moles of new gas mixture enters the system;

ÿ 2H2 + CO —> CH3OH

ÿ A) The number of moles of methyl alcohol obtained

ÿ B) Calculate the number of moles of the returning gas mixture .


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ÿ Basic: 100 moles of gas mixture entering the system

2H2 + CO
CH3OH
Reactor Separator

Example 1 - Reflux 2% CH3OH


A) Let's say x is the number of moles of methyl alcohol obtained if 100 moles of
Solution new gas mixture enters the system . According to the reaction equation, 3 moles
of gas mixture creates 1 mole of methyl alcohol. So: x = 100/3 = 33.3 mol CH3OH

B) When 100 moles of new gas mixture enters the system, let the return gas
mixture be x. The returning gas mixture contains 2% methyl alcohol and 98%
H2+CO gas mixture. If the conversion rate of CO is 20%.
From the CO equivalence around the reactor:

[(0.98x)/3 + (100/3)]0.80 = 0.98x/3 Here x = 408.2 moles of gas mixture.


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ÿ Reproduction and product formation is a complex


event that occurs as a result of thousands of
biochemical reactions occurring inside the cell.

Stoichiometry ÿ Substrates or microorganisms for various process


calculations ; It is necessary to compare biomass
of Biological yield, product yield and heat released.

reactions ÿ We may also want to know how close a process is to


its thermodynamic limit.

ÿ Although intracellular activities are complex, it is


possible to represent the conversion of substrate to
biomass and product with a chemical equation.
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ÿ Reproduction occurs as a result of substrate consumption.


is an event.

ÿ Substrates provide raw materials and energy for biomass


synthesis.

ÿ In macroscopic terms, the environment in which the cell is


located must contain the necessary chemical substances
Reproduction:
for biomass synthesis.
1. Restrictive
ÿ From a thermodynamic point of view, the free energies of the substrates
Substrate: should be higher than the free energies of the biomass and metabolic

products.

ÿ In addition, the chemical substances in the


environment must be compatible with the enzymatic
structure in the cell (ie the cell must have enzymes
that can break down these substrates and convert
them into suitable compounds).
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The substrate must contain the necessary


nutrients to ensure the growth of the
microorganism, optimal biosynthesis and other
activities.

A substrate containing the required nutrients in


sufficient quantities and in appropriate forms is
the first step for successful production.

The chemical composition of the substrate


must meet all the elemental requirements for
cell and product synthesis, as well as provide
the necessary energy for cell maintenance and
metabolic activities.
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P, products

Substrates
S P+X
Cell
Reproduction:
1. Restrictive Substrate: Reactions necessary for cell growth
(S: substrate, P: product, X: biomass)

In the system in which a number of cells act as a catalyst


Cell is synthesized in parallel with substrate consumption.
and new products are created.
Products: Organic compound different from cell matter.

Numerous chemical substrates during reproduction


used as.
Microorganisms obtain the energy they
need by using the stored energy in the
chemical bonds of some compounds in
the environment. These can be organic
or inorganic substances. The best
Reproduction: sources of energy are carbohydrates.
1. Restrictive Substrate: The second nutritional factor is the main
elements and trace elements such as C,
H, O, N, P, S, which are necessary for
biomass formation and biosynthesis.
They can be found in the substrate as
simple compounds or as complex
compounds.
The substrate composition is regulated differently
according to specific purposes. For example, the
growth medium is prepared in a composition that
will enable the active growth of the microorganism,
whereas the storage medium is prepared only to
preserve the viability of the microorganism in
conditions that are not suitable for growth.

The concentration of the carbon source is kept low


in substrates prepared for biomass production, and
higher in substrates to be used for metabolic
product synthesis.
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The number of substrates in the environment of


the cell is quite high. For this reason, we will use
the concept of limiting substrate to facilitate
operations.

Determination of the restrictive substrate can be


made based on growth cytoichiometry.
Reproduction: Generally, the growth media is prepared
1. Restrictive Substrate:
according to the restrictiveness of a single
component.

That is, increasing the concentration of other


components does not change the rate of
reproduction. However, it is possible for multiple
substrates to limit simultaneous growth.
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• The limiting substrate determined based on the


growth rate may not be the same as the
stoichiometrically limiting component.

• That is: under certain conditions, a substrate may


limit the growth rate, but another compound may
inhibit cell growth in batch culture.
Reproduction:
1. Restrictive Substrate: • The distinction between the growth rate-restricting
substrate and the stoichiometrically restrictive
substrate is often neglected in quantitative
modeling of microbial growth.

• This application causes difficulties when


interpreting bioreactor performance.

• Here we will assume that for the most part, growth


is restricted by a single substrate.
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• Intracellular reactions are divided into


catabolic and anabolic reactions.

• The breaking down of compounds taken from


the environment into smaller compounds is
Reproduction: 2. called catabolism.
Mechanism
of product formation • Catabolism produces the necessary energy for
the cell. The synthesis of cell building blocks
and complex molecules is called anabolism.

• Anabolic reactions are reactions that require


energy, and the energy released during
catabolic reactions is used to drive these
reactions.
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ÿ Exergonic reactions: These


are reactions that give net
energy to the environment .
(Gives energy out.)

ÿ Respiration, O2 -free
respiration (Fermentation)

Biological Energy
Mechanisms
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ÿ Endergonic reactions: These are reactions that take net


energy from the environment .

ÿ All synthesis reactions (oil synthesis, photosynthesis,


ATP synthesis…)
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ÿ Living cell to a miniature chemical factory


similar.

ÿ Intracellular activities by extracting stored energy such as


sugar in the process called cellular respiration
continues.
Biological Energy
ÿ All chemical reactions in the organism
Mechanisms It is called metabolism.

ÿ Management of the cell's material and energy resources •


Reactions are organized into branched metabolic pathways
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ÿ Production of ATP is endergonic. In other words, if we


accept ATP as a substance, energy is required for its formation.
That's why it's endergonic.

ÿ ADP+P+Energy=ATP+H2O

The breakdown of ATP is exergonic . So energy is


released

ÿ ATP+H2O=ADP+P+Energy
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ÿ Production process - Anabolic pathways - The process


of synthesizing new molecules from small molecules
taken into the cell by digestion is called anabolism.

ÿ Destruction process - Catabolic pathways - The


breakdown of large molecules into simple compounds -
The breakdown of substances formed as a result of
anabolism to obtain energy - The cell breaks down the
carbohydrate, lipid and protein molecules it receives from
its environment or in its structure into small molecules.
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ÿ Energy transformations in a substance –


thermodynamics –

ÿ Two laws of thermodynamics;


ÿ 1- Energy cannot be regenerated or destroyed - the energy
of the universe is constant.

ÿ 2- When energy is displaced, entropy (the disorder of the universe)


occurs.
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ÿ Organisms live by expending free energy, –

ÿ Free energy • Energy that does work when the temperature in


a system is uniformly constant

ÿ Chemical reactions according to free energy changes;

ÿ Exergonic reaction - occurs spontaneously


gives out energy.
ÿ Endergonic reaction-energy-absorbing reaction-neural
transmission from its environment.

ÿ Metabolic imbalance - reactions closed in the system


reach equilibrium and do no work.

ÿ The state of imbalance in the cell is the main factor in the


maintenance of cell activities - open system
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ÿ ATP (Adenosine Triphosphate) endergonic


Exergonic reactions with endergonic reactions pairing
= energy for the cell = ATP
The bond between the ATP phosphate groups is broken
by hydrolysis.

ATP ADP (EXERGONIC REACTION) = Energy


is revealed.

• Cells hydrolysis of ATP with the help of specific enzymes


energize directly with endergonic events
It has the ability to match.
• Specific enzymes remove a phosphate group from ATP
they transfer to another molecule and become phosphorylated
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.
Energy production in organisms in general
takes place in stages:
Stage 1: Large molecules are broken down into small
molecules. Proteins are converted to amino acids,
polysaccharides to simple sugars such as glucose, and
fats to glycerol and fatty acids.

Stage 2: These molecules are broken down


Reproduction: 2. into simpler units that play an important role
Mechanism of in metabolism. Most of the sugars, fatty
acids, glycerol and amino acids are
product formation
converted to Acetyl-CoA. Some of the ATP is
produced at this stage
Stage 3: It includes the Citric Acid cycle and oxidative
phosphorylation. Acetyl-CoA brings the acetyl units into the
citric acid cycle, from which they are completely oxidized
to CO2.
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ÿ Four electron pairs from the oxidized acetyl group


Transferred to NAD+ and FAD. Later on
by the transfer of electrons from these carriers to O2
ATP is produced. This step is oxidative phosphorylation.
known as. Most of the ATP
produced in stages.

ÿ About the other half of the carbon source


Reproduction: 2.
used for biosynthetic reactions.
Mechanism of
ÿ Microorganisms form from 95% more
product formation
macromolecules.

Approximately 55% of the cell weight consists of


Proteins, 24% of Nucleic acids and the remaining 3%
of low molecular organic compounds and salts.
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ÿ Experimentally, it has been reported in the literature that the total mass of
the cell is proportional to the total mass of the substrate consumed.
is found.

ÿ Yield: Ratio of substrate amount to biomass amount


Reproduction: is defined as.
3. Yield
ÿ 𝑌x = Δ𝑋
Δ𝑆
ÿ S: Substrate

ÿ X: Biomass
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ÿ If the yield is constant for any case, this relation is


very useful as it allows to calculate the other based
on stoichiometry.
In other words, one of the variables can be calculated
in terms of the other, so one of the variables is
eliminated in the bioreactor design calculations.
Reproduction:
3. Yield
ÿ This stoichiometric correlation is also useful for
monitoring the bioreactor.

ÿ Measuring the substrate concentration means


estimating the cell concentration if the initial values of
both are known.
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ÿ It is easier to measure some product concentrations


leaving the bioreactor (eg CO2).

ÿ In this case, the stoichiometric approach allows one


of the unmeasurable variables to be expressed in
terms of the measurable.
ÿ The stoichiometric ratio may vary depending on the
reproductive rate.
Reproduction:
3. Yield ÿ In order to understand these changes, it is necessary
to know the intracellular metabolic reactions and to
understand in which metabolic events the substrates
are used .
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ÿ Substrates are used in three metabolic pathways:

ÿ 1. Cell synthesis

Reproduction: 3. Yield ÿ 2nd product (extracellular organic compound) synthesis

ÿ 3. energy production
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ÿ Energy obtained during reproduction


ÿ in cell material synthesis,

Reproduction: 3. Yield ÿ In product synthesis

ÿ It is used to perform maintenance


functions.

ÿ Maintenance: keeping the cell alive


The minimum energy required for
(basal metabolism).
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ÿ Carbon source is also energy source for chemotrophs.

ÿ Chemotroph: It is a living thing that provides energy from electrons released by the oxidation
of electron donor/donor molecules in its environment.

ÿ The total substrate consumption can be written as:

ÿ ÿS = ÿDriving + ÿDriving + ÿSmaintenance


Reproduction: 3. Yield
ÿ ÿX/ ÿDuring is defined as efficiency factor.

ÿ ÿDuration = ÿSassimilation + ÿDurationenergy

ÿ ÿX/ ÿAssimilation = coefficient of efficiency

ÿ The coefficient of efficiency is a stoichiometric well-defined quantity


and its value is fairly constant.

ÿ ÿSassimilation: only spent in biosynthetic reactions


is the amount of substrate.

ÿ ÿProcess energy: required to drive biosynthetic reactions


the amount of substrate used to obtain the energy
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ÿ Substrate is more abundant in rapidly reproducing populations.


energy is spent on assimilation and reproduction.

ÿ However, in non-reproducing but active populations


the substrate is spent more on maintenance.

ÿ microorganism substrate yield

ÿ Acetobacter aerogenes maltose 0.46 g/g

ÿ
glucose 0.40 g/g

ÿ Candida utilis acetate 0.36 g/g

ÿ Klebsielle sp. Methanol 0.38 g/g


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ÿ For biological reactions, the substance balance can be


written easily if the composition of the substrate, product,
and cell material is known.

ÿ Another yield is based on ATP. ATP yield is the


amount of biomass synthesized per mole of ATP using
YX/ATP .

ÿ Most heterotrophic organisms have been found to


have ATP yields of 10-11 g/mol ATP under anaerobic
conditions on a variety of substrates.

ÿ For autotrophic (CO2 binding) organisms, this value is


around 6.5 g/mol ATP.
ÿ ATP yield is usually greater than 10.5 under aerobic
conditions.
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ÿ Acetobacter acedi bacterium converts it to acid under


ethanol acetic aerobic conditions.
Using the system immobilized on gelatin particles of
Acetobacter acedi cells .
It is aimed to produce 2 kg of acetic acid per hour
during the fermentation process, which produces
vinegar continuously . The maximum acetic acid
Example 2 concentration that cells can tolerate is 12%. If dry air is
given to the fermenter at a flow rate of 200 mol/h

ÿ A) Minimum ethanol requirement required

ÿ B) The amount of water that must be added to the


alcohol to prevent acid inhibition (poisoning).

ÿ C) Determine the composition of the off-gas of the fermenter and the excess air

find the percentage.


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ÿ Single cell protein production from hexadecane is


recognized by the following reaction. where cCH1,66O0,27N0,2
defines biomass. CO2 production and O2 consumption rate can be measured
Example 3 and it was obtained as 0.43 mol/mol . Determine the stoichiometric coefficients.

ÿ C16H34 + aO2 + bNH3 cCH1,66O0,27N0,2 + dCO2 + eH2O


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ÿ Klebsiella aerogenes is produced from glycerine in


aerobic culture using ammonia as a nitrogen source.
The biomass contains 8% ash and 0.4 g is produced per gram of glycerine
consumption (no metabolic products are formed during this time). Determine

Example 4 the oxygen required for this culture .

ÿ C3H8O3 + aO2 + bNH3 cCH1,75O0.43N0.22 + dCO2 + eH2O

ÿ (glycerin) (K. Aerogenes)


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ÿ Ethyl alcohol can be obtained by anaerobic fermentation of glucose


with both Saccharomyces cerevisia yeast and Zymomonas mobilis
bacteria.
Yeast biomass yield 0.11 g/g; bacteria is 0.05g/g. The nitrogen source for both
organisms is NH3 , and their molecular structures can be taken as CH1,8O0.5N0,2 .

Calculate ethanol yields from glucose for both organisms.


Homework

ÿ C6H12O6 + bNH3 cCH1,8O0.5N0,2 + dCO2 + eH2O + fC2H6O

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