2.

6 PHYSICAL AND CHEMICAL PROPERTY DATA

Some handbooks of physical and chemical data, including:

• International Critical Tables

• CRC Handbook of Chemistry and Physics
• Lange’s Handbook of Chemistry

To these can be added:

• Perry’s Chemical Engineers’ Handbook

and, for information about biological materials:

• Biochemical Engineering and Biotechnology Handbook

2.7 STOICHIOMETRY

In chemical or biochemical reactions, atoms and molecules rearrange to form new

groups. Mass and molar relationships between the reactants consumed and products
formed can be determined using stoichiometric calculations.

As an example, consider the principal reaction in alcohol fermentation: of glucose to

ethanol and carbon dioxide:
C 6 H 12 O6 → 2C 2 H 6 O+2CO 2

This reaction equation states that one molecule of glucose breaks down to give two
molecules of ethanol and two molecules of carbon dioxide. Applying molecular weights,
the equation also shows that reaction of 180g glucose produces 92g ethanol and 88g
carbon dioxide.

During chemical or biochemical reactions, the following two quantities are conserved:
1. Total mass, so that total mass of reactants 5 total mass of products
2. Number of atoms of each element, so that, for example, the number of C, H, and O
atoms in the reactants 5 the number of C, H, and O atoms, respectively, in the products

Note: there is no corresponding law for conservation of moles: the number of moles of
reactants is not necessarily equal to the number of moles of products.

EXAMPLE 2.4 STOICHIOMETRY OF AMINO ACID SYNTHESIS

The overall reaction for microbial conversion of glucose to L-glutamic acid is:

C 6 H 12 O6 + NH 3 +1.5 O2 → C5 H 9 NO 4 +CO 2+ 3 H 2 O
(glucose) (glutamic acid)
Required: What mass of oxygen is required to produce 15 g glutamic acid?

Solution:

Molecular weights:
• Oxygen = 32
• Glutamic acid =147

Because stoichiometric equations give relationships between moles, g glutamic acid is

first converted to gmol using the unity bracket for molecular weight:

15 g glutamic acid=15 g glutamic acid ∙ |147 g glutamicic acid |

1 gmol glutamic acid
=0.102 gmol glutamic acid

According to the reaction equation, production of 1 gmol of glutamic acid requires 1.5
gmol O2. Therefore, production of 0.102 gmol glutamic acid requires (0.102×1.5)=0.153
gmol O2. This can be expressed as mass of oxygen using the unity bracket for the
molecular weight of O2:

0.153 gmol O 2=0.153 gmolO 2 ∙ |

32 g O 2
1 gmol O 2 |
=4.9 g O 2

Therefore, 4.9 g oxygen is required. More oxygen will be needed if microbial growth also
occurs

Chemical reactions equations suggest that all the reactants are converted into the products
specified in the equation, and that the reaction proceeds to completion. This is often not
the case for industrial reactions. Because the stoichiometry may not be known precisely,
or in order to manipulate the reaction beneficially, reactants are not usually supplied in
the exact proportions indicated by the reaction equation. Excess quantities of some
reactants may be provided; this excess material is found in the product mixture once the
reaction is stopped.Several terms are used to describe partial and branched reactions.

1. The limiting reactant or limiting substrate is the reactant present in the smallest
stoichiometric amount. While other reactants may be present in smaller absolute
quantities, at the time when the last molecule of the limiting reactant is consumed,
residual amounts of all reactants except the limiting reactant will be present in the
reaction mixture.
As an illustration, for the glutamic acid reaction of Example 2.4, if 100 g glucose, 17 g
NH3, and 48 g O2 are provided for conversion, glucose will be the limiting reactant even
though a greater mass of it is available compared with the other substrates.

2. An excess reactant is a reactant present in an amount in excess of that required to

combine with all of the limiting reactant. It follows that an excess reactant is one
remaining in the reaction mixture once all the limiting reactant is consumed.
The percentage excess is calculated using the amount of excess material relative to the
quantity required for complete consumption of the limiting reactant:
( moles present −moles required ¿ react ¿¿ completely withthe limiting reactant )
%excess= ×100
( moles required ¿ react ¿¿ completely with the limitingreactant )
or
( mass present − mass required ¿ react ¿¿ completely with the limiting reactant )
%excess= ×100
( mass required ¿ react ¿¿ completely withthe limitingreactant )

The required amount of a reactant is the stoichiometric quantity needed for complete
conversion of the limiting reactant.
Preceding glutamic acid example: the required amount of NH3 for complete
conversion of 100 g glucose is 9.4 g; therefore, if 17g NH3 are provided, the percent
excess NH3 is 80%. Even if only part of the reaction actually occurs, required and excess
quantities are based on the entire amount of the limiting reactant.

Other reaction terms are not as well defined, with multiple definitions in common
use:

3. Conversion is the fraction or percentage of a reactant converted into products.

4. Degree of completion is usually the fraction or percentage of the limiting reactant

converted into products.

5. Selectivity is the amount of a particular product formed as a fraction of the amount that
would have been formed if all the feed material had been converted to that product.

6. Yield is the ratio of mass or moles of product formed to the mass or moles of reactant
consumed. If more than one product or reactant is involved in the reaction, the
particular compounds referred to must be stated.
Example: the yield of glutamic acid from glucose was 0.6g g− 1 . Because of the
complexity of metabolism and the frequent occurrence of side reactions.

EXAMPLE 2.5 INCOMPLETE REACTION AND YIELD

Depending on culture conditions, glucose can be catabolised by yeast to produce ethanol
and carbon dioxide, or can be diverted into other biosynthetic reactions. An inoculum of
yeast is added to a solution containing 10 g1−1 glucose. After some time, only 1g 1−1
glucose remains while the concentration of ethanol is 3.2 g 1−1 .

Determine:
a. The fractional conversion of glucose to ethanol
b. The yield of ethanol from glucose

Solution:
a. To find the fractional conversion of glucose to ethanol, we must first determine how
much glucose was directed into ethanol biosynthesis. Using a basis of 1 litre, we can
calculate the mass of glucose required for synthesis of 3.2 g ethanol. First, g ethanol is
converted to gmol using the unity bracket for molecular weight:

3.2 g ethanol=3.2 g ethanol ∙ |146gmolg ethanol

ethanol
|=0.0070 gmol ethanol
According to Eq. (2.36) for ethanol fermentation, production of 1 gmol of ethanol
requires 0.5 gmol glucose. Therefore, production of 0.070 gmol ethanol requires (0.070×
0.5) = 0.035 gmol glucose. This is converted to g using the molecular weight unity
bracket for glucose:

0.035 gmol glucose=0.035 gmol glucose ∙ |1180gmolg glucose

glucose|
=6.3 g glucose

Therefore, as 6.3 g glucose was used for ethanol synthesis, based on the total amount of
glucose provided per litre (10 g), the fractional conversion of glucose to ethanol was
0.63.
Based on the amount of glucose actually consumed per litre (9 g), the fractional
conversion to ethanol was 0.70.

b. Yield of ethanol from glucose is based on the total mass of glucose consumed. Since
9g glucose was consumed per litre to provide 3.2 g l21 ethanol, the yield of ethanol from
glucose was 0.36 g g21 . We can also conclude that, per litre, (9 2 6.3) 5 2.7 g glucose
was consumed but not used for ethanol synthesis.

2.8 METHODS FOR CHECKING AND ESTIMATING RESULTS

Professional engineers and scientists develop the habit of validating the outcomes of
their mathematical analyses and calculations, preferably using independent means.
Several approaches for checking and estimating results are available.

1. Ask yourself whether your answer is reasonable and makes sense. In some cases,
judging whether a result is reasonable will depend on your specific technical
knowledge and experience of the situation being examined. For example, you may find
it difficult at this stage to know whether or not 2 ×1012 is a reasonable value for the
Reynolds number in a stirred bioreactor. Nevertheless, you will already be able to judge
the answers from other types of calculation.

2. Simplify the calculation and obtain a rough or order-of-magnitude estimate of the

answer.Instead of using exact numbers, round off the values to integers or powers of 10,
and continue rounding off as you progress through the arithmetic. If the estimated answer
is of the same order of magnitude as the result found using exact parameter values, you
can be reasonably sure that the exact result is free from gross error.
EXAMPLE 2.6 ORDER-OF-MAGNITUDE CALCULATION

The impeller Reynolds number ℜi for fluid flow in a stirred tank is defined as:
2
N i Di ρ
ℜi =
μ
ℜi was calculated as 1.10 ×105 for the following parameter values: N i=¿ 30.6 rpm,
D i=¿ 1.15 m, ρ=1015 kg m−3, and μ=6.23× 10−3 kg m−1 s −1 . Check this answer using
order-of-magnitude estimation.

Solution:
The calculation using exact parameter values:

ℜi =
| 60 s |
( 30.6 min−1 ) ∙ 1 min ∙ ( 1.15 m )2 ( 1015 kg m −3 )
6.23 ×10− 3 kg m−1 s −1

can be rounded off and approximated as:

ℜi =
| 60 s |
( 30.6 min−1 ) ∙ 1 min ∙ ( 1 m)2 ( 1× 103 kg m−3 )
−3 −1 −1
6 × 10 kg m s

Combining values and canceling units gives:

0.5 × 106 0.6 ×106
ℜi = ≈ =0.1 ×106 =105
6 6

This calculation is simple enough to be performed without using a calculator. As the

rough answer of 105 is close to the original result of 1.10 3 105 , we can conclude that no
gross error was made in the original calculation.

Note: Units must still be considered and converted using unity brackets in
order-of-magnitude calculations.

The following methods for checking calculated results can also be used.

3. Substitute the calculated answer back into the equations for checking.
For example, If ℜi (Example 2.6) was determined as 1.1 ×105 , this value could be used
to back-calculate one of the other parameters in the equation such as ρ:
ℜi μ
ρ= 2
N i Di
If the value of ρ obtained in this way is 1015 kg m−3 , we would know that our result
for ℜi was free of accidental calculator error.

4. If none of the preceding approaches can be readily applied, a final option is to check
your answer by repeating the calculation from the beginning. This strategy has the
disadvantage of using a less independent method of checking, so there is a greater chance
that you will make the same mistakes in the checking calculation as in the original.

Note: Methods 2 through 4 only address the issue of arithmetic or calculation mistakes.
Your answer will still be wrong if the equation itself contains an error or if you are
applying the wrong equation to solve the problem. You should check for this type of
mistake separately. If you get an unreasonable result as described in method 1 but find
you have made no calculation error, the equation is likely to be the cause.