Material Balances on Reactive Systems

Fundamentals of Chemical Processes for Energy and Environment

Energy Engineering – Politecnico di Milano
Prof. Alessandro Donazzi
[email protected]
 Chemical Reaction Stoichiometry

Stoichiometry: theory of relative quantities of reactants and products in chemical reactions

Atomic weight (mass): relative mass of an atom weighted on a scale which assigns a value of 12 to the mass

of the 12C isotope of carbon. The molecular weight of a chemical species is the sum of the atomic weights of all

its atoms. E.g.: the atomic weight of O (atomic oxygen) is 16, hence the molecular weight of molecular oxygen

(O2) is equal to 32.

Mole: the amount of a chemical species having a mass expressed in grams equal to its molecular weight : one

mole of O2 corresponds to 32 g of oxygen. One mole of any chemical species contains a constant number,

6.022x1023 (Avogadro number), of molecules. For molecular species with ideal gas behavior moles are also

proportional to volumes at given T and P through the state equation: V = nRT/P

 Chemical Reaction Stoichiometry

Example: stoichiometry equation

2 H2 + O2  2 H2O

2 moles (2 molecules) or 4 g of hydrogen (MM = 2 g/mole) react with 1 mole (1 molecule) or 32 g of oxygen

(MM = 32 g/mole) producing 2 moles (2 molecules) or 36 g of water (MM = 18 g/mole). The numbers before

the chemical formulas of any species are the stoichiometric coefficients which define the relative quantities of

reactants and products involved in the chemical reaction.

The stoichiometry is balanced when all atomic balances are closed, i.e. when reactants and products contain

the same number of atoms of each chemical element (atoms are not transformed in chemical reactions),

consequently the law of conservation of mass is respected (36 g = 36 g). Conversely the number of mole can

change (from 3 to 2 mole in the given example).

 Combustion chemistry

Chemical reactions under stoichiometric control can proceed up to completion (i.e. up to total consumption of

all the reactants) only when the reactants are supplied in stoichiometric amounts. If deviations from the

stoichiometric ratio occur, only the limiting reactant, which is supplied in amounts lower than the

stoichiometric one, can be completely consumed. Other species cannot and are defined excess reactants.

Fuel: any chemical substances that, under appropriate conditions, can react with an oxidant, usually O2,

releasing a large amount of energy.

Combustion (complete combustion, total oxidation): reaction with oxygen of all combustible species in a

fuel. Complete combustion is achieved when carbon (C) is totally converted into carbon dioxide (CO2),

hydrogen (H) into water, sulfur into sulfurous dioxide (SO2) and nitrogen (N) into molecular nitrogen:

C + O2  CO2 2 H + ½ O2  H2O S + O2  SO2 2 N  N2

 Combustion chemistry

Incomplete combustion (partial combustion) occurs when unconverted fuel and/or carbon monoxide (CO)

are present in the products.

Atmospheric air is typically used as source of oxygen in most of combustion processes. Molar composition of

dry air is:

1
Species % molar NSpecies
 NSpecies i 
N2 78.03% MM mixture   yi  MM i    
i  i MM i 
O2 20.99%
Ar 0.94% yi molar fraction, ωi weight fraction
CO2 0.03%
H2, He, Ne, Kr, Xe 0.01%

For practical purposes, the following approximation applies:

79% N2, 21% O2

nair / n O2 = 4.76; mair / mO2 = 4.31

MMair = 28.96 g/mol

 Combustion chemistry

Theoretical oxygen: is the stoichiometric amount of O2 required to achieve complete fuel combustion.

Theoretical air is defined as the amount of air which contains the theoretical oxygen.

Stoichiometric air to fuel ratio (αst): air mass to fuel mass stoichiometric ratio (stoichiometric air supply ratio).

Air to fuel ratio (α): air mass to fuel mass effective ratio.

Percent excess combustion air:

   st
e%   100
 st
 e% 
   st  1  
 100 

Comments: 1) the theoretical air (or the stoichiometric air to fuel ratio) required for complete fuel combustion

only depends on the fuel composition, but not on the actual amount of burned fuel; 2) the percent excess

combustion air only depends on theoretical and effective amount of air, but not on the oxygen consumption, i.e.

an appropriate α is a necessary but not sufficient condition for complete combustion.

 Combustion chemistry

Starting from the elemental composition of the fuel, provided as weight percentages of hydrogen (H), carbon

(C), sulfur (S) and oxygen (O), the stoichiometric air to fuel ratio can be obtained as follows:

2 H +1/2 O2  H2O
 st  4.31
 2.667  C %  8  H %  S %  O %  kg DryAir
2 g + 16 g = 18 g  16/2 = 8 100 kg Fuel

C + O2  CO2

12 g + 32 g = 44 g  32/12 = 2.667

S + O2  SO2

32 g + 32 g = 64 g  32/32 = 1

The choice of the percent excess of combustion air depends on several factors: 1) fuel nature, being lower (5 –

20%) for gaseous and liquid fuels, and higher for solid fuels; 2) the type of combustion systems. The

combustion temperature decreases on increasing the excess of air, resulting in lower material stress and lower

noxious emissions (until a lowest limit is reached).

 Heterogenous fuels

Coal has an extremely complex chemical structure, which includes both organic (macerals) and inorganic

(minerals) components. From a practical viewpoint, simple and fast characterization techniques are needed:

the ultimate (elemental) analysis determines the weight fractions of H, C, S, O, N; the proximate

analysis determines the content of volatiles, fixed carbon, moisture and ash.

Sub-
Peat Lignite Bituminous Coal Anthracite
bituminous Coal

Humidity (total basis) >75 38.7 31.2 3.7 1.0

Ultimate analysis
Dry & Ash Free Basis –
% weight fraction

C 58.2 71.4 73.4 82.6 92.2

H 5.63 4.79 4.86 4.97 3.30

N 1.94 1.34 1.16 1.55 0.15

S 0.21 0.60 0.31 1.50 0.98

O 34.02 21.87 20.27 9.38 3.37

Lower Heating Value

23.5 28.5 29.4 30.6 35.7
DAF basis (MJ/kg)
 Material balances on reactive systems

Mass balances of reacting system are an application of the mass conservation law. Considering a

macroscopic control volume and assuming steady state conditions (no accumulation term) the formal

expression of the mass balance is:

Mass (molar) flow out – Mass (molar) flow in = Generation

When either total mass or atomic species are considered, the generation term is null according to the

conservation law of mass (and atoms). This is not the case when considering either the total molar flow or the

i-th species molar (and mass) flow, which can change when chemical reactions occur. The relative

consumption/generation quantities of reactants/products are described by reaction stoichiometries, which

implicitly satisfy the conservation law of atoms and total mass.

To solve mass balances we need: i) the stoichiometries of reactions, necessary to describe the chemical

evolution of the system; ii) the conversion of the limiting reactants; iii) the selectivity towards the desired

products. The problem is solved starting from an arbitrary calculation basis (e.g. 1 mole or 1 kg of fuel), which

should be conveniently chosen to ease the calculations.

 Conversion, Selectivity and Yield

Considering the general reaction:

 A A  B B  ...   P P   Q Q  ...
The conversion cA of the reactant A is defined as:

n A,reacted n inA  n out

cA   A

n inA in
nA

with nA = number of moles of A.

The selectivity of the product P with reference to the reactant A is defined as:
nP , formed
P nPout  nPin  A
 
P
 in 
nA  nA  P
A
n A, reacted out

A
The yield of product P with respect to the reactant A is defined as:

nP , formed
P nPout  nPin  A
 
P
   c A   AP
A
n inA nAin
P
A