Processes with Chemical Reactions

In chemical reactions, one or more substances (reactants) are converted to one or more different
substances (products). Substances are either chemical elements or compounds. A chemical
reaction rearranges the constituent atoms of the reactants to create different substances as products.
Stoichiometry is used to estimate reactant and product quantities.

By successful completion of this lesson, the student will be able

1. Apply mass and heat balances to solve problems involving chemical reactions

Stoichiometry:
When chemical reactions occur, it is usually required to predict the mass or moles needed for the
reaction(s), and the mass or moles of each species remaining after the reaction has occurred.
Reaction stoichiometry allows us to accomplish this task. Stoichiometry provides a quantitative
means of relating the amount of products produced by chemical reactions to the amount of
reactants.

The numbers that are precede the chemical substances involved in the chemical reaction equation
are known as “stoichiometric coefficients". These coefficients represent quantity of any reactant
that is theoretically required for complete conversion of other reactants. As an example, the
reaction of nitrogen and hydrogen to produce ammonia:
N2 + 3H2 → 2NH3.
The values in front of elements (1, 3 and 2) are the stoichiometric coefficients.

Balanced chemical equations are used to estimate the masses of reactants and the masses of
products.

Hess's Law
The Hess’s Law is important for estimating energies involve in chemical reactions. The heat of
any reaction ∆𝐻𝑓 for a specific reaction is equal to the sum of the heats of reaction for any set of
reactions which in sum are equivalent to the overall reaction:

The pictorial view of Hess's Law as applied to the heat of equation is illustrated, below.

∆𝐻𝑟 = −∆𝐻𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 + ∆𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠

∆𝐻𝑟 = −(−483.6) + (−393.5) kJ
∆𝐻𝑟 = 90.1 kJ

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Standard Heats of Formation
The standard enthalpy of formation ∆𝐻𝑓0 of a compound is defined as the enthalpy change when
one mol of the compound is formed from its constituent elements in the standard state. The
enthalpy of formation of the elements is taken as zero. The standard condition is 25º C temperature
and 1 atm pressure.

The standard heat of any reaction can be calculated from the heats of formation ∆𝐻𝑓0 of the products
and reactants; if these are available or can be estimated.

Heats of Combustion
The heat of combustion of a compound ∆𝐻𝑐0 is the standard heat of reaction for complete
combustion of the compound with oxygen. Heats of combustion are relatively easy to determine
experimentally. The heats of reactions can be easily calculated from the heats of combustion of
the reactants and products.
The general expression for the calculation of heats of reaction from heats of combustion is
0 0
∆𝐻𝑟0 = ∑ ∆𝐻𝑐,𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 − ∑ ∆𝐻𝑐,𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
0 0
where ∆𝐻𝑐,𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 is the heat of combustion of reactants at standard condition and ∆𝐻𝑐,𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
is the heat of combustion of products at standard condition.

Note: For compounds containing nitrogen, the nitrogen will not be oxidized to any significant
extent in combustion and is taken to be unchanged in determining the heat of combustion.
Caution: The Heats of combustion are large compared with heats of reaction. Do not round off the
numbers before subtraction; round off the difference.

Calorific Value
The calorific value of a fuel is the quantity of heat obtained per kilogram (for solids and liquids)
or per cubic meter (for gases) when the fuel is burnt with an excess amount of oxygen in
a calorimeter. If H2O is present in the products of combustion as a liquid, then the ‘higher calorific
value’ (HCV) is obtained (i.e., the heat of condensation is also accounted). If the H2O is present
as a vapour then the ‘lower calorific value’ (LCV) is obtained.

Higher Calorific Value (or Gross Calorific Value or Higher Heating Value): the water of
combustion is entirely condensed and that the heat contained in the water vapor is recovered.

Lower Calorific Value (or Net Calorific Value or Lower Heating Value): the products of
combustion contain the water vapor and that the heat in the water vapor is not recovered.

Dulong’s Formulae for theoretical calculation of Calorific Value

1   O 
GCV  8080  C   34500   H    2240  S  , kCal/kg of the fuel
100   8 
where C, H, O and S are percentage of carbon, hydrogen, oxygen and Sulphur, respectively.
NCV  GCV 
1
9  H  587  M , kCal/kg of the fuel
100
where M is the moisture % in the fuel
2
 Examples

Q1. Given a simple chemical equation with the variables A, B and C representing different
compounds:
A+B ⇋ C
and the standard enthalpy of formation values:
ΔHfo[A] = 433 KJ/mol
ΔHfo[B] = -256 KJ/mol
ΔHfo[C] = 523 KJ/mol
Estimate the standard enthalpy change of formation.

Solution:
The equation for the standard enthalpy change of formation is as follows:
ΔHreactiono = ΔHfo[C] - (ΔHfo[A] + ΔHfo[B])

ΔHreactiono = (1 mol)(523 kJ/mol) - ((1 mol)(433 kJ/mol) + (1 mol)(-256 kJ/mol)\)

Because there is one mole each of A, B and C, the standard enthalpy of formation of each reactant
and product is multiplied by 1 mole, which eliminates the mol denominator:
ΔHreactiono = 346 kJ

The standard enthalpy change of formation for the creation of component "C" 346 kJ/mole of C.

Q2. Consider the formation of chlorine trifluoride from chlorine monofluoride and fluorine:
ClF(g)+F2(g)→CIF3(g)
What is the ΔH∘ for the desired reaction?

Data
Number Reaction ΔH∘ (kJ)
1 2 OF2(g) → O2(g) + 2 F2(g) -49.4
2 2 ClF(g) + O2(g) → Cl2O(g) + OF2(g) 214.0
3 ClF3(g) + O2(g) → ½ Cl2O(g) + 3/2 OF2(g) 236.2

Solution:
Step 1: Determine what reaction will give us ClF in the reactants.
Since ClF(g) is needed as a reactant, we can multiply reaction 2 by 1/2 to obtain:
ClF(g)+1/2 O2(g)→1/2 Cl2O(g)+1/2 OF2(g)
ΔH∘=1/2(214.0kJ) =107.0.kJ

Step 2: Determine what reaction will give us F2 in the reactants.

Since F2 is needed as a reactant, we can multiply reaction 1 by -1/2 to obtain:
F2(g)+1/2 O2(g)→OF2(g)
ΔH∘=−1/2(−49.4kJ) =24.7kJ
3
Step 3: Determine what reaction will give us ClF3 as a product.
Since ClF3 is needed as a product, we can multiply reaction 3 by -1 to obtain:
½ Cl2O(g)+3/2 OF2(g)→ClF3(g)+O2(g)
ΔH∘=−(236.2kJ) =−236.2kJ

Step 4: Add the reactions up to ensure that the desired reaction is obtained:
ClF(g)+1/2 O2(g)→1/2 Cl2O(g)+1/2 OF2(g)
F2(g)+1/2 O2(g)→OF2(g)
½ Cl2O(g)+3/2 OF2(g)→ClF3(g)+O2(g)
↓(+)
ClF(g)+F2(g)→ClF3(g)

Step 5: Add up all the manipulated heat of reactions to obtain the desired ΔH∘
ΔH∘= (107.0+24.7) − 236.2 kJ
ΔH∘ = −104.5kJ

4
Problems

1. In the combustion of heptane (C7H16), CO2 and water vapour are produced. Dry ice can be
produced by cooling and solidifying CO2. Assume that you are asked to produce 500 kg of dry
ice per hour, and that 50% of the CO2 produced in the combustion can be converted into dry
ice. How many kilograms of heptane must be burned per hour?

2. A limestone analyses is given below:

Components weight %
CaCO3 92.89
MgCO3 5.41
Inert 1.70

By heating the limestone, oxides known as lime can be recovered. If the oxidation formation
is complete, estimate;
(a) how many kilograms of calcium oxide (CaO) can be made from 1 ton of this limestone?
(b) how many kilograms of CO2 can be recovered per 1 ton of limestone?
(c) how many kilograms of limestone are needed to make 1 ton of lime?

Additional Data
The chemical reactions involve in the process are:
CaCO3 → CaO + CO2
MgCO3 → MgO + CO2

Molecular masses of Ca, Mg, C and O are 40.08, 24.31, 12.01 and 16.00 kg/kmol, respectively.

3. Calculate the heat of reaction for the synthesis of ammonia from hydrogen and nitrogen at 150
0
C.
N 2  3H 2  2 NH 3

a) Standard heat of formation of ammonia is ∆𝐻𝑓0 = - 46107 kJ/mol.

b) Specific heat capacities of hydrogen, nitrogen and ammonia are 29.25 kJ/mol.K, 29.22
kJ/mol.K and 37.32 kJ/mol.K, respectively.

5
4. Calculate the theoretical flame temperature of a gas having 80% CO and 20% N2 when burnt
with 150% excess air. Both air and gas being at 25 0C. The percentage values are given in mole
basis.

Data:
Heat of formation of CO2 = -94,052 Cal/mole
Heat of formation of CO = -26,412 Cal/mole
Specific heat capacities:
CO2 = 12.1 Cal/mol.K, O2 = 7.9 Cal/mol.K, N2 = 7.55 Cal/mol.K,

5. A furnace burns liquid coal tar fuel derived from a coke oven at a rate of 100 kg/h. Calculate
the heat transferred in the furnace if the combustion gasses leave at 1500 K. Burners operate
with 20% excess air. The fuel supply temperature is 50 0C and the combustion air temperature
is 15 0C. Air contains 23% of oxygen and 77%of nitrogen by weight.

The properties of coal fuel are given as follows:

Composition: C = 87.5 % (w/w); H2 = 8.0 % (w/w); O2 = 3.5 % (w/w);
N2 = 1.0 % (w/w); S (trace)
Net calorific value = 39,540 kJ/kg
Latent heat of vaporization of liquid coal tar = 35 kJ/kg
Specific heat capacity of liquid coal tar = 1.6 kJ/kg.K

C p0 values of gasses in kJ/kmol.K; C p0  A  BT  CT 2  DT 3

Component A B C D
CO2 19.763 7.332x10-2 -5.518x10-5 17.125x10-9
H2O 32.190 19.207x10-2 10.538x10-6 -3.591x10-9
O2 28.06 -3.674x10-2 17.431x10-6 -10.634x10-9
N2 31.099 -1.354x10-2 26.752x10-6 -11.662x10-9

6. Benzene is hydrogenated to produce cyclohexane in a reactor. Calculate the standard heat of

reaction for the hydrogen at reaction given below:
C6H6 (g) + 3 H2 (g) C6H12 (g)

Heats of combustion of C6H6 (g), C6H12 (g), and H2 (g) are given
C6H6 (g) + 7.5 O2 (g) 6 CO2 (g) + 3 H2O (l); H c0  3287 .4kJ
C6H12 (g) + 9 O2 (g) 6 CO2 (g) + 6 H2O (l); H c0  3949 .2kJ
H2 (g) + 0.5 O2 (g) H2O (l); H c0  285 .58kJ

Note: The standard state of water for heats of combustion is liquid.

(for additional support, refer

https://www.youtube.com/watch?app=desktop&v=Xe_N7WYl5BI)

6
7
 Model solution

Air Wt.% kg
Q6. O2 23 293.8*1.2 = 352.6 kg
N2 77 (77/23)*352.6 = 1180.4 kg

Furnace

50 0C

Coal tar Wt.% kg Coal tar Wt.% kg kmole

C 87.5 87.5 CO2 87.5 (44/12)*87.5 = 320.8 320.8/44 = 7.3
H2 8.0 8.0 H2O 8.0 (18/2)*8 = 72.0 72/18 = 4.0
O2 3.5 3.5 O2 3.5 [(32/12)*87.5+(16/2)*8] 58.8/32 = 1.8
N2 1.0 1.0 -3.5 = 293.8
N2 1.0 1180.4 + 1 = 1181.4 kg 1181.4/28 = 42.2

Stoichiometric relationships:
𝐶 + 𝑂2 → 𝐶𝑂2
12 + 32 → 44

𝐻2 + 1⁄2 𝑂2 → 𝐻2 𝑂
2 + 16 → 18

Estimation of air requirement by balancing masses

Theoretical O2 requirement = [(32/12)*87.5+(16/2)*8] = 297.3 kg
Theoretical amount of O2 to be supplied = 297.3 – 3.5 = 293.8 kg
Actual amount of O2 to be supplied = 293.8*1.2 = 352.6 kg
N2 in the air = (77/23)*352.6 = 1180.4 kg

Estimation Flue gas composition by balancing masses

CO2 in the flue gas = (44/12)*87.5 = 320.8 kg = 320.8/44 =7.3 kmole
H2O in the flue gas = (18/2)*8 = 72.0 kg = 72/18 = 4.0 kmole
O2 in the flue gas = 352.6 - 293.8 = 58.8 kg = 58.8/32 = 1.8 kmole
N2 in the flue gas = 1180.4 + 1,o = 1181.4 kg = 1181.4/28 = 42.2

Estimation of Energy quantities (Reference temperature 25 0C, Basis of calculation: per hour)

Heat in the feed = 100 × 1.6 × (50 − 25) = 4000.0 kJ

Heat liberated = 100 × 39540 = 3954000.0 kJ
8
 1500
Heat in flue gas = ∑41 {∫298 𝑚 × 𝐶𝑝 × 𝑑𝑇} =
1500
= ∑41 {∫298 𝑚𝑖 × (𝐴𝑖 + 𝐵𝑖 𝑇 + 𝐶𝑖 𝑇 2 + 𝐷𝑖 𝑇 3 ) × 𝑑𝑇}
𝐵 𝐶 𝐵
= ∑41 {𝑚𝑖 × {[𝐴𝑖 × |𝑇|1500 𝑖 2 1500 𝑖 3 1500 𝑖 4 1500
298 ] + [ 2 × |𝑇 |298 ] + [ 3 × |𝑇 |298 ] + [ 4 × |𝑇 |298 ]}}

7.332×10−2 −5.518×10−5
= 7.3 × {[19.763 × (1500 − 298)] + [ × (15002 − 2982 )] + [ ×
2 3
17.125×10−9
(15003 − 2983 )] + [ × (15004 − 298 4 )]}
4
19.207×10−2 10.538×10−6
+ 4.0 × {[32.190 × (1500 − 298)] + [ × (15002 − 2982 )] + [ ×
2 3
−3.591−9
(15003 − 2983 )] + [ × (15004 − 2984 )]}
4
−3.674×10−2 17.431×10−6
+ 1.8 × {[28.06 × (1500 − 298)] + [ × (15002 − 2982 )] + [ ×
2 3
−10.634×10−9
(15003 − 2983 )] + [ × (15004 − 2984 )]}
4
−1.354×10−2 26.752×10−6
+ 42.2 × {[31.099 × (1500 − 298)] + [ × (15002 − 2982 )] + [ ×
2 3
−11662×10−9
(15003 − 2983 )] + [ × (15004 − 2984 )]}
4

=
1500 1500
Component A B B D ∫ 𝐶𝑃 𝑑𝑡 𝑚∫ 𝐶𝑃 𝑑𝑡
298 298
CO2 1.98E+01 7.33E-02 -5.52E-05 1.71E-08 63033.9 459622.1
H2 O 3.22E+01 1.92E-01 1.05E-05 -3.59E-09 253467.4 1013869.4
O2 2.81E+01 -3.67E-02 1.74E-05 -1.06E-08 45.4 83.3
N2 3.11E+01 -1.35E-02 2.68E-05 -1.17E-08 37873.0 1598028.5

= 3071603.3 kJ

Heat consumed for evaporation = 100 × 35 =3500 kJ

Apply heat balance (assuming steady state):

In + Gen = Out + Con+ Acc+ Loss
4000.0 + 3954000.0 = 3071603.3 + 3500.0 + 0.0 + Q
Q = 882,896.7 kJ/h