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Chemical Process Calculations: Autumn 2021
Chemical Process Calculations: Autumn 2021
Autumn 2021
Instructor:
Laws of Thermochemistry:
At a given temperature and pressure, the quantity of energy required to decompose a chemical
compound into its elements is precisely equal to that evolved in the formation of that compound
from its elements.
Hence, using this principle, it is possible to calculate the heat of formation of a compound from
a series of reactions not involving the direction formation of the compound from the elements.
the majority of chemical compounds cannot be formed in the pure state directly from the
elements (such as CO):
𝐶 + 𝑂2 = 𝐶𝑂2 ∆𝐻1
𝐶𝑂 + 0.5𝑂2 = 𝐶𝑂2 ∆𝐻2
The heat of combustion of a substance is the heat of reaction resulting from the oxidation
of the substance with molecular oxygen. Note: the heat of combustion is negative.
The standard heat of combustion is that resulting from the combustion of a substance, in the
state that is normal to 25°C and atmospheric pressure, with the combustion beginning and
ending at a temperature of 25°C.
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Energy Balances
Heat of formation:
Species ∆𝑯𝒇
CaC2 (s) -15000 cal
2H2O (l) -68317.4 cal
C2H2 (g) -54182.6 cal
Ca(OH)2 (s) -235800 cal
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Energy Balances
For organic compounds, the standard heat of reaction can be conveniently calculated by using
directly the standard heats of combustion instead of standard heats of formation.
Note:
1. Heat of formation of organic compounds are small in comparison to the heats of combustion
2. Heats of reaction are small in the systems involving only combinations of organic compounds
If ∆𝐻𝑐 is the heat of combustion of this compound corresponding to the final products,
CO2(g), H2O(l), Br(l), Cl2(g), HF(aq), I(s), N2(g), SO2(g), and ∆𝐻𝑓 its heat of formation, then,
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Energy Balances
If ∆𝐻′𝑐 is the heat of combustion of this compound corresponding to the final products,
CO2(g), H2O(l), Br2(g), HCl(aq), I(s), HNO3(aq), H2SO4(aq), and ∆𝐻𝑓 its heat of formation, then,
Ques. 2: Calculate the standard heat of formation for (a) CH3Cl (g) (b) CH3OH (l)
Given: standard heat of combustion, ∆𝐻𝑐 for (a) 182.81 kcal (b) 173.65 kcal
Answer:
𝑎 ∆𝐻𝑓 = 182810−94501.8 1 − 34158.7 3 − 5864.3 1 = −19582 cal
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Energy Balances
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Ques. 4: Calculate the standard heat of reaction at 25°C when gaseous ammonia is dissolved
in water to form 2% by mass of its solution for the generation of weak anion exchanger of
a water treatment plant.
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Energy Balances
For each species associated with the reaction for an unsteady-state, closed system (no
flow in or out):
𝑓𝑖𝑛𝑎𝑙
𝑛𝑖 = 𝑛𝑖 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 + ν𝑖 ε
𝑛𝑖 𝑜𝑢𝑡 = 𝑛𝑖 𝑖𝑛 + ν𝑖 ε
Thus, for a steady-state flow system
= ε σ ν𝑖 ∆𝐻
𝑓,𝑖 = ε∆𝐻𝑟𝑥𝑛
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Energy Balances
X= 0.8
C6H6 (g) , 25°C, 1 atm
C6H12 (g) , 25°C, 1 atm
Reactor
3H2 (g) , 25°C, 1 atm
Solution:
−𝑓 (𝑛𝑖𝐿𝑅 ) −0.8 (1)
ε= = = 0.8
ν𝐿𝑅 −1
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Energy Balances
Calculate heat of reaction for a process in which the reactants enter and products exit
at temperature other than 25°C and 1 atm.
Note: Enthalpy is a state variable (path independent).
Reactants :
{Sensible heats} Products :
∆𝑯 = 𝑯 𝟐𝟓°𝑪 − 𝑯(𝑻𝒊)
∆𝑯 = 𝑯 𝑻 − 𝑯(𝟐𝟓°𝑪)
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Energy Balances
If any slight pressure and mixing effects are ignored, for a steady-state system, the heat of
reaction at temperature T other than the reference temperature is
𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠
∆𝐻𝑟𝑥𝑛 T = 𝑖 25°𝐶 − 𝐻
𝑛𝑖 𝐻 𝑖 𝑇 + ∆𝐻𝑟𝑥𝑛 25°𝐶 + 𝑖 𝑇 − 𝐻
𝑛𝑖 𝐻 𝑖 25°𝐶
𝑖 𝑖
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Energy Balances
Thu 10/28/2021
Ques. 6: Public concern about the increase in the carbon dioxide in the atmosphere has led
to numerous proposals to sequester or eliminate the carbon dioxide. An inventor believes
he has developed a new catalyst that can make the gas phase reaction
proceed with 40% conversion of the CO2. the source of they hydrogen would be from the
electrolysis of water using electricity generated from solar cells. Assume that 1.5mol CO2
enter the reactor at 700°C together with 4 mol of H2 at 100°C. Determine the heat of reaction
if the exit gases leave at 1 atm and 500°C.
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Energy Balances
Compounds 𝒌𝑱 𝒌𝑱
∆𝑯𝒇 ( ) ∆𝑯𝑻𝟐𝟓𝑪 ( )
𝒈𝒎𝒐𝒍 𝒈𝒎𝒐𝒍
25°C 100°C 500°C 700°C
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Energy Balances
The neutralization of a dilute aqueous solution of NaOH with a dilute solution of HCl may
be represented by the following thermochemical equation:
The heat of reaction ∆𝐻25 may be calculated from the respective heats of formation.
Note: The net result of the neutralization of dilute solutions of strong acids and bases is the
production of water from hydrogen and hydroxyl ions. The evolved heat is 13.36kcal/g-mol.
However, in the neutralization of dilute solutions of weak acids and weak bases, the heat
given off is less than 13.36kcal/g-mol.
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Energy Balances
When dilute aqueous solutions of two neutral salts are mixed, there is no thermal effect
provided there is no precipitation, or evolution of gas.
At high temperature, the elementary gases are known to dissociate into their atomic states
with absorption of great amounts of energy. Upon cooling, these monatomic gases rapidly
recombine to form the original molecular gas. An interesting phenomenon of this type is
the association of monatomic hydrogen, H(g), to form molecular gas, H2(g) in the hydrogen
welding process.
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Energy Balances
Q. 7 Chlorinated diphenyl (Diphyl A-30) is heated from 40°C to 280°C at the rate of 4000 kg/h in
an indirectly fired heater. In this particular temperature range, the heat capacity of the
fluid is given by the equation
𝐶𝑙 = 0.7511 + 1.465 ∗ 10−3 𝑇 𝑘𝐽/ 𝑘𝑔. 𝐾
Also, the heat capacity data of Diphyl A-30 at 40°C and 280°C are 1.1807 and 1.5198 kJ/(kg.K),
respectively.
Calculate the heat to be supplied to the fluid in the heater using the heat capacity equation.
Also, calculate the %error involved in using the mean heat capacity data for the heat
change calculations.
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Energy Balances
Q. 8 Obtain an expression relating the heat of reaction and the temperature of the reaction
∆𝐻𝑟0 = −98910𝑘𝐽/𝑚𝑜𝑙
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Q. 9 Acetic acid is esterified in the liquid phase with ethanol at 100C and atmospheric pressure
to produce ethyl acetate and water.
∆𝐻𝑟0 = −4.43𝑘𝐽/𝑚𝑜𝑙
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