LESSON 04: THERMOCHEMISTRY
Unit 03: Heat of Reaction
Introduction:
In the previous lesson, it was established that the internal energy and enthalpy of a system is
related to both work and heat that is applied either by or to the system. In addition, the work
component of the system, particularly on the concept of the PV-work, was elaborated. In this
lesson, the HEAT component is put into focus particularly on combustion reactions which is the
focus of the study on the relationship of fuels and energy.
Lesson Objectives:
After successful completion of this lesson, the students are expected to:
1) Differentiate constant pressure and constant volume processes.
2) Interpret thermochemical equations and enthalpy diagrams properly.
3) Solve problems involving Hess Law of Heat Summation.
4) Demonstrate an ability to solve involving enthalpies of reaction.
Course Materials:
Heats of Reaction
The Heat of Reaction pertains to the amount of energy that accompanies a chemical reaction.
They can either be equivalent to the internal energy or the enthalpy of reactions, depending on
the circumstances:
A. Heat Of Reaction At Constant Volume:
Consider a mechanical reversible non-flow process at constant V
B. Heat Of Reaction At Constant Pressure:
Consider a mechanical reversible non-flow process at constant P
C. Heat Of Reaction Of Solids And Liquids At Very Low Pressure:
D. Heat Of Reaction Of Ideal Gases At Constant Pressure:
Note:
A positive value of ΔH and ΔE shows that heat is absorbed during the process while
A negative value of ΔH and ΔE shows that heat is liberated during the process.
However, since most of the reactions that are considered in our study of thermochemistry are
done under constant pressure:
The Heat of Reaction is synonymous as the Enthalpy of the Reaction; hence, ΔH,
instead of ΔE.
Thermochemical Equations and Enthalpy Diagrams:
Thermochemical Equations are balanced chemical equations that show the associated
enthalpy changes.
When dealing with Thermochemical Equations, there are important notes that are needed to be
considered:
1. Enthalpy is an extensive property.
2. The enthalpy change for a reaction is equal in magnitude, but opposite in sign, to ΔH for
the reverse reaction.
3. The enthalpy change in a reaction depends on the states of the products and reactants.
Enthalpy Diagrams
Show changes in enthalpy of a chemical reaction as the chemicals move from reactants
to products and vice versa
Figure 1: Enthalpy diagram of the combustion of methane. Image Source: Brown, 2011
A positive value of ΔH shows an endothermic reaction, while a negative value of ΔH shows that
a reaction is exothermic.
Sample Problem 1:
Ozone, O3(g), is a form of elemental oxygen that is important in the absorption of ultraviolet
radiation in the stratosphere. It decomposes to O2(g) at room temperature and pressure
according to the following reaction:
(a) What is the enthalpy change for this reaction per mole of O3(g)?
(b) Which has the higher enthalpy under these conditions, 2O3(g) or 3O2(g)?
Given: Thermochemical equation for O3(g) decomposition to O2(g)
Required:
(a) ΔH per mole of O3
(b) Which has higher enthalpy, 2O3(g) or 3O2(g)
Solution:
Sample Problem 2:
Consider the following reaction:
(a) Is this reaction exothermic or endothermic?
(b) Calculate the amount of heat transferred when 3.55 g of Mg(s) reacts at constant pressure.
(c) How many grams of MgO are produced during an enthalpy change of -234 kJ?
(d) How many kilojoules of heat are absorbed when 40.3 g of MgO(s) is decomposed into Mg(s)
and O2(g) at constant pressure?
Given:
a) Type of reaction
b) Q when 3.55 g of Mg is reacted
c) Grams of MgO produced for ΔH = -234 kJ
d) Q (kJ) when 40.3g of MgO is decomposed
Solution:
a) ΔH is negative; hence, the process is exothermic
b) Solving for Q when 3.55 g of Mg is reacted
Sample Problem 3:
From the following data for three prospective fuels, calculate which could provide the most
energy
per unit volume:
Given: Three fuels with data on density and molar enthalpy of combustion
Required: The fuel with the most energy
Solution:
a) Solving for energy from nitroethane
b) Solving for energy from ethanol
Hess’ Law of Constant Summation
The heat evolved or absorbed in a given reaction must be independent of the particular
manner in which the reaction takes place.
Because enthalpy and internal energies are state functions, whether a particular reaction
is carried out in one step or a series of steps, the sums of the enthalpy and internal
changes associated with the individual steps must be the same as the enthalpy change
associated with the one step process.
Hess’ Law
“States that of a chemical reaction out in a series of steps, ΔH for the overall reaction
equals the sum of the enthalpy changes for the individuals steps.”
Sample Problem 4:
Calculate the enthalpy change for the reaction
Given: Thermochemical reaction for the formation of P4O6 and P4O10 from its elemental
constituents
Required: Enthalpy change for
Sample Problem 5:
Given: Thermochemical reaction for the formation of HF, CF 4 and C2H4 from its elemental
constituents
Required: Enthalpy change for
Common Enthalpies of Reaction
Enthalpy of Formation (Heat of Formation, ΔHf):
refers to the thermal change involved in the formation of a substance from its constituent
elements
Standard Enthalpies of Reaction, ΔH°
It should be noted that the magnitude of any enthalpy change depends on the
temperature, pressure and state of the reactants and products. With this, it is important
to establish a standard basis when dealing with enthalpies of reaction to keep the scope
within a narrow range. More often than not, the standard state of a substance is
considered as a standard basis; hence, the enthalpy accompanying a reaction involving
substances in their standard states is known as the Standard Enthalpy of a Reaction,
ΔH°.
At STP:
The standard state of a substance is its pure form at atmospheric pressure (1 atm) and the
temperature of interest which is usually chosen to be 298K (25°C).
The Standard Enthalpy Of A Reaction Is Calculated As:
Standard Enthalpies of Formation of a Compound, ΔHf°
The Standard Enthalpy of Formation of a compound is the change in enthalpy for the reaction
that forms from one mole of the compound from its elements with all substances in their
standard states.
The Standard Enthalpies of Formation can be accessed through the appendices of this module.
Sample Problem 6:
Ethanol (C2H5OH) is currently blended with gasoline as an automobile fuel.
(a) Write a balanced equation for the combustion of liquid ethanol in air.
(b) Calculate the standard enthalpy change for the reaction, assuming H2O(g) as product.
(c) Calculate the heat produced per liter of ethanol by combustion of ethanol under constant
pressure. Ethanol has a density of 0.789 g/mL.
(d) Calculate the mass of CO2 produced per kJ f heat emitted.
Given: Liquid ethanol with density of 0.789 g/mL burning in air
Required:
a) Balanced equation for the combustion of liquid ethanol in air.
b) Standard enthalpy change for the reaction, assuming H2O(g) as product.
c) Heat produced per liter of ethanol
d) Calculate the mass of CO2 produced per kJ of heat emitted.
Solution:
a) Balanced combustion equation
Watch the following videos for further education, information and review:
ASSIGNMENTS, EXAMINATIONS and QUIZZES will be based from these VIDEOS…
Enthalpy Change of Reaction & Formation - Thermochemistry & Calorimetry
Practice Problems
https://www.youtube.com/watch?v=Xe_N7WYl5BI
Activities and Assessments: ASSIGNMENT (SUBMIT your answers at EDMODO
ASSIGNMENT SECTION )
1.) It is interesting to compare the “fuel value” of a hydrocarbon in a world where fluorine rather
than oxygen is the combustion agent. The enthalpy of formation of CF4(g) is -679.9 kJ/mol. The
enthalpy of formation two reactions is the more exothermic?
2.) Calculate the standard enthalpy of formation of gaseous di-borane (B2H6) using the
following thermochemical information:
3.) At the end of 2009, global population was about 6.8 billion people. What mass of glucose
(C6H12O6) in kg would be needed to provide 1500 Cal/person/day of nourishment to the global
population for one year? Assume that glucose is metabolized entirely to CO2 and H2O(l).
