MODULE 5: THERMOCHEMISTRY

Most Essential Learning Competencies:

1. Explain the First Law of Thermodynamics (STEM_GC11TCIIIg-i-124)
2. Explain Enthalpy of the Reaction (STEM_GC11TCIIIg-i-125); and
3. Calculate the change in enthalpy of a given reaction using Hess Law (STEM_GC11TCIIIg-i-
127)
1.
Discussion of the Lessons

The First Law of Thermodynamics

To understand and perform any sort of thermodynamic calculation, we must first
understand the fundamental laws and concepts of thermodynamics.
Heat is the transfer of thermal energy between two bodies that are atdifferent temperatures and
is not equal to thermal energy.

Work is the force used to transfer energy between a system and itssurroundings and
is needed to create heat and thermal energy transfer.

Both work and heat allow systems to exchange energy. The relationship between the two
concepts can be analyzed through the topic of thermodynamics, which is the scientific study of
the interaction of heat and other types of energy.

The First Law of Thermodynamics states that "energy cannot be created nor destroyed. It
can be transformed into another form, but the total amount of energy remains the same. How
energy is conserved is shown when you eat your meal. The chemical energy in the food will be
converted into mechanical energy that enables you to perform your daily task. But not all the
chemical energy from the food you take will be transformed into mechanical energy. Someof it will
be released from your body as heat when you sweat or feel warm. Thelaw deals with energy, work,
and heat.
According to the Law of Conservation of Energy, energy can neither be created nor
destroyed. It can only be transferred between the system and the surroundings. The energy of the
system (ΔEsys) and the energy of its surroundings (ΔEsurr) are related by the following equation:

The negative sign indicates the flow of energy. As the system releases energy, the
surroundings absorb it. Whatever amount of energy that is lost by the surroundings must be
gained by the system.
The First Law of Thermodynamics states that in the process, the change in energy of a
system is equal to the heat absorbed (q) by the system and the work (w) done on it.

The law implies that the net energy flow to or from any system comes in the form of either
work or heat. When work is done on the system, it gains energy, and work is denoted as positive
(+w). When the system does the work, it uses up or transfers some of its energy so that work is
denoted as negative (–w). Moreover, the system may also absorb heat (endothermic) for which q is
positive (+q), or it may release heat (exothermic) to the surroundings for which q is negative (–q).
Thus, the net change in energy can either be positive or negative, depending on the means and
direction of the energy transfer involved.

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 The table below shows the sign of the values of the q and w as it enters orleaves the
system.

Heat added to the system → → Heat evolved by the system(-q)

(+q) Exothermic

SYSTEM
Endothermic

Work done on the system → → Work done by the system(–

(+w) w)

Heat (q) and work (w) are positive when they enter the system and negative when they leave
the system. As to the internal energy (ΔEsys), the table preceding table serves as a guide in
determining the sign of the value of ΔEsys.

q w ΔEsys (internal energy)

+ + + (internal energy increases)

– – – (internal energy decreases)

+ – The sign of ΔE depends on the

– + magnitude of q and w.

The internal energy of a system would decrease if the system gives off heat or does work.
Therefore, the internal energy of a system increases when the heat increases (this would be done
by adding heat into a system). The internal energy would also increase if work were done on a
system. Any work or heat that goes into or out of a system changes the internal energy. However,
since energy is never created nor destroyed as the first law of thermodynamics states, then the
change in internal energy always equals zero. If energy is lost by the system, then it is absorbed
by the surroundings. If energy is absorbed into a system, then that energy was released by the
surroundings.

Sample Problem
A gas in a system has constant pressure. The surroundings around the system lose 62 J of
heat and do 474 J of work onto the system. What is the internal energy of the system?

Solution
To find internal energy, ΔEsys, we must consider the relationship between the system and
the surroundings. Since the First Law of Thermodynamics states that energy is not created nor
destroyed. We know that anything lost by the surroundings is gained by the system. The
surrounding area loses heat and does work on the system.

Activity 1: Calculate the change in energy for the following processes. Determine if the
process is endothermic or exothermic.
1. A gas releases 35 J of heat as 84 J of w was done to compress it.
2. A gas absorbs 48 J of heat as it does 72 J of work by expanding.

An interesting observation whenever energy is utilized to do work is that some of it seem to

escape. It just doesn't go to where we want it to go. That means that the utilization of energy is
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almost always less than 100% efficient. If the released energy is not used, it will escape and be
"wasted," usually as heat.
All forms of energy can be quantitatively converted into heat. For example, when a moving
car stops, where does all the mechanical energy go? It is converted entirely into heat by the
frictional action of the brakes, which become very hot. When electrical energy is directed to a
material that is a poor conductor of the electricity, such as a filament in flat irons, the electrical
energy is converted entirely into heat. The full convertibility of the different forms of energy into
heat gives us a way of measuring energy.
Activity 2: The Energy Deal
Directions: A. Write TRUE if the statement is true and FALSE if the statementis not true.
1. The heat added to a system is used to decrease the system’sinternal energy.
2. The First Law of Thermodynamics describes how chaotic is theenergy of the universe.
3. Steam engines operate by boiling water to produce steam. Thework done by the steam is due
to the expansion of water as it turns into steam.
4. Heat is the transfer of thermal energy between two bodies thatare of equal temperatures.
5. Work is required to create heat and causes the transfer of energybetween the system and its
surroundings.

B. Refer to the First Law of Thermodynamics. Decide whether the statement is TRUE or FALSE.
Support your answer. "Our energy supply is running out."

Enthalpy of a Chemical Reaction

Most chemical reactions in laboratories and even in living systems occur under constant
pressure. When such chemical reactions are carried out in vessels exposed to atmospheric
pressure, energy changes between the system and the surroundings usually involve heat transfer
only since the amount of work involved is negligible under this condition.
We have stated that the change in energy (ΔE) is equal to the sum of the heat produced and
the work performed. Work done by an expanding gas is called pressure-volume work or PV work.

Consider the example of work performed by a

reaction carried out at constant pressure in a closed
container, as shown in the figure.

Initially, the system (a copper penny and

concentrated nitric acid) is at atmospheric pressure, as
shown in (a). When the penny is added to the nitric acid, the volume of NO2 gas that is formed
causes the piston to move upward to maintain the system at atmospheric pressure, as shown in
(b). In doing so, the system is performing work on its surroundings.
The chemical equation for this reaction is,

If the reaction is carried out in a closed system that is maintained at constant pressure by
a movable piston, the piston rises as nitrogen dioxide gas is formed.

The system is performing work by lifting the piston against the downward force exerted by
the atmosphere (i.e., atmospheric pressure). We find the amount of PV work done by multiplying
the external pressure P by the change in volume caused by the movement of the piston (ΔV). At a
constant external pressure (here, atmospheric pressure), W = −PΔV.

The negative sign associated with PV work done indicates that the system loses energy when
the volume increases. If the volume increases at constant pressure (ΔV>0), the work done by the
system is negative, indicating that a system has lost energy by performing work on its
surroundings. Conversely, if the volume decreases (ΔV<0), the work done by the system is positive,

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which means that the surroundings have performed work on the system, thereby increasing its
energy.
The internal energy ΔE of a system is the sum of the kinetic energy and potential energy of
all its components. It is the change in internal energy that produces heat plus work. To measure
the energy changes that occur in chemical reactions, chemists usually use a related
thermodynamic quantity called enthalpy (H) (from the Greek enthalpein, meaning "to warm").

The enthalpy of a system is defined as the sum of its internal energy ΔE plus the product of
its pressure P and volume V:
Because internal energy, pressure, and volume are all state functions, enthalpy is also a
state function. So, we can define a change in enthalpy (ΔH) accordingly by the equation:

If a chemical change occurs at constant pressure (i.e., for a given P, ΔP = 0), the change in
enthalpy (ΔH) is

Substituting q +w for ΔE (First Law of Thermodynamics) and −w for PΔV, we obtain,

From the equation above, we see that at constant pressure, the change in enthalpy, ΔH of
the system, is equal to the heat gained or lost.

Just as with ΔE, because enthalpy is a state function, the magnitude of ΔH depends only
on the initial and final states of the system, not on the path taken. Most importantly, the enthalpy
change is the same even if the process does not occur at constant pressure.

When we study energy changes in chemical reactions, the most important quantity is
usually the enthalpy of reaction (ΔHrxn), the change in enthalpy that occurs during a reaction
(such as the dissolution of a piece of copper in nitric acid). If heat flows from a system to its
surroundings, the enthalpy of the system decreases, so ΔHrxn is negative.
Conversely, if heat flows from the surroundings to a system, the enthalpy of the system
increases, so ΔHrxn is positive. Thus:

The sign conventions for heat flow and enthalpy changes are summarized in the following
table:

Reaction Type Q ΔHrx

n
Exothermic <0 – (heat flows from a system to its surroundings)
Endothermic >0 + (heat flows from the surroundings to a system)

If ΔHrxn is negative, then the enthalpy of the products is less than the enthalpy of the
reactants; that is, an exothermic reaction is energetically downhill. Conversely, if ΔHrxn is positive,

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then the enthalpy of the products is greater than the enthalpy of the reactants; thus, an
endothermic reaction is energetically uphill.
Two important characteristics of enthalpy and changes in enthalpy are summarized in the
following discussion.

In chemical reactions, bond breaking requires

an input of energy and is, therefore, an endothermic
process, whereas bond making releases energy,
which is an exothermic process.
Energy changes in chemical reactions are
usually measured as changes in enthalpy. (a) If heat flows from a system to its surroundings, the
enthalpy of the system decreases, ΔHrxn is negative, and the reaction is exothermic; it is
energetically downhill. (b) Conversely, if heat flows from the surroundings to a system, the
enthalpy of the system increases, ΔHrxn is positive, and the reaction is endothermic; it is
energetically uphill.

Activity 3: Endothermic or Exothermic

Direction: Identify whether each process involves an exothermic or endothermic reaction.
1. Melting ice
2. Subliming naphthalene balls
3. Thermal decomposition
4. Dissolving ammounium chloride in water
5. Photosynthesis
6. Cellular respiration
7. Water freezing into ice cubes
8. Rusting of iron
9. Burning of candleas
10. Setting of cement and concrete

Enthalpy of Formation and Reaction

Standard States and Standard Enthalpy Changes

The standard enthalpy of formation refers to the enthalpy change when one mole of a
compound is formed from its elements.

Standard States
In Chemistry, the standard state of a material, be it a pure substance, mixture, or solution,
is a reference point used to calculate its properties under different conditions. In principle, the
choice of the standard state is arbitrary, although the International Union of Pure and Applied
Chemistry (IUPAC) recommends a conventional set of standard states for general use. A standard
pressure of 1 bar (101.3 kilopascals) has been accepted.

Strictly speaking, temperature is not part of the definition of a standard state. The standard
state of a gas is conventionally chosen to be 1 bar for an ideal gas, regardless of the temperature.
However, most tables of thermodynamic quantities are compiled at specific temperatures, most
commonly 298.15 K (exactly 25°C) or, somewhat less commonly, 273.15 K (exactly 0°C).
Standard states for atomic elements are given in terms of the most stable allotrope for each
element. For example, white tin and graphite are the most stable allotropes of tin and carbon,
respectively. Therefore, they are used as standard states or reference points for calculations of
different thermodynamic properties of these elements.

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Standard Molar Enthalpy of Formation, ΔHf

The standard enthalpy of formation, or standard heat of formation, of a compound, is the

change in enthalpy that accompanies the formation of one mole of the compound from its elements
in their standard states. For example, the standard enthalpy of formation for carbon dioxide would
be the change in enthalpy for the following reaction:

Note that standard enthalpies of formation are always given in units of kJ/mol of the
compound formed.
Standard Molar Enthalpy of Reaction, ΔHrxn

The standard molar enthalpy of formation can be calculated by subtracting the sum (Σ) of
the enthalpy of formation of the product and the sum of the enthalpies of formation of the
reactants.

Consider the hypothetical equation, aA + bB → cC + dD

Enthalpy of formation of product: ΣΔHf (products) = cΔHf(C) + ΔHf(D)

Enthalpy of formation of reactant: Σ ΔHf (reactants) = aΔHf(A) + bΔHf(B)

Then the standard molar enthalpy of the hypothetical reaction is calculated as,

Σ ΔHf (rxn) = ΔHf (products) – ΔHf (reactants)

Sample Problem:

Consider the combustion of ethanol, C 2H5OH to produce CO2 and H2O.

Calculating the Standard Enthalpy of Reaction

Calculate the standard enthalpy of reaction for the combustion of methane:

To calculate the standard enthalpy of reaction, we need to look up the standard enthalpies
of formation for each of the reactants and products involved in the reaction. These are typically
found in an appendix or in various tables online. For this reaction, we need the ΔHf of the following
substances:

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 Note that because it exists in its standard state, the standard enthalpy of formation for
oxygen gas is 0 kJ/mol. Next, we sum up our standard enthalpies of formation. Keep in mind that
because the units are in kJ/mol, we need to multiply by the stoichiometric coefficients in the
balanced reaction equation.

Now, we can find the standard enthalpy of reaction,

As we would expect, the standard enthalpy for this combustion reaction is strongly
exothermic.
Activity 4: Check Your Knowledge Temperature
Direction: Calculate the heat of reaction of the combustion of ethane gas, C2H4. The balanced
equation for the reaction is,
C2H4(g) + 3O2(g) → 2CO2(g) + 2H2O(l)

The enthalpy or enthalpy change is how much energy (in the form of heat) has been
transferred out or taken in during a chemical reaction. Many compounds cannot be directly
synthesized from their elements. In some cases, the reaction proceeds too slowly, or side reactions
produce substances other than the desired compound. In these cases, ΔH°f (enthalpy change) can
be determined by an indirect approach, which is based on Hess's Law of Heat Summation, or
simply Hess's Law, named after the Swiss chemist, Germain Henri Hess.

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Hess's Law

Hess's Law sums the changes in enthalpy for a series of intermediate reaction steps to find
the overall change in enthalpy for a reaction.
This law states that if a reaction takes place in several steps, then the standard reaction
enthalpy for the overall reaction is equal to the sum of the standard enthalpies of the intermediate
reaction steps, assuming each step takes place at the same temperature.
Hess's Law derives directly from the Law of Conservation of Energy, as well as its expression
in the First Law of Thermodynamics. Since enthalpy is a state function, the change in enthalpy
between products and reactants in a chemical system is independent of the pathway taken from
the initial to the final state of the system. Hess's Law can be used to determine the overall energy
required for a chemical reaction, especially when the reaction can be divided into several
intermediate steps that are individually easier to characterize.
A negative enthalpy change for a reaction indicates an exothermic process, while a positive
enthalpy change corresponds to an endothermic process.

Activity 5: The Truth About Enthalpy

Direction: Write TRUE if the statement is correct and FALSE if it is not.

1. The enthalpy change accompanying a chemical change is independent of the route by which
the chemical change occurs.
2. Hess's Law says that if you convert reactants A into products B, the overall enthalpy change
will be exactly different whether you do it in one step or two steps or however many steps.
3. The enthalpy change is the heat evolved or absorbed during a reaction happening at
constant pressure.
4. All steps in enthalpy change have to proceed at the same temperature and the equations for
the individual steps must balance out.
5. Enthalpy is a state function that the magnitude of ΔH does not depend on the path.

Calculating Standard Enthalpies of Reaction Using Hess's Law

Problem 1. What is the ΔHrxn of the following reaction?

C(s){graphite} → C(s){diamond} ΔHrxn=?

Turning graphite into diamond requires extremely high temperatures and pressures, and
therefore is impractical in a laboratory setting. The change in enthalpy for this reaction cannot be
determined experimentally. However, because we know the standard enthalpy change for the
oxidation of these two substances, we can calculate the enthalpy change for this reaction using
Hess's Law.

Our intermediate steps are as follows:

In order to get these intermediate reactions to add to our overall net reaction, we need to
reverse the second step. Keep in mind that when reversing reactions using Hess's Law, the sign of
ΔH will change. Sometimes, you will need to multiply a given reaction intermediate by an integer.
In such cases, you need always multiply your ΔH value by that same integer. Restating the first
equation and flipping the second equation, we have:

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 Adding these equations together, carbon dioxides and oxygens cancel, leaving us only with
C(s){graphite} and C(s){diamond} in our net equation. By Hess's Law, we can sum the ΔH values
for these intermediate reactions to get our final value, ΔHrxn.

Problem 2: What is the value of ΔH for the following reaction?

Solution
Hess's Law says the total enthalpy change does not rely on the path taken from beginning
to end. Enthalpy can be calculated in one grand step or multiple smaller steps.

Step 1: Manipulate given equations to most closely resemble the equation of interest. To solve this
type of problem, organize the given chemical reactions where the total effect yields the reaction
needed. There are a few rules that you must follow when manipulating a reaction.
1. The reaction can be reversed. This will change the sign of ΔHf.
2. The reaction can be multiplied by a constant. The value of ΔHf must be multiplied by the same
constant.

 We see a resemblance of value from the equation of interest (Eq.1) to Equation 2

 Flip Equation 2 so that 2CO(g) will be on the reactant side as reflected by the equation of
interest. Applying rule #1, this will become:

 Another resemblance from the equation of interest (Eq. 1) to equation 3.

 Both resemblances are on the product side, but their coefficients are not the same;
therefore, multiply the whole equation 3 to have a coefficient of 2. Applying rule #2, this will
become:

Step 2: Add new reactions together.

 Add equation 4 and equation 5 together with their ΔHf This will become

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Step 3: Cancel out any compounds that are the same on both sides of the reaction arrow. Anything
that is the same on both of the reaction arrows can be canceled out

Step 4: Write the new equation and double-check to make sure it matches the equation of interest.

Therefore the value of ΔH for the following reaction,

A chemical equation that shows the value and direction of heat involved in a reaction is
specifically called thermochemical reaction. It also indicates the physical state of the reactants
and products involved in the reaction.

The amount of heat absorbed or released by a chemical reaction at constant atmospheric

pressure is called enthalpy (H). It is a form of chemical energy. The difference between the enthalpy
of the products and the reactants is called enthalpy of a reaction (ΔH).

When (ΔH) is positive, the chemical reaction is described as endothermic. When (ΔH) is
negative, the reaction is exothermic. Consider the exothermic combustion of methane (CH 4) into
carbon dioxide (CO2) and water (H2O).

This thermochemical equation means that 890.4 kJ of heat is released when one mole of
gaseous methane and two moles of oxygen gas combust to form one mole of gaseous carbon dioxide
and two moles of liquid water.

Enthalpy is an extensive property. Its magnitude is proportional to the amount of reactants

and products in the reaction. For example, if the amount of reactants and products in a
thermochemical equation is multiplied by 2, the value of the enthalpy is also multiplied by 2. If
multiplied by ½ the enthalpy is also reduced to half.

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Activity 6: The Heat is On!
Direction: Determine the ΔHrxn from ΔHf values
The reaction of liquid hydrogen peroxide, H2O2, with liquid hydrazine has also been
suggested as a source of energy for small rockets. Find out ΔHrxn for this reaction and compare
the usefulness of the reaction.

ASSESSMENT (MODULE 5)
Direction: Encircle the letter of the best answer.
1. The First Law of Thermodynamics is the Law of __________________
A. Conservation of energy C. Conservation of mass
B. Conservation of work D. Conservation of heat
2. The First Law of Thermodynamics is about ______.
A. entropy B. enthalpy C. temperature D. internal energy
3. Which statement about enthalpy is true?
A. Heat is given off to the surroundings in endothermic reactions.
B. The sign of ΔH is always negative in exothermic reactions.
C. Some substances have a negative specific heat capacity.
D. Specific heat capacity is the same for all liquids.
4. What happens to the value of ΔH for a thermochemical reaction if the reaction is reversed?
A. ΔH is the reciprocal of the original value, and the sign remains the same.
B. ΔH has the same numerical value, and the sign remains the same.
C. ΔH is the reciprocal of the original value and the sign changes.
D. ΔH has the same numerical value and the sign changes.
5. Which is an exothermic process?
A. Water vapor condensing C. Water boiling
B. Water evaporating D. Ice melting
6. Which is not true about entropy?
A. It is denoted by the symbol S
B. It is a measure of the randomness or disorder of a system.
C. It is a measure of how much energy is unavailable for conversion into work.
D. A positive value of a change in entropy indicates that the final state is less random
than the initial state.

7. Which reaction below is endothermic?

A. 2NO2(g) ⇌ N2O4(g), ΔH = -58.0 kJ
B. PCl5(g) ⇌ PCl3(g) + Cl2(g), ΔH = 87.9 kJ
C. N2(g) ⇌ 3H2(g) + 2NH3(g), ΔH = -92.38 kJ
D. 2PCl3(g) + O2(g) ⇌ 2POCl3(g), ΔH = -508 kJ

8. The branch of thermodynamics which deals with the interconversion of energy between
heat and work.
A. thermochemistry B. Kinetics C. thermodynamics D. equilibria

9. Which of the following equations represents an endothermic reaction?

A. 2H2(g) + O2(g) → 2H2O(l) ΔH = -572 kJ
B. 2H2(g) + O2(g) → 2H2O(l) + 572 kJ
C. 2BrCl(g) + -29.3 kJ → Br2(g) + Cl2(g)
D. N2O4(g) + 59 kJ → 2NO2(g)
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10. Which of the following is true following the law of conservation of energy?
A. ΔEsys + ΔEsurr = 0 C. ΔEsys = –ΔEsurr
B. ΔEsys = ΔEsurr D. ΔEsys – ΔEsurr = 0
11. Which of the following will have a standard enthalpy of formation equal to zero?
A. N2 (g) B. CO2 (g) C. NO2 (g) D. MgCl2 (g)
12. Living plants produce glucose during photosynthesis according to the equation:
6CO2(g) + 6H2O(l) → C6H12O6(s) + 6O2(g)
Is the reaction endothermic or exothermic, and is the value of ΔH positive or negative?
A. exothermic, positive C. endothermic, positive
B. exothermic, negative D. endothermic, negative

13. Given the hypothetical thermochemical equation: A + B → C + D ΔH = - 430 kJ.

Which among the following statements is correct about this reaction?
A. The reaction is endothermic.
B. The equation may be written as A + B + 430 kJ → C + D
C. The heat content of A and B is greater than the heat content of C and D
D. The heat content of C and D is greater than the heat content of A and B.

14. Given the following data: 2 O3(g) → 3 O2(g) ΔH° = -427 kJ

O2(g) → 2 O(g) ΔH° = +495 kJ
NO(g) + O3(g) → NO2(g) + O2(g) ΔH° = -199 kJ
Which of the following option shows the ΔH° for the reaction,
NO(g) + O(g) → NO2(g)?
A. 233 kJ B -233 kJ C. -465 kJ D. 465 KJ

15. Given: CH3OH(l); ΔH = –238.6 kJ/mol

CO2(g) ; ΔH = –393.5kJ/mol
H2O (l) ; ΔH = –285.8kJ/mol
The standard enthalpy change, ΔH°, for the following reaction,
2CH3OH(l) + 3O2(g) → 2CO2(g) + 4H2O (l)
A. ΔH = –1299.5 kJ
B. ΔH = –1075 kJ
C. ΔH = –424.8 kJ
D. ΔH = –3267.8 kJ
------------------------------------------------- End of Module 5 ------------------------------------------------

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