ADAMSON UNIVERSITY

Chemical Engineering Department

A.Y. 2023-2024

PHYSICAL CHEMISTRY I LECTURE

Module 5
THERMOCHEMISTRY
Prepared by: Engr. Elen Cris Manangan (Instructor)

HEAT TRANSACTIONS

It is the energy that spontaneously passes between a system and its surroundings in some way
other than through work or the transfer of matter. When a suitable physical pathway exists, heat
flows spontaneously from a hotter to a colder body.

First Law of Thermodynamics:

∆𝑈 = 𝑄 + 𝑊
Internal energy can be written as:
𝑑𝑈 = 𝑑𝑄 + d𝑊𝑒𝑥𝑝 + d𝑊𝑒
Where dQ is the heat energy transferred across boundary due to difference in T; dWexp is the
work due to expansion; and dWe is extra sources of work (e.g., electrical current)

At constant V, dWexp=0 (system cannot expand). If no additional work (e.g., no battery, etc.),
dWe = 0.
𝑑𝑈 = 𝑑𝑄𝑣
Which implies infinitesimal change at constant volume. Thus, for a measurable finite change:
∆𝑈 = 𝑄𝑣
Note: q > 0 (heat supplied to system)
q < 0 (heat lost from system)

CALORIMETRY

Calorimetry is the process of measuring the amount of heat released or absorbed during a
chemical reaction. By knowing the change in heat, it can be determined whether or not a
reaction is exothermic (releases heat) or endothermic (absorbs heat). Calorimetry also plays a
large part of everyday life, controlling the metabolic rates in humans and consequently
maintaining such functions like body temperature.

CONSTANT PRESSURE CALORIMETRY

Because calorimetry is used to measure the heat of a reaction, it is a crucial part of

thermodynamics. In order to measure the heat of reaction, the reaction must be isolated so that
no heat is lost to the environment. This is achieved by the use of a calorimeter, which insulates
the reaction to better contain heat. Coffee cups are often used as a quick and easy-to-make
calorimeter for constant pressure. More sophisticated bomb calorimeters are built for use at
constant volumes.

Physical Chemistry 1 by Engr. Elen Cris O. Manangan | 1

Using calorimetry, it is possible to calculate the amount of heat gained and lost by each part of
the system. The amount of heat lost or gained by any part of the reaction is related to the heat
capacity of the substance. Heat capacity is the amount of energy, Q, needed to raise the
temperature 1°C or 1 K. To calculate the amount of heat released or absorbed by a reaction in
terms of ∆T, the equation for objects total heat capacity below is used:

𝑄 = 𝐶∆𝑇

Where Q is the amount of heat gained or lost, C is the object’s total heat capacity, and ∆T is the
difference in temperature.

Fig. 1. Coffee Cup Calorimeter

www.brainkart.com

Specific heat capacity takes into account the mass of a substance and the energv needed to
raise its temperature by ∆T, as shown by combining equations:
𝑄 = 𝑚𝐶𝑝 ∆𝑇

Where m is the mass of the object in units of g, 𝐶𝑝 is the specific heat capacity of the object in
units of 𝐽/𝑔 ∙ ℃.

Theoretically, the 𝑞𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 should be equivalent to 𝑞𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 because the amount of heat
gained by one substance should be equal to the amount lost by another. However, the
calorimeter also absorbs some of the heat form the reaction. Because of this, the heat capacity
of the calorimeter is also necessary for calculations and results in the following equation:

𝑞𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 + 𝑞𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 + 𝑞𝑐𝑎𝑙𝑜𝑟𝑖𝑚𝑒𝑡𝑒𝑟 = 0

CONSTANT VOLUME CALORIMETRY

Constant Volume Calorimetry, also known as bomb calorimetry, is used to measure the heat
of a reaction while holding volume constant and resisting large amounts of pressure. Since
the process takes place at constant volume, the reaction vessel must be constructed to

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withstand the high pressure resulting from the combustion process, which amounts to a
“confined explosion”, hence the name bomb calorimetry.

Calorimetry is used to measure quantities of heat and can be used to determine the heat of
reaction through experiments. Usually coffee-cup calorimeter is used since it is simpler than
a bomb calorimeter, but to measure the heat evolved in a combustion reaction, constant
volume or bomb calorimetry is ideal.

Most serious calorimetry carried out in research laboratories involves the determination of
heats of combustion, since these are essential to the determination of standard enthalpies of
formation of the thousands of new compounds that are prepared and characterized each month.
In a constant volume calorimeter, the system is sealed or isolated from its surroundings, and
this accounts for why its volume is fixed and there is no volume-pressure work done. A bomb
calorimeter structure consists of the following:

▪ Steel bomb which contains the reactants

▪ Water bath in which the bomb is submerged
▪ Thermometer
▪ A motorized stirrer
▪ Wire for ignition

Another consequence of the constant-volume condition is that the heat released corresponds
to 𝑞𝑣 , and thus to the internal energy change ∆𝑈 rather than to ∆𝐻. The enthalpy change is
calculated according to the formula:
∆𝐻 = 𝑞𝑣 + ∆𝑛𝑔 𝑅𝑇
In which ∆𝑛𝑔 is the change in the number of moles of gases in the reaction.

Fig. 2. Bomb Calorimeter

Encyclopaedia Britannica

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THERMOCHEMISTRY

Fig. 3. Heat Transaction

https://general.chemistrysteps.com/
It is a branch of physical chemistry which deals with the thermal changes accompanying
chemical and physical transformations. It aims to determine the quantities of energy being
emitted or absorbed as heat in various processes, as well as the development of methods for
calculating these readjustments without recourse to experiment.

Measurements of Thermal Changes

To directly determine the heat change involved in a reaction, calorimeters are employed. A
calorimeter consists of essentially of an insulated container filled with water in which is
immersed the reaction chamber in an exothermic reaction the heat generated is transferred to
the water, and the consequent temperature rise of the water is read from an accurate
thermometer immersed in it. Knowing the quantity of water present, its specific heat, and the
change in temperature, the amount of heat involved in the reaction may be calculated.
Heat of Reaction at Constant Volume
There are two general conditions under which thermochemical measurements are made:
constant volume and constant pressure. The magnitudes of the thermal changes obtained
under these two conditions are in general, different. At constant volume any thermal change
taking place must be due only to the difference in the sum of the internal energies of the
products and those of the reactants. At constant pressure, however, not only does the change
in the internal energy take place but work is also involved.

STANDARD ENTHALPY CHANGES

Numerical values describing ∆𝑈 or ∆𝐻 of a system when some chemical or physical change

occurs depend upon the nature of the reaction, as well as the physical states of reactants and
products.

It is useful to define a standard enthalpy change, ∆𝐻° which is the change in enthalpy for a
process chemical or physical) where initial and final substances are in standard states.

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Standard states - pure form of a substance at specified temperature at a pressure of 1 bar. For
example, the standard state of liquid water at 298 K is pure liquid water at 298 K and 1 bar.
The standard state of liquid ethanol at 298 K is pure liquid ethanol at 298 K and 1 bar.

ENTHALPIES OF PHYSICAL CHANGE

The standard enthalpy of transition, ∆𝑡𝑟𝑠 𝐻° is the standard enthalpy change accompanying a
phase change.
Enthalpy is a state function, independent of path between initial and final states: same value of
∆𝐻° occurs regardless of how change occurs: For example, we can picture the conversion of a
solid to a vapour either as occurring by sublimation (the direct conversion from solid to vapour),

or as occurring in two steps, first fusion (melting) and then vaporization of the resulting liquid:

Thus,

Another consequence of enthalpy being a state function is that ∆𝐻° differs only in sign for
forward and reverse processes.

For instance, because the enthalpy of vaporization of water is +44 kJ mol−1 at 298 K, its enthalpy
of condensation at that temperature is −44 kJ mol−1.

Fig. 4. Enthalpies of Physical Change

Atkins’ Physical Chemistry, 8th edition

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 Enthalpies of Transition
Table 2.4 of Atkins’ Physical Chemistry, 8th edition

The Phase Transition Diagram

Fig. 5. Phase Change Diagram

https://general.chemistrysteps.com/
In the A-B region, there is no phase change, and it is only the increase of temperature for the
substance in solid phase. The B-C region represents the melting where the temperature stays
constant, and the heat absorbed by the substance is used to melt the solid to liquid. In the C-D
region, the temperature of the liquid is increasing without a phase change, and from D to E
region, we have the vaporization (evaporation) of the substance from liquid to gas state. The
temperature of the substance in the gas state is increasing in the E-F segment.

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Example:
How much heat is required to convert 135 g of ice at -15 °C into water vapor at 120 °C? Show
all your work. 𝐶𝑙𝑖𝑞𝑢𝑖𝑑 𝑤𝑎𝑡𝑒𝑟 = 4.184 J/g °C ; 𝐶𝑠𝑡𝑒𝑎𝑚 = 1.84 J/g °C ; 𝐶𝑖𝑐𝑒 = 1.84 J/g °C ;
∆𝐻𝑣𝑎𝑝 = 40.65 kJ/mol; ∆𝐻𝑣𝑎𝑝 = 6.01 kJ/mol.
Ans: 409 kJ

ENTHALPIES OF CHEMICAL CHANGE

°
The standard reaction enthalpy, ∆𝐻𝑟𝑥𝑛 is the change in enthalpy when reactants in their
standard states change to products in their standard states:

Pure, separate reactants in their standard states → pure, separate products in their standard
states

Where in each case the molar enthalpies of the species are multiplied by their stoichiometric
coefficients, ν.
Some standard reaction enthalpies have special names and a particular significance. For
°
instance, the standard enthalpy of combustion, ∆𝐻𝑐𝑜𝑚𝑏 , is the standard reaction enthalpy
for the complete oxidation of an organic compound to CO2 gas and liquid H2O if the compound
contains C, H, and O, and to N2 gas if N is also present.

STANDARD ENTHALPIES OF FORMATION

The standard enthalpy of formation, ∆𝐻𝑓° , of a substance is the standard reaction enthalpy for
the formation of the compound from its elements in their reference states.
The reference state of an element is its most stable state at the specified temperature and 1
bar. For example, at 298 K the reference state of nitrogen is a gas of N2 molecules, that of
mercury is liquid mercury, that of carbon is graphite, and that of tin is the white (metallic)
form.
Standard enthalpies of formation are expressed as enthalpies per mole of molecules or (for
ionic substances) formula units of the compound. The standard enthalpies of formation of
elements in their reference states are zero at all temperatures because they are the enthalpies
of such ‘null’ reactions as N2(g)→N2(g).
The reaction enthalpy in terms of enthalpies of formation:

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Example:
Calculate the heat of reaction for the combustion of ammonia:
°
4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g), ∆𝐻𝑟𝑥𝑛 =?

Example:
Combustion of butane (C4H10) releases 5755 kJ of energy according to the following chemical
equation.
°
2C4H10(g) + 13O2(g) → 8CO2(g) + 10H2O(l), ∆𝐻𝑟𝑥𝑛 = −5755 kJ
Calculate the molar enthalpy of formation of butane.
Example:
The standard enthalpy of formation of phenol is −165.0 kJ mol−1. Calculate its standard
enthalpy of combustion.
Ans: -3053.6 kJ/mol

Example:
If the enthalpy of combustion of gaseous cyclopropane, C3H6, is -2091.2 kJ/mol at 25°C,
calculate the standard enthalpy of formation. The enthalpy of formation of propene is +20.42
kJ mol−1. Calculate the enthalpy of isomerization of cyclopropane to propene.

HESS’S LAW

Fig. 6. State Function

https://general.chemistrysteps.com/

Remember, a state function is a variable that only depends on the initial and final states and
not how it was achieved. For example, altitude is a state function and wouldn’t matter how two

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hikers meet at a 500 ft altitude. One may be on his way to the top, and the other going back
having behind a longer walk distance.
Now, by the same analogy, suppose we need to determine the enthalpy of the reaction 2A + B
→ 2D, given the enthalpies of the other two reactions:

And because enthalpy is a state function, it does not matter how “2A + B” goes to “2D”, so
we add the enthalpy changes for these two routes/reactions to find the enthalpy change for
going “2A + B” to “2D” directly.
Standard enthalpies of individual reactions can be combined to obtain the enthalpy of another
reaction. This application of the First Law is called Hess’s law:
The standard enthalpy of an overall reaction is the sum of the standard enthalpies of
the individual reactions into which a reaction may be divided.
Exercise:
From the following data, determine ∆𝐻𝑓° for diborane, B2H6(g), at 298 K:

HOMEWORK:
Discuss and give at least one example on the temperature dependence of reaction enthalpies.

EXERCISES:

1. A sample of liquid acetone weighing 0.700 g was burned in a bomb calorimeter for which
the heat capacity (including the sample) is 6937 J/K. The observed temperature rise was
from 25.00°C to 26.69°C.
a. Calculate ∆𝑈 for the combustion of 1 mol of acetone.
b. Calculate ∆𝐻 for the combustion of 1 mol of acetone.

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2. A sample of liquid benzene weighing 0.633 g is burned in a bomb calorimeter at 25.00°C
and 26.54 kJ of heat are evolved.
a. Calculate ∆𝑈 per 1 mol of benzene.
b. Calculate ∆𝐻 per 1 mol of benzene.

3. A sample of sucrose, C12H22011 weighing 0.1328 g, was burned to completion in a bomb

calorimeter at 25°C, and the heat evolved was measured to be 2186.0 J.
a. Calculate the ∆𝑈 and ∆𝐻 for the combustion of sucrose.
b. Calculate the ∆𝐻 for the formation of sucrose.

4. For the reaction

1 3
𝑁𝐻3 → 𝑁2 (𝑔) + 𝐻2 (𝑠)
2 2
°
∆𝐻25℃ = 11040 cal. Find the value of ∆𝑈° of the reaction at 25°C.

5. From the following equations and heats of reactions, calculate the standard molar heat of
formation of AgCl at 25°C.

𝐴𝑔2 O(s) + 2HCl(g) → 2AgCl(g) + 𝐻2 O(l) ∆𝐻° = −77610 𝑐𝑎𝑙

1
Ag(s) + 𝑂2 (g) → 𝐴𝑔2 O(s) ∆𝐻° = −7310 𝑐𝑎𝑙
2
1
𝐻 (g) + 𝐶𝑙2 (g) → HCl(g) ∆𝐻° = −22060 𝑐𝑎𝑙
2 2
𝐻2 (g) + 𝑂2 (g) → 𝐻2 O(l) ∆𝐻° = −68320 𝑐𝑎𝑙

6. Estimate the heat of formation of gaseous water at 100°C.

7. The standard reaction enthalpy for the combustion of hydrogenation of propene is -124
kJ/mol:
CH2 = CHCH3 (g) + H2 (g) → CH3CH2CH3 (g)
The standard reaction enthalpy for the combustion of propane is -2220 kJ/mol:
CH3CH2CH3 (g) + 5 O2 (g) → 3 CO2 (g) + 4 H2O (l)
Using Hess' Law, calculate the standard enthalpy of combustion of propene and compare
it with the one obtained from the handbook.

8. A 0.500-g sample of n-butane (l) burned in a constant volume calorimeter to CO2 (g) and
H2O (l) causes a temperature rise of 2.934°C, if the heat capacity of the calorimeter and
its accessories is 1954 cal/°C, and the mean heat capacity Of the calorimeter is 25°C,
calculate:
a. The heat of combustion per mole of the heptane at constant volume
b. The heat of combustion of the heptane per mole at constant pressure

9. From the heat of combustion of n-butane, calculate the standard heat of formation of this
compound per mole at 25°C.

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10. Na2CO3 (s) dissolves in a large excess if H2O with the evolution of 5500 cal of heat per
mole at 25°C. Calculate the heat for formation per mole of Na2CO3 in a dilute solution.

11. At 18°C the heat of solution of anhydrous CuSO4 in a large volume of water is -15,800
cal/mole, while that of CuSO4 ∙5H2O is 2750 cal/mole. Find at 18°C the heat of the
reaction:
CuSO4(s) + 5H2O(l) → CuSO4·5H2O(s)

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