ENERGY: THERMOCHEMISTRY

Types of boundaries

• Adiabatic
NATURE OF ENERGY AND TYPES OF ENERGY • Diathermal
Energy is defined as the capacity to do work. • Permeable
• Impermeable
Work is the directed energy change resulting from a process. • Movable
• Rigid
is the energy associated with the random motion of
atoms and molecules Three types of systems depending on boundary conditions
is the energy stored within the structural units of
What can pass through?
chemical substances Type of System Boundary Condition
Matter Heat
is the energy relative to the position or arrangement of an diathermal, permeable
object
diathermal, impermeable
is the energy in motion. adiabatic, impermeable

Different types of energy can be converted from one form to another due to the law
of conservation of mass, which states that the total quantity of energy in the
universe is constant.
INTRODUCTION TO THERMODYNAMICS
Thermodynamics is the study of energy conversion from one form to another
Chemical reactions generally absorb or produce energy, in the form of heat. Heat is
the transfer of thermal energy between two bodies that are different in temperature.
Spontaneously, heat flows from the region possessing high thermal energy to low
thermal energy. The study of heat changes in chemical reactions is called
thermochemistry.
Properties of Systems
• Extensive properties are properties that are dependent on the amount of
matter present. Some examples include volume, number of moles, internal
energy, and entropy.
• Intensive properties are properties that are independent on the amount of
matter present. Some examples include temperature, pressure, and
density.
States of system
The state of a system is the values of all relevant macroscopic properties, like
composition, energy, temperature, pressure, and volume.

Chemical reactions take place in a specific place called the system, with the • State functions are values/properties that are determined by the state of
surroundings around it. the system, regardless of how the condition was achieved.
• Path Functions are values/properties that depend on the process to get
into another state.
the rest of the universe
INTERNAL ENERGY (E)

Internal energy is the total energy of a system at equilibrium.

part of the universe in focus separates the parts of the universe

Could be
𝐸 = ∑ 𝑃𝐸 + ∑ 𝐾𝐸 (1)
• Adiabatic, diathermal
• Permeable, impermeable
• Movable, rigid Practically, the internal energy itself cannot be determined, however, the changes
in internal energy (Δ𝐸) can be measured in terms of transferring internal energy as
heat (𝑞), or work (𝑤).
CHEMISTRY FOR ENGINEERS (CH1 L1) THERMOCHEMISTRY
Δ𝐸 = 𝑞 + 𝑤 (2)

The sign conventions for 𝑞 and 𝑤 are as follows

• Positive quantities for 𝑞 and 𝑤 if the transfer happens from the

surroundings to the system
• Negative quantities for 𝑞 and 𝑤 if the transfer happens from the system to
the surroundings

System
Expansion Compression
Derivation of 𝑤

The changes in internal energy also is the difference of the internal energy of the
final state from its initial state, that is

Δ𝐸 = 𝐸𝑓𝑖𝑛𝑎𝑙 − 𝐸𝑖𝑛𝑖𝑡𝑖𝑎𝑙 (3)

Whatever changes in the internal energy of the system is, that has to be transferred
to the surroundings.

Δ𝐸𝑠𝑦𝑠𝑡𝑒𝑚 = −Δ𝐸𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 (4)

thus, the sum of the energy change must be zero

Δ𝐸𝑠𝑦𝑠𝑡𝑒𝑚 + Δ𝐸𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 = 0 (5)

This is the concept of first law of thermodynamics.

HEAT (𝑞) AND WORK (𝑤)

Heat is the transfer of thermal energy between two bodies that are different in
temperature. Heat is a process, not a quantity.

Work is the transfer of energy accomplished by a force moving a mass some 𝑑𝑤 = −𝑃𝑑𝑉 (7)
distance against resistance
𝑑𝐸 = 𝑑𝑞 − 𝑃𝑑𝑉 (8)
𝑑𝑤 = −𝐹𝑑𝑥 (6)

where 𝐹 is the force applied and 𝑑𝑥 is the displacement. 𝐿𝑎𝑡𝑚 8.314𝐽

1 𝑎𝑡𝑚 = 101.3 𝐽; 𝑅 = 0.08206 =
𝑚𝑜𝑙𝐾 𝑚𝑜𝑙𝐾
One way to illustrate work is by expansion or compression of a gas in a piston

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CHEMISTRY FOR ENGINEERS (CH1 L1) THERMOCHEMISTRY
Isobaric Work Isochoric Work Isothermal Work 2. A gas expands from 264 mL to 971 mL at constant temperature.
Constant Pressure Constant Volume Constant Temperature Calculate the work done (in joules) by the gas if it expands
a. against a vacuum

b. against a constant pressure of 4.00 atm.

ACTIVITY
1. A certain gas expands in volume from 2.0 L to 6.0 L at constant
temperature. Calculate the work done by the gas if it expands
a. against a vacuum
3. Consider an ideal gas in a piston chamber where the initial volume is
2.00 L and the initial pressure is 8.00 atm. Assume that the piston is
moving up (that is, the system is expanding) to a final volume of 5.50 L
against a constant external pressure of 1.75 atm. Assume constant
temperature for the process.
a. Calculate the work for the process.

b. against a constant pressure of 1.2 atm.

b. Calculate the final pressure of the gas.

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CHEMISTRY FOR ENGINEERS (CH1 L1) THERMOCHEMISTRY
4. The work done when a gas is compressed in a cylinder is 462 J. During Derivation of enthalpy at constant pressure
this process, there is a heat transfer of 128 J from the gas to the
surroundings. Calculate the energy change for this process.

5. A gas expands and does P - V work on the surroundings equal to 279 J.

At the same time, it absorbs 216 J of heat from the surroundings. What
is the change in energy of the system?

𝑞𝑝 = Δ𝐻 (12)

For any reactions, the change in enthalpy is called the enthalpy of reaction, which is
the difference between the enthalpies of the products and the enthalpies of the
reactants:
ENTHALPY OF CHEMICAL REACTIONS
Δ𝐻 = 𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 (13)
To apply the first law of thermodynamics, we have to consider common laboratory
situations: one in which the volume is kept constant, and the other in which the If the change in enthalpy is negative, then it the chemical reaction underwent an
pressure applied on the system is kept constant. Recall equation (3.8), exothermic process. Otherwise, if the change in enthalpy is positive, then it
underwent an endothermic process.
Δ𝐸 = 𝑞 − 𝑃Δ𝑉
Enthalpy changes in a chemical reaction can be paired with the mass relationships
At constant volume, Δ𝑉 = 0, therefore that took place. For example, the combustion of methane gas is accompanied by a
release of 890.4 kJ of energy. This can be represented by a thermochemical
Δ𝐸𝑣 = 𝑞𝑣 (9)
equation
At constant pressure,
𝐶𝐻4 (𝑔) + 2𝑂2 (𝑔) → 𝐶𝑂2 (𝑔) + 2𝐻2 𝑂(𝑙) Δ𝐻 = −890.4 𝑘𝐽
Δ𝐸𝑝 = 𝑞𝑝 − 𝑃Δ𝑉 (10)
It is essential that an equation must be balanced. Also, the following guidelines are
Enthalpy (𝐻), on the other hand, is another thermodynamic function of a system used to interpret thermochemical equations:
defined by the equation
1. Always specify the physical states of all reactants and products.
𝐻 = 𝐸 + 𝑃𝑉 (11) 2. If multiplying both sides of a thermochemical equation by a factor n, the Δ𝐻
must also change by the same factor
3. Writing the reverse equation would make the sign of Δ𝐻 reversed.

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CHEMISTRY FOR ENGINEERS (CH1 L1) THERMOCHEMISTRY
ACTIVITY COMPARISON OF ENTHALPY AND INTERNAL ENERGY
1. Calculate the heat evolved when 87.9 kg of SO2 (64.07 g/mol) is
converted to SO3. Enthalpy and internal energies are both energies involving heat involved in a
2𝑆𝑂2 (𝑔) + 𝑂2 (𝑔) → 2𝑆𝑂3 (𝑔) Δ𝐻 = −198.2 𝑘𝐽 reaction. However, internal energy do also include work in its equation. To derive a
general equation relating these two energies, recall equation (10) and (12).
Combining the two equations would give

Δ𝐸 = Δ𝐻 − 𝑃Δ𝑉 (14)

Since the work done by or to the system is due to the fact that gases expand and
compress, assuming ideal gas behavior of this gas,

Derivation of Enthalpy and Internal Energy Relationship

2. Calculate the heat evolved when 27 kg of white phosphorus (P4) burns

in air according to the equation
𝑃4 (𝑠) + 5𝑂2 (𝑔) → 𝑃4 𝑂10 (𝑠) Δ𝐻 = −3013 𝑘𝐽

Δ𝐸 = Δ𝐻 − Δ𝑛𝑅𝑇 (15)

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CHEMISTRY FOR ENGINEERS (CH1 L1) THERMOCHEMISTRY
ACTIVITY CALORIMETRY
1. Calculate the change in internal energy when 2 moles of CO are
converted to 2 moles of CO2 at 1 atm and 25OC. Heat changes involved in physical or chemical processes are measured with a
2𝐶𝑂(𝑔) + 𝑂2 (𝑔) → 2𝐶𝑂2 (𝑔) Δ𝐻 = −566.0 𝑘𝐽 calorimeter. Calorimetry is the measurement of heat changes involved in any
processes.

SPECIFIC HEAT AND HEAT CAPACITY

Specific heat (𝒄) of the substance is defined as the amount of heat required to raise
the temperature of one gram of the substance by one degree Celsius. It has a unit
of J/g°C.

Heat capacity (𝑪) of the substance is the amount of heat required to raise the
temperature of a given substance by one degree Celsius. It has a unit of J/°C.

The relationship between heat capacity and the specific heat of a substance is

2. What is the Δ𝐸 for the formation of 1 mole of CO aat 1 atm and 25 OC? 𝐶 = 𝑚𝑐 (16)
1
𝐶(𝑔𝑟𝑎𝑝ℎ𝑖𝑡𝑒) + 𝑂2 (𝑔) → 𝐶𝑂(𝑔) Δ𝐻 = −110.5 𝑘𝐽 where 𝑚 is the mass of the substance in grams.
2
To determine the amount of heat 𝑞 the substance has absorbed or released, the
following equations can be used

𝑞 = 𝑚𝑐Δ𝑇 (17)

𝑞 = 𝐶Δ𝑇 (18)

ACTIVITY
1. A 6-kg sample of water is heated from 8.50°C to 74.60°C. Calculate the
amount of heat absorbed (in kilojoules) by the water. (c = 4.184 J/g OC)

3. Which of the constant-pressure processes shown here has the smallest

difference between Δ𝐸 and Δ𝐻? Why?
a. Water to water vapor
b. Water to ice
c. Ice to water vapor

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CHEMISTRY FOR ENGINEERS
2. An iron bar of mass 3200 g cools from 94°C to 5°C. Calculate the heat
released (in kilojoules) by the metal. (c = 0.444 J/gOC)
CONSTANT-VOLUME CALORIMETRY
Heat of combustion is measured by placing a known mass of a substance in a steel
container called the constant-volume bomb calorimeter. This instrument is enclosed
in an insulating container or dewar (to make an adiabatic system), a sample
container, stainless steel bomb, water, a stirrer, a thermometer, and ignition circuit
connected to the bomb.
Retrieved from https://www.learner.org/courses/chemistry/images/lrg_img/BombCalorimeter.jpg
Since the instrument is enclosed in an isolated jacket, there would be no heat flow
between the system and the surroundings, thus, heat flow is only contained between
the calorimeter and the reaction in the bomb, that is
−𝑞𝑟𝑥𝑛 = 𝑞𝑐𝑎𝑙
(CH1 L1) THERMOCHEMISTRY
Before using the bomb, it has to be calibrated first with a compound with known
heat of combustion value. For example, a gram of benzoic acid is known to release
26.24 kJ of heat. The temperature rise due to the transfer of heat to the water is
recorded. Using equation (3.18), the 𝐶𝑐𝑎𝑙 can be determined.
ACTIVITY
1. A quantity of 1.435 g of naphthalene (C10H8), a pungent-smelling
substance used in moth repellents, was burned in a constant-volume
bomb calorimeter. Consequently, the temperature of the water rose from
20.28°C to 25.95°C. If the heat capacity of the bomb plus water was
10.17 kJ/°C, calculate the heat of combustion of naphthalene on a
molar basis; that is, find the molar heat of combustion.
2. A quantity of 1.922 g of methanol (CH3OH) was burned in a constant-
volume bomb calorimeter. Consequently, the temperature of the water
rose by 4.20°C. If the heat capacity of the bomb plus water was 10.4
kJ/°C, calculate the molar heat of combustion of methanol.
(19)
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CHEMISTRY FOR ENGINEERS
3. Methylhydrazine (CH6N2) is commonly used as a liquid rocket fuel. The
combustion of methylhydrazine is shown below
2𝐶𝐻6 𝑁2 (𝑙) + 5𝑂2 (𝑔) → 2𝑁2 (𝑔) + 2𝐶𝑂2 (𝑔) + 6𝐻2 𝑂(𝑔)
When 4.00 g of methylhydrazine is combusted in a bomb calorimeter,
the temperature of the calorimeter increases from 25.00°C to 39.50°C.
In a separate experiment, the heat capacity of the calorimeter is
measured to be 7.794 kJ/°C. What is the heat of reaction for the
combustion of a mole of CH6N2 in this calorimeter?
4. A 0.5865 g sample of lactic acid (HC3H5O3) is burned in a calorimeter
whose heat capacity is 4.812 kJ/°C. The temperature increases from
23.10°C to 24.95°C. Calculate the heat of combustion
(CH1 L1) THERMOCHEMISTRY
CONSTANT-PRESSURE CALORIMETRY
Heat changes that are non-combustion in nature can be determined by a constant-
pressure coffee cup calorimeter. This setup usually constructed by two Styrofoam
cups, a thermometer, stirrer, and an insulated stopper as shown below.
Retrieved from https://www.learner.org/courses/chemistry/images/lrg_img/CoffeeCalorimeter.jpg
Since all heat changes measured here are at constant pressure conditions, it is then
equal to the enthalpy changes. Insulated stoppers and cups provides an isolated
system thus, all heat changes measured are solely coming from the reaction
mixture.
ACTIVITY
1. A lead (Pb) pellet having a mass of 26.47 g at 89.98°C was placed in a
constant-pressure calorimeter of negligible heat capacity containing
100.0 mL of water. The water temperature rose from 22.50°C to
23.17°C. What is the specific heat of the lead pellet?
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CHEMISTRY FOR ENGINEERS
2. A 30.14-g stainless steel ball bearing at 117.82°C is placed in a
constant-pressure calorimeter containing 120.0 mL of water at
18.44°C. If the specific heat of the ball bearing is 0.474 J/g°C, calculate
the final temperature of the water. Assume the calorimeter to have
negligible heat capacity.
3. A quantity of 1.00x102 mL of 0.500 M HCl was mixed with 1.00x10 2 mL
of 0.500 M NaOH in a constant-pressure calorimeter of negligible heat
capacity. The initial temperature of the HCl and NaOH solutions was the
same, 22.50°C, and the final temperature of the mixed solution was
25.86°C. Calculate the heat change for the neutralization reaction on a
molar basis.
(CH1 L1) THERMOCHEMISTRY
4. When a student mixes 50 mL of 1.0 M HCl and 50 mL of 1.0 M NaOH in
a coffee-cup calorimeter, the temperature of the resultant solution
increases from 21.0°C to 27.5°C. Calculate the enthalpy change for the
reaction, assuming that the calorimeter loses only a negligible amount
of heat, that the total volume of the solution is 100 mL with a density of
1.0 g/mL, and the specific heat of the solution is 4.18 J/g°C.
5. When 50.0 mL of 0.100 M AgNO3 and 50.0 mL of 0.100 M HCl are mixed
in a constant-pressure calorimeter, the temperature of the mixture
increases from 22.30°C to 23.11°C due to the reaction
𝐴𝑔𝑁𝑂3 (𝑎𝑞) + 𝐻𝐶𝑙(𝑎𝑞) → 𝐴𝑔𝐶𝑙(𝑠) + 𝐻𝑁𝑂3 (𝑎𝑞)
Calculate the molar enthalpy change for the reaction, assuming that the
combined solution has a mass of 100.0 g and a specific heat of 4.18
J/g°C.
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