LESSON 2

FIRST LAW OF THERMODYNAMICS: THERMAL ENERGY AND WORK

2.1 INTRODUCTION

Welcome to our second lesson on the first law of thermodynamics. From the first lesson you
were introduced to thermodynamics and the basic concepts. In this lesson we will build further
on the first law of thermodynamics and describe how pressure, volume, and temperature relate to
one another and to work, based on the ideal gas law. We will also explain pressure–volume
work. Finally we will solve problems involving the first law of thermodynamics.

2.2 Lesson Learning Outcomes

By the end of this lesson, you will be able to;

2.2.1 Describe the first law of thermodynamics verbally and mathematically

2.2.2 Describe how pressure, volume, and temperature relate to one another and to work,
based on the ideal gas law

2.2.3 Explain pressure–volume work

2.2.4 Solve problems involving the first law of thermodynamics

2.2.1 Expression of The first law of thermodynamics

Recall that the principle of conservation of energy states that energy cannot be created or
destroyed, but it can be altered from one form to another.

In a closed system

dU =dq+ dw

∆ U =q+ w

Where U is the internal energy of the system, a state function; q is heat; and w is thermodynamic
work.

The equation dU=dq+dw is the differential form of the first law, and ∆U=q+w is the integrated
form.

The heat and work appearing in the first law are two different modes of energy transfer.
They can be defined in a general way as follows:

Heat refers to the transfer of energy across the boundary caused by a temperature gradient at the
boundary. Heat (denoted by the symbol Q), may be, defined in an analogous way to work as
follows:

“Heat is ‘something’ which appears at the boundary when a system changes its state due to a
difference in temperature between the system and its surroundings”.

Heat, like work, is a transient quantity which only appears at the boundary while a change is
taking place within the system.

Sign convention:
If the heat flows into a system from the surroundings, the quantity is said to be positive and,
conversely, if heat flows from the system to the surroundings it is said to be negative.
In other words:
Heat received by the system = + Q
Heat rejected or given up by the system = – Q.

Work refers to the transfer of energy across the boundary caused by the displacement of a
macroscopic portion of the system on which the surroundings exert a force, or because of other
kinds of concerted, directed movement of entities (e.g., electrons) on which an external force is
exerted. Work is said to be done when a force moves through a distance. If a part of the
boundary of a system undergoes a displacement under the action of a pressure, the work done W
is the product of the force (pressure × area), and the distance it moves in the direction of the
force

Work is a transient quantity which only appears at the boundary while a change of state is
taking place within a system. Work is ‘something’ which appears at the boundary when a system
changes its state due to the movement of a part of the boundary under the action of a force.

Sign convention:

If the work is done by the system on the surroundings, e.g., when a fluid expands pushing a
piston outwards, the work is said to be positive.

i.e., Work output of the system = + W

If the work is done on the system by the surroundings, e.g., when a force is applied to a rotating
handle, or to a piston to compress a fluid, the work is said to be negative.
i.e., Work input to system = – W

It is apparent that neither δW or δQ are exact differentials and therefore any integration of the
elemental quantities of work or heat which appear during a change from state 1 to state 2 must be
written as
2

∫ δw=w 1−2 0 r 1W2 (or W), and

1

∫ δQ=wQ 1−2 0 r 1Q2 (or Q)

1

Comparison of Work and Heat

Similarities:

i. Both are path functions and inexact differentials.

ii. Both are boundary phenomenon i.e., both are recognized at the boundaries of the system
as they cross them.
iii. Both are associated with a process, not a state. Unlike properties, work or heat has no
meaning at a state.
iv. Systems possess energy, but not work or heat.

Dissimilarities:

i. In heat transfer temperature difference is required.

ii. In a stable system there cannot be work transfer, however, there is no restriction for the
transfer of heat.
iii. The sole effect external to the system could be reduced to rise of a weight but in the case
of a heat transfer other effects are also observed

Numbering, pacing and sequencing 2.2.1

Title
Expression of The first law of thermodynamics
Purpose Describe the first law of thermodynamics verbally
and mathematically
 Brief summary of overall task Watch this video on The First Law of Thermodynamics
Describe the various ways of expressing the first law of
thermodynamics mathematically.

Spark

Explain the metabolisms shown in (a) and (b)

according to the first law of thermodynamics
Individual task After watching the video explain the significance of
the first law of thermodynamics
Give the answer to the question on the spark
Post your answers on the discussion forum 2.2.1
provided
Interaction begins ● Read what your colleagues have posted in the
discussion forum 2.2.1
● Keeping netiquette in mind, comment on what three
of your colleagues have posted.
● Read the facilitator’s comments too to get feedback
Add any new point you have learnt to your
notes/portfolio
E-moderator interventions

Schedule and time This task should take you 30 minutes

Next Relationship of pressure, volume, and temperature
relate to one another and to work, based on the ideal
gas law

2.2.2 Relationship of pressure, volume, and temperature to one another and to work,
based on the ideal gas law

During the seventeenth and especially eighteenth centuries, driven both by a desire to understand
nature and a quest to make balloons in which they could fly , a number of scientists established
the relationships between the macroscopic physical properties of gases, that is, pressure, volume,
temperature, and amount of gas. Although their measurements were not precise by today’s
standards, they were able to determine the mathematical relationships between pairs of these
variables (e.g., pressure and temperature, pressure and volume) that hold for an ideal gas—a
hypothetical construct that real gases approximate under certain conditions. Eventually, these
individual laws were combined into a single equation—the ideal gas law—that relates gas
quantities for gases and is quite accurate for low pressures and moderate temperatures. We will
consider the key developments in individual relationships (for pedagogical reasons not quite in
historical order), then put them together in the ideal gas law.

Pressure and Temperature: Amontons’s Law

Imagine filling a rigid container attached to a pressure gauge with gas and then sealing the
container so that no gas may escape. If the container is cooled, the gas inside likewise gets colder
and its pressure is observed to decrease. Since the container is rigid and tightly sealed, both the
volume and number of moles of gas remain constant. If we heat the sphere, the gas inside gets
hotter (Figure 2.2) and the pressure increases.

Figure 2.2 The effect of temperature on gas pressure:

When the hot plate is off, the pressure of the gas in the sphere is relatively low. As the gas is
heated, the pressure of the gas in the sphere increase
This relationship between temperature and pressure is observed for any sample of gas confined
to a constant volume. An example of experimental pressure-temperature data is shown for a
sample of air under these conditions in Figure 2.3. We find that temperature and pressure are
linearly related, and if the temperature is on the kelvin scale, then P and T are directly
proportional (again, when volume and moles of gas are held constant); if the temperature on the
kelvin scale increases by a certain factor, the gas pressure increases by the same factor.

Figure 2.3. For a constant volume and amount of air, the pressure and temperature are directly
proportional, provided the temperature is in kelvin. (Measurements cannot be made at lower
temperatures because of the condensation of the gas.) When this line is extrapolated to lower
pressures, it reaches a pressure of 0 at –273 °C, which is 0 on the kelvin scale and the lowest
possible temperature, called absolute zero.

the P–T relationship for gases is known as either Amontons’s law or Gay-Lussac’s law. Under
either name, it states that the pressure of a given amount of gas is directly proportional to its
temperature on the kelvin scale when the volume is held constant. Mathematically, this can be
written:

P ∝TorP=constant × TorP=k ×T

where ∝ means “is proportional to,” and k is a proportionality constant that depends on the
identity, amount, and volume of the gas.

Volume and Temperature: Charles’s Law

The volume increases as the temperature increases, and decreases as the temperature decreases.
Volume-temperature data for a 1-mole sample of methane gas at 1 atm are listed and graphed in
Figure 2.4.

Figure 2.4. The volume and temperature are linearly related for 1 mole of methane gas at a
constant pressure of 1 atm. If the temperature is in kelvin, volume and temperature are directly
proportional. The line stops at 111 K because methane liquefies at this temperature; when
extrapolated, it intersects the graph’s origin, representing a temperature of absolute zero.

The relationship between the volume and temperature of a given amount of gas at constant
pressure is known as Charles’s law mathematically written as;

V ∝TorV =constant ⋅TorV =k ⋅TorV 1/T 1=V 2/T 2

with k being a proportionality constant that depends on the amount and pressure of the gas.

Volume and Pressure: Boyle’s Law

If we partially fill an airtight syringe with air, the syringe contains a specific amount of air at
constant temperature, say 25 °C. If we slowly push in the plunger while keeping temperature
constant, the gas in the syringe is compressed into a smaller volume and its pressure increases; if
we pull out the plunger, the volume increases and the pressure decreases. This example of the
effect of volume on the pressure of a given amount of a confined gas is true in general.
Decreasing the volume of a contained gas will increase its pressure, and increasing its volume
will decrease its pressure. In fact, if the volume increases by a certain factor, the pressure
decreases by the same factor, and vice versa. Volume-pressure data for an air sample at room
temperature are graphed in Figure 2.5.
Figure 2.5. When a gas occupies a smaller volume, it exerts a higher pressure; when it occupies
a larger volume, it exerts a lower pressure (assuming the amount of gas and the temperature do
not change). Since P and V are inversely proportional, a graph of 1/P vs. V is linear.

Unlike the P–T and V–T relationships, pressure and volume are not directly proportional to each
other. Instead, P and V exhibit inverse proportionality: Increasing the pressure results in a
decrease of the volume of the gas. Mathematically this can be written:

P ∝1/VorP=k ⋅1/VorP⋅V =korP 1 V 1=P 2V 2

with k being a constant.

Moles of Gas and Volume: Avogadro’s Law

The Italian scientist Amedeo Avogadro advanced a hypothesis in 1811 to account for the
behavior of gases, stating that equal volumes of all gases, measured under the same conditions of
temperature and pressure, contain the same number of molecules. Over time, this relationship
was supported by many experimental observations as expressed by Avogadro’s law: For a
confined gas, the volume (V) and number of moles (n) are directly proportional if the pressure
and temperature both remain constant.

In equation form, this is written as:

V ∝n orV =k × n orV 1/n1=V 2/ n2

The Ideal Gas Law

To this point, four separate laws have been discussed that relate pressure, volume, temperature,
and the number of moles of the gas:

 Boyle’s law: PV = constant at constant T and n

 Amontons’s law: P/T = constant at constant V and n
 Charles’s law: V/T = constant at constant P and n
 Avogadro’s law: V/n = constant at constant P and T

Combining these four laws yields the ideal gas law, a relation between the pressure, volume,
temperature, and number of moles of a gas:

PV =nRT

where P is the pressure of a gas, V is its volume, n is the number of moles of the gas, T is its
temperature on the kelvin scale, and R is a constant called the ideal gas constant or the universal
gas constant.

Gases whose properties of P, V, and T are accurately described by the ideal gas law (or the other
gas laws) are said to exhibit ideal behavior or to approximate the traits of an ideal gas
Numbering, pacing and sequencing 2.2.2
Title Relationship of pressure, volume, and
temperature to one another and to work, based
on the ideal gas law

Purpose Describe how pressure, volume, and temperature

relate to one another and to work, based on the
ideal gas law
Brief summary of overall task Visit this interactive PhET simulation to investigate the
relationships between pressure, volume, temperature,
and amount of gas. Use the simulation to examine the
effect of changing one parameter on another while
holding the other parameters constant (as described on
the various gas laws).
Spark

Explain the concept of breathing using Boyle’s law

Individual task After investigating the simulation summarize the gas
laws
Give the answer to the question on the spark
Post your answers on the discussion forum
2.2.2provided
Interaction begins ● Read what your colleagues have posted in the
discussion forum 2.2.2
● Keeping netiquette in mind, comment on what three
of your colleagues have posted.
● Read the facilitator’s comments too to get feedback
Add any new point you have learnt to your
notes/portfolio
E-moderator interventions

Schedule and time This task should take you 45 minutes

Next pressure–volume work
2.2.3 Pressure- Volume work

Pressure–volume work is the work that is done by the compression or expansion of a fluid.
Whenever there is a change in volume and external pressure remains constant, pressure–volume
work is taking place. During a compression, a decrease in volume increases the internal pressure
of a system as work is done on the system. During an expansion (Figure 2.6), an increase in
volume decreases the internal pressure of a system as the system does work

Figure 2.6 :An expansion of a gas requires energy transfer to keep the pressure constant. Because
pressure is constant, the work done is PΔV .

Recall that the formula for work is W=Fd. We can rearrange the definition of pressure, P=F/A,

to get an expression for force in terms of pressure.

F=PA

Substituting this expression for force into the definition of work, we get

W=PAd.

Because area multiplied by displacement is the change in volume, W=PΔV

, the mathematical expression for pressure–volume work is

W=PΔV.
 Just as we say that work is force acting over a distance, for fluids, we can say that work is the
pressure acting through the change in volume. For pressure–volume work, pressure is analogous
to force, and volume is analogous to distance in the traditional definition of work.

Numbering, pacing and sequencing 2.2.3

Title Pressure- Volume work
Purpose To describe pressure-volume work

Brief summary of overall task Watch the video on pressure volume work. If the
volume of a system increases while pressure remains
constant, is the value of work done by the system W
positive or negative? Will this increase or decrease the
internal energy of the system?
Spark

Write an expression of work in terms of pressure

and volume from the spark
Individual task After watching the video summarize your findings
Give the answer to the question on the spark
Post your answers on the discussion forum 2.2.3
provided
Interaction begins ● Read what your colleagues have posted in the
discussion forum 2.2.3
● Keeping netiquette in mind, comment on what three
of your colleagues have posted.
● Read the facilitator’s comments too to get feedback
Add any new point you have learnt to your
notes/portfolio
E-moderator interventions

Schedule and time This task should take you 25 minutes

Next problems involving the first law of thermodynamics
2.2.4 Problems involving the first law of thermodynamics

Calculating Change in Internal Energy

Suppose 40.00 J of energy is transferred by heat to a system, while the system does 10.00 J of
work. Later, heat transfers 25.00 J out of the system, while 4.00 J is done by work on the system.
What is the net change in the system’s internal energy?

Strategy

You must first calculate the net heat and net work. Then, using the first law of thermodynamics,
ΔU=Q−W,

find the change in internal energy.

Solution

The net heat is the transfer into the system by heat minus the transfer out of the system by heat,
or

Q=40.00 J−25.00 J=15.00 J.

The total work is the work done by the system minus the work done on the system, or

W=10.00 J−4.00 J=6.00 J.

The change in internal energy is given by the first law of thermodynamics.

ΔU=Q−W=15.00 J−6.00 J=9.00 J

Numbering, pacing and sequencing 2.2.4

Title Problems involving the first law of
thermodynamics

Purpose Solve problems involving the first law of

thermodynamics

Brief summary of overall task Using the example shown in above express another
strategy of calculating change in internal energy
 Spark

What is the change in internal energy of a system

when a total of 150.00 J of heat transfer occurs out
of (from) the system and 159.00 J of work is done
on the system?
Individual task Show your work out on the strategy
Give the answer to the question on the spark
Post your answers on the discussion forum 2.2.4
provided
Interaction begins ● Read what your colleagues have posted in the
discussion forum 2.2.4
● Keeping netiquette in mind, comment on what three
of your colleagues have posted.
● Read the facilitator’s comments too to get feedback
Add any new point you have learnt to your
notes/portfolio
E-moderator interventions

Schedule and time This task should take you 20 minutes

Next Application of first law to non-flow processes

2.3 Assessment Questions

1. What is the pressure-volume work done by a system if a pressure of 20 Pa causes a change in

volume of 3.0m3?

a. 0.15J
b. 6.7 J
c. 23 J
d. 60 J

2. What is the net heat out of the system when 25J is transferred by heat into the system and 45J
is transferred out of it?
 a. -70J
b. -20 J
c. 20 J
d. 70J

3. A gas in a closed container is heated with 10J of energy, causing the lid of the container to rise
2m with 3N of force. What is the total change in energy of the system?

a. 10J
b. 6J
c. 4J
d. −4J

4. If a fixed quantity of an ideal gas is held at a constant volume, which variable relates to
pressure, and what is that relation?

a. Temperature; inverse proportionality (P∝ 1/T)

b. Temperature, direct proportionality to square root (P∝ √T)
c. Temperature; direct proportionality (P∝ T)
d. Temperature; direct proportionality to square (P∝T2)

5. By convention, if Q is positive, what is the direction in which heat transfers energy with
regard to the system?

a. The direction of the heat transfer of energy depends on the changes in W, regardless of
the sign of Q.
b. The direction of Q cannot be determined from just the sign of Q.
c. The direction of net heat transfer of energy will be out of the system.
d. The direction of net heat transfer of energy will be into the system

6. What is net transfer of energy by heat?

a. It is the sum of all energy transfers by heat into the system.
b. It is the product of all energy transfers by heat into the system.
c. It is the sum of all energy transfers by heat into and out of the system.
d. It is the product of all energy transfers by heat into and out of the system.

7. When heat adds energy to a system, what is likely to happen to the pressure and volume of the
system?

a. Pressure and volume may both decrease with added energy.

b. Pressure and volume may both increase with added energy.
c. Pressure must increase with added energy, while volume must remain constant.
d. Volume must decrease with added energy, while pressure must remain constant.
8. Three hundred ten joules of heat enter a system, after which the system does 120 J of work.
What is the change in its internal energy? Would this amount change if the energy transferred by
heat were added after the work was done instead of before?

a. -190J ; this would change if heat added energy after the work was done
b. 190J; this would change if heat added energy after the work was done
c. -190 J; this would not change even if heat added energy after the work was done
d. 190J; this would not change even if heat added energy after the work was done

What is pressure?

a. Pressure is force divided by length.

b. Pressure is force divided by area.
c. Pressure is force divided by volume.
d. Pressure is force divided by mass.

What are the ways to add energy to or remove energy from a system?

a. Transferring energy by heat is the only way to add energy to or remove energy from a
system.
b. Doing compression work is the only way to add energy to or remove energy from a
system.
c. Doing expansion work is the only way to add energy to or remove energy from a system.
d. Transferring energy by heat or by doing work are the ways to add energy to or remove
energy from a system.

2.4 E-References

Relating Pressure, Volume, Amount, and Temperature: The Ideal Gas Law

Available on https://cnx.org/contents/e4twRo8c@16/Relating-Pressure-Volume-Amount-and-
Temperature-The-Ideal-Gas-Law

First law of Thermodynamics: Thermal Energy and Work

Available on https://cnx.org/contents/q33c2ZMt@13/First-law-of-Thermodynamics-Thermal-
Energy-and-Work

Phet interactive simulation on gas properties available on

https://phet.colorado.edu/sims/html/gas-properties/latest/gas-properties_en.html

Audiopedia (2009) More on internal energy | Thermodynamics | Physics | Khan Academy.

Retrieved July 28, 2020 from
https://youtu.be/aOSlXuDO4UU