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First Law of Thermodynamics

(Lecture in Physics Fundamentals 2)

Reynold V. Luna
Physics Instructor, College of Science 1

Pioneer of
Isenthalpic entropy;
Pioneer of heat
Pioneer of expansion; Heat engine thermodynamic
and first law;
thermodynamics SI unit of statement definition of
SI unit of energy
temperature entropy and its
unit

Sadi Carnot James Prescott Joule Lord Kelvin Max Planck Rudolf Clausius

Pioneer of
Free energy
statistical Inventor of the Ensembles,
relations; Ideal Pioneer of the
mechanics; term potential free energy and
gas speed third law
statistical energy phase
distribution
definition of transitions
function
entropy

Ludwig Boltzmann James Clerk Maxwell Walther Nernst William Rankine J. Willard Gibbs
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• Thermodynamics is the set of laws that govern the properties of matter at

the macroscopic scale. It is the study of relationship involving heat,
mechanical work, and other aspects of energy and energy transfer - a
phenomenological theory of equilibrium states and transitions among
them.
• Kinetic Theory or Kinetics provides microscopic description of the
transition process between equilibrium states.
• Pure thermodynamics is concerned only with macroscopic quantities
which describe large-scale properties of matter. The macroscopic
quantities such as pressure, volume, temperature, and composition, are
called macroscopic coordinates. They can in general be measured directly.
• Classical thermodynamics is derived from molecular treatment.
• Statistical mechanics or sometimes statistical thermodynamics is
concerned with the microscopic quantities or properties of matter. It
applies statistical methods to calculate the number of molecules in each of
the molecular energy states. 3

What is a System?
System – a set of interacting or interdependent
elements (components) forming an integrated whole or
a set of elements and relationships which are different
from relationships of the set or its elements to other
elements or sets.

Environment – or surroundings is the remainder of the

universe that lies outside the boundaries of the system.
A valid system may:
 be a single object or particle
 be a collection of objects or particles
 be a region of space (i.e. interior of automobile engine combustion cylinder)
 vary in size and shape (i.e. a rubber ball, which deforms upon striking a wall) 4

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Example of Open and Closed Systems

Thermodynamic System
Type of transfer
System Type of wall (boundary) Mass and
Work Heat
Energy
Open Permeable to matter and energy   
Permeable to energy but not to
Closed
matter
  
Isolated Isolating   
Thermally Isolated Adiabatic   
Mechanically Adynamic (impermeable to
Isolated matter)
  
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Physical State
It is determined by a complete description of physical system based on
measurement or scientific theory
• Microscopic State or Microstate – Molecular state (described in terms of
speed, kinetic energy of molecules)
• Macroscopic State or Macrostate – Thermodynamic state (described in
terms of pressure, volume, temperature, etc.)

Conditions of Thermodynamic States

• Steady-state – states that are time independent near equilibrium transitions
• Transient-state – states that are time dependent near equilibrium transitions

Thermodynamic Property
a.k.a. Thermodynamic Quantity is a quantifiable macroscopic characteristic of a system.

A. According to the amount of B. According to measurement

material
• Extensive property –depends on the
system size or the amount of material
in the system.
• Intensive property – does not depend
on the system size or amount of
material in the system.
• Specific property – the ratio of an
extensive property to unit mass
• Measurable property - can be directly
measured using an appropriate
instrument. (i.e. mass, temperature,
pressure, volume, velocity, elevation, and
specific heat)
• Derived property - cannot be measured.
(i.e. internal energy, enthalpy and
entropy)
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Thermodynamic Parameter
a.k.a Thermodynamic Variables

State Parameter Process or Path Parameter

- Variables that are dependent on - Variables that are dependent on
thermodynamic state (i.e. pressure, the mode of transferring energy
volume, temperature) (i.e. heat and work).

Thermodynamic Process
It is the change of thermodynamic state.

 Natural – Spontaneous, irreversible or non-equilibrium process

 Unnatural – Impossible process
 Fictively Reversible – quasi-equilibrium process (i.e. quasi-static process -
one that occurs slowly so that the system moves through a series of
equilibrium states.)
 Reversible – process close to equilibrium at all times
 Cyclic – the initial and final states are the same
 Conjugate variables – process involving a pair of parameters

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Basic Thermodynamic Quantities

Quantity Symbol Definition SI Unit
Mass Quantity of matter kilogram, kg
Volume Space occupied by an object meter3, m3
Density Ratio of mass and volume of a homogenous substance kg/m3
Pressure Force acting normal to the surface of an object pascal, Pa
Temperature Relative hotness of an object kelvin, K
No. of moles macroscopic measure of the amount of substance mole, mol
Particle Number microscopic measure of the amount of substance molecule
Specific Volume Inverse of density m3/kg
Transfer of energy, measured as product of force perpendicular to the
Work joule, J
object and distance moved by that object in the direction of force

Heat Energy transfer due to spatial temperature difference or phase change joule, J
Internal Energy Total energy within a system joule, J
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Systems with Large Number of Particles

• Includes GASES (air in room), LIQUIDS (chemical reagents) and SOLIDS
(atoms and molecules in a piece of gold)

• Its measurable properties ( i.e. p, V, T) are described by statistical means. 12

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First Law of Thermodynamics

A restatement of the law of energy conservation

∆ = −

+ Q if heat is absorbed by the system

– Q if heat is released by the system

+ W if work is done by the system

– W if work is done on the system

For infinitesimal changes of state:

= −
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Activity
In the blank columns of the following table, fill in the boxes with the system
considered in each situation and the correct signs (+, -, or 0) for , , and ∆ .

Situation System ∆
Rapidly pumping up
Air in the tire
a bicycle tire
Pan of room-
temperature water Water in the pan
sitting on a hot stove
Air quickly leaking
Air in the balloon
out of a balloon
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Some Applications of First Law

On cyclic processes On isolated systems
The initial and final states are From the operational
the same: = definition of isolated system:
Then, = =0
∆ = − Then,
becomes ∆ =0
= or
= constant

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Internal Energy of an Ideal Gas

Internal energy is all the energy of a system that is associated with its
microscopic components — atoms and molecules — when viewed from a
reference frame at rest with respect to the center of mass of the system.

Joule’s Law states that the internal energy of an ideal gas depends only
on its temperature , not on its pressure or volume:
= ( )

Isobaric, isochoric and adiabatic processes of same initial states have the
same change in internal energy if their final states are in an isotherm.
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Mechanical Interaction of an Ideal Gas

Doing work transfers energy coherently.

The piston is pushed inward and the gas is

compressed quasi-statically (to kept internal thermal
equilibrium constant at all times).

The differential work done on the gas is:

= ⃗∙ ⃗= − =− =−

The net infinitesimal work

done on gas from to is:

=−

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Work: for Quasi-static Process

Time for the gas to return to equilibrium
after change of state:
∆
=

Characteristic time of the process:

∆
=

where: The process is quasi-static when:

= mean speed of gas molecules
≪
= speed of the piston ≪
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Work done on a system undergoing a quasi-static cyclic process

Cyclic process – a thermodynamic
process that starts and ends in the
same state.

=− ,

where: Γ = a closed path

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Activity
Arrange the work done by the system in increasing order.

A B C
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Activity
When a gas is taken from a to c along the curved path in the figure,
the work done by the gas is = −35 J and the heat added to the
gas is = −175 J. Along path abc, the work done by the gas is
= −56 J. (That is, 56 J of work is done on the gas.)
(a) What is for path abc?
(b) If = , what is for path cda?
(c) What is for path cda?
(d) What is − ?
(e) If − = 42 J, what is for path da?
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Work
General expression for work done on a system undergoing a quasi-static
thermodynamic process:

=
where:
Γ = path representing the thermodynamic process taken by the system
= generalized force (intensive state variable)
= generalized displacement (extensive state variable)

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Expressions for work done on

thermodynamic systems
Thermodynamic Generalized Infinitesimal
Generalized Force,
System Displacement, Work,
PVT system (fluid) Pressure, Volume, −
Stretchable Wire Force, Length,
Surface Film Surface Tension, Surface area,
Electrochemical Cell Electromotive force, Charge,
Dielectric Solid Electric field, Polarization,
Paramagnetic Solid Magnetic field, Magnetization,

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Thermal Interaction of an Ideal Gas

Heating transfers energy incoherently .

Heat absorbed by a system due to temperature

change ∆ ,
Isochoric process: = ∆
Isobaric process: = ∆

where:
= molar specific heat at constant volume
= molar specific heat at constant pressure

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First Law and Conjugate

Parameters Processes
Activity:
Match the 4 thermodynamic processes
of the pV diagram presented on the
right to the table below.

A.
B.
C.
D.
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Adiabatic Process

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First Law and Ideal Gas under

Conjugate mechanical parameters process
Isochoric process (e.g. heating of gas in a sealed metal container)
Restriction: = constant; = ∆
Prediction: = 0 since ∆ = 0
∆ = = ∆

Isobaric process (e.g. heating of air under 1 atm)

Restriction: = constant; = ∆
Prediction: =∫ = − = ∆ = ∆
∆ = ∆ − ∆ = ( − )∆

For both process, their ∆ are same. Thus, = −

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Activity
1) A gas undergoes an isochoric process in which the
pressure increases from 50.0 kPa to 100. kPa. How much
work is done?
2) 1.00 mol of an ideal gas is at a temperature of 293 K and a
volume of 22.0 L. It is compressed in an isobaric process to a
volume of 10.0 L. Find the work done, the heat flow, and the
change in internal energy

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First Law and Ideal Gas under

Conjugate thermal parameters process
Isothermal process (e.g. expanding steam at constant 110C)
Restriction : = constant; ∆ = 0; =

Prediction: =∫ ( ) = ∫

= = ln
Adiabatic process (Quasi-static) or Joule-Thomson Effect
Restriction : = constant; = 0; =
= (same as isochoric process)
Prediction: =−
Taking the total differential of = ,
+ = 29

Quasi-static Adiabatic or Isentropic process …

Then,
( − )
+ =− =−

Let ≡ = adiabatic index

Divide both side by ,
+ = (1 − γ)
Simplifying and integrating, The work done by is:
ln + ln = constant =− ( − )
or
= ( − )
= constant
Using ideal gas law, =
= constant
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Activity
1) 1.00 mol of an ideal gas is compressed in an isothermal
process at a temperature of 293. K. The initial volume is 22L,
and the final volume is 10L. Calculate the work done and
the heat flow into the system
2) A gas undergoes an isothermal expansion from a certain
pressure, temperature, and volume. The volume of the gas
doubles. The same gas undergoes an adiabatic expansion
from the same starting point, and again the gas doubles in
volume. In which process is more work done? In which
process is there a heat flow?
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3. Heat is removed from an ideal

gas as its pressure drops from
200 kPa to 100 kPa. The gas then
expands from a volume of 0.05
m3 to 0.1 m3 as shown in the PV
diagram. If curve AC represents
an isotherm, find the work done
by the gas and the heat added to
the gas.

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Molar Heat Capacities of Gases

In an isobaric process, the first law Recall,
reduces to: = +
∆ = ∆ The molar heat capacity of monatomic
The change in internal energy of gas at constant pressure is:
monatomic gas is: 5
3 =
∆ = ∆ 2
2 For diatomic gas:
The molar heat capacity of monatomic 5
gas at constant volume is: =
2
3 7
= =
2 2
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Molar Heat Capacities of Solids

Applying the equipartition theorem to the simple
model for a solid (each atom with 6 dof = 3 doftrans+3dofvib ) ,
the total energy of an atom in a solid is:
=6 =3
and the total energy of crystal containing atoms or
moles is:
=3 =3
The molar heat capacity of ideal monatomic solid at
constant volume is:
= 3 = 24.9J/mol ∙ K
This result is known as the Dulong–Petit law. Experimental values of in agreement
with Dulong-Petit law. 34

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Activity
1. A 2.00-mol sample of a diatomic ideal gas expands slowly and
adiabatically from a pressure of 5.00 atm and a volume of 12.0
L to a final volume of 30.0 L.
(a) What is the final pressure of the gas?
(b) What are the initial and final temperatures?
Find (c) , (d) ∆ , and (e) for the gas during this process.
2. Calculate the change in internal energy of 3.00 mol of helium
gas when its temperature is increased by 2.00 K.

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Human Metabolism
Metabolism is the total of all the chemical
processes that occur in the cells of a body.
It consists of anabolism in which molecules are
built-up and catabolism in which enzymes
break down the food consumed through
hydrolysis and phosphorolysis (at cellular level).
The metabolic rate is the rate at which internal
energy is transformed within the body. It is
usually specified in kcal/h or in watts. Typical
metabolic rates for a variety of human activities
for an average 65-kg adult is shown:
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What is the relevance of physics in a

discussion on energy and metabolism?
Physics relates to metabolic processes through the laws of thermodynamics.

<0 For an energy balance, under steady-state conditions

where the core body temperature and the ambient
temperature remain constant, the quantity of energy
produced will equal the quantity of energy dissipated.
decreases
= +
> 0 Where:
= metabolic rate (total energy produced in the body)
= total metabolic energy production of the body
= the external work done by the body
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Activity
1. Calculate the average metabolic rate of a 65-kg person who sleeps 8.0 h,
sits at a desk 6.0 h, engages in light activity 6.0 h, watches TV 2.0 h, plays
tennis 1.5 h, and runs 0.50 h daily.
2. A 65-kg person decides to lose weight by sleeping one hour less per day,
using the time for light activity. How much weight (or mass) can this person
expect to lose in 1 year, assuming no change in food intake? Assume that 1
kg of fat stores about 40,000 kJ of energy.

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References
1. Young, H., Freedman, R. and Ford, A. (2016) University Physics with Modern Physics, 14e,
Pearson Prentice Hall
2. Hewitt, P. (2013) Conceptual Physics, 12e, Addison-Wesley
3. Giancoli, D. (2014) Physics: Principles with Application, 7ed., Pearson Prentice Hall
4. Poirier, B. (2014) A Conceptual Guide to Thermodynamics, John Wiley & Sons
5. Blundell, S.J. and Blundell, K.M. (2010) Concepts in Thermal Physics, 2ed., Oxford University
Press
6. Zemansky, M. and Dittman, R. (1997) Heat and Thermodynamics, 7ed., McGraw-Hill Ltd.
7. Callen, H. (1985) Thermodynamics and an Introduction to Thermostatistics 2ed., John Wiley &
Sons

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