LAWS OF

THERMODYNAMICS
GROUP 3
Estenzo, Necca A.
Fulgencio, Marco Angelo D.
Galagar, Crizel M.
Gierran, Renz Allen G.
 CONTENTS OF THIS PRESENTATION

01 02
ZEROTH LAW OF FIRST LAW OF
THERMODYNAMICS THERMODYNAMICS
Fulgencio, Marco Angelo D. Gierran, Renz Allen G.

03 04
SECOND LAW OF THIRD LAW OF
THERMODYNAMICS THERMODYNAMICS
Estenzo, Necca A. Galagar, Crizel M.
 ZEROTH LAW OF
01 THERMODYNAMICS
Reporter: Marco Angelo D. Fulgencio
 Terms to Remember
● System - the collection of objects we are examining
● Surroundings - the environment surrounding the system
● Diathermal walls - between two thermodynamic systems allows heat
transfer but do not allow transfer of matter across it
● Adiabatic walls - between two thermodynamic systems does not allow
heat or chemical substances to pass across
● Thermal equilibrium - when two bodies are brought into contact with
each other and separated by a barrier that is permeable to heat, there will
be no transfer of heat to one another
 ZEROTH LAW OF THERMODYNAMICS
This law of Thermodynamics states that if two systems are in thermal
equilibrium with a third system, then those two systems are in thermal
equilibrium with each other.

A = B

A B C = =
C
ZEROTH LAW OF THERMODYNAMICS

Ralph H. Fowler (1889 - 1944)

- British physicist and astronomer
 ZEROTH LAW OF THERMODYNAMICS

● Daniel Gabriel
● William Thomson a.k.a.
Fahrenheit ● Anders Celsuius
Lord Kelvin
○ Invented the ○ Invented the Celsius
○ Invented the Kelvin
Fahrenheit temperature scale
scale
temperature Scale
Utilizes the expansion of Uses thermoresistors to
mercury or other liquids under measure temperature
heat

Mercury Thermometer Modern Digital Thermometer

SAMPLE PROBLEMS
1. Three substances are added to a mug to make coffee: the coffee, which is 65
degrees Celsius, the milk which is 65 degrees thermal equilibrium with the
coffee. Describe the thermal state of the sugar.
 1. Three substances are added to a mug to make coffee: the coffee, which is 65
degrees Celsius, the milk which is 65 degrees thermal equilibrium with the
coffee. Describe the thermal state of the sugar.

Answer:
Based on the zeroth law of thermodynamics, the sugar is in equilibrium with
the milk. Therefore, its temperature is also 65 degrees Celsius.
2.) Gas A is in thermal equilibrium, with gases B and C. Which of the following is a
valid Conclusion?
a. Gases B and C are in thermal equilibrium with each other
b. Gases A and B have equal amounts of entropy
c. No conclusion can be drawn
d. Thermal equilibrium of gas B is indirectly proportional to that of Gas C
e. Thermal equilibrium of Gas B is directly proportional to that of Gas C
2.) Gas A is in thermal equilibriu, with gases B and C. Which iof the following is a
valid Conclusion?
a. Gases B and C are in thermal equilibrium with each other
b. Gases A and B have equal amounts of entropy
c. No conclusion can be drawn
d. Thermal equilibrium of gas B is indirectly proportional to that of Gas C
e. Thermal equilibrium of Gas B is directly proportional to that of Gas C

Answer:
a.) Gases B and C are in thermal equilibrium with each other.
FIRST LAW OF
THERMODYNAMICS
Reporter: Renz Allen G. Gierran
02
 1ST LAW OF THERMODYNAMICS
The first law of thermodynamics states that energy can
neither be created nor destroyed, only altered in form. Energy
transfer occurs when mass crosses the control boundary,
external work is performed, or heat is transferred across the
boundary in any system. These cause a change in the amount
of stored energy in the control volume. The First Law of
Thermodynamics applies the principle of energy conservation
to the boundaries of a system of interest.
 1ST LAW OF THERMODYNAMICS
The First Law says that the change in internal energy is equal to the heat
added to the system minus the work done by the system to the
surroundings. This is written
ΔU = Q − W

where
● ΔU is the change in internal energy,
● Q is the heat added to the system,
● and W is the work done by the system to the surroundings.
 Processes derived from the equation ΔU = Q − W
1. Constant volume - no work is done on or by the system.
W = 0 —> ∆U = Q - 0 —> ∆U = Q Isochoric Process
2. Constant temperature - heat transfered is completely used for work.
∆U = 0 —> 0 = Q - W —> Q = W Isothermal Process
3. No heat transfer - the internal energy is used exclusively for work only.
Q = 0 —> ∆U = 0 - W —> ∆U = -W Adiabatic Process
4. Q and W are both equal to 0 - no change in internal energy
∆U = 0 - 0
 FOUR KINDS OF SYSTEM
OPEN SYSTEM CLOSED SYSTEM ISOLATED SYSTEM ADIABATIC SYSTEM
Work done during Volume Changes

When the piston moves out an infinitesimal distance dX, the Work dW done by this force is
dW = Fdx = pAdx
But Adx = dV
Therefore, work done by the system in this infinitesimal change is
dW = pdV
In a finite change of volume from V1 to V2 :

If the pressure p remains constant while the volume changes from V1 to V2, the work done by
the system is
Infinitesimal Changes of State

Since dW is equals to pdV

Therefore, we can rewrite the equation to
dU = dQ - pdV
 Sample Problems
1. One gram of water (1 cm3) becomes 1671 cm3 of steam when boiled at a constant
pressure of 1 atm (1.013 x 105 Pa). The heat of vaporization at this pressure is 2.256 X
106 J/kg. Compute the work done by the water when it vaporizes

Solution
Given: V1 = 1 cm³ = 1×10-6 m³ ; V2 = 1671 cm³ = 1671×10-6 m³ ; p = 1.013 × 10⁵ Pa

W = p × (V)|Vf

W = p(Vf - Vi)
W = (1.013×105 Pa)(1671×10-6 m³ - 1×10-6 m³)
W = 169 Joules
 Sample Problems
2. The process of water evaporation at constant
pressure is shown schematically in the figure on the
right. In the initial state, 1 mol of liquid water
occupies the volume Vi 18 cm3 and fills up the
whole available space of the vessel. The pressure is
constant and equals Pext= 1 atm. In the final state,
only water vapour is present, which ocupies the
volume Vf = 30.6 L. A change of 1 mol of liquid water
into vapour at the pressure of 1 atm requires supply
of the heat Q = 40670 J. Find the change in the
internal energy of the system.
 Sample Problems
Given:
Q = 40, 670 J Vf = 30.6×10-3 m³
p = 101, 325 Pa Vi = 18×10-6 m³

Solution:
Since

W = p × (V)|Vf
W = p(Vf - Vi) or W = p(V2 - V1 )

Then, ∆U = Q - p(Vf - Vi)

∆U = 40, 670 J × 101, 325 Pa × (30.6×10-3 m³ - 18×10-6 m³)
∆U ≈ 37, 569 Joules
SECOND LAW OF
THERMODYNAMICS
Reporter: Estenzo, Necca A.

03
 After a period of
COOL DOWN
time…

A HOT COFFEE BECOME EVEN HOTTER

 SPONTANEOUS PROCESSES
Spontaneous Processes are
processes that have the ability to
occur on their own, without the
need of an energy input from an
external source.
SECOND LAW OF THERMODYNAMICS
● The second law of thermodynamics
specifically states that:
“Energy can flow spontaneously
from a system at a higher
temperature to a system at a
lower temperature. Energy does
not flow spontaneously from a
lower to higher temperature.”
SECOND LAW OF THERMODYNAMICS
● But its generalized version declares
that:
“The entropy of an isolated
system never decreases. It
either remains constant
(reversible process) or increases
(irreversible process).”
𝝙S ≥ 0
 WHAT ARE REVERSIBLE AND
IRREVERSIBLE PROCESSES?
● Reversible Processes are processes in which both the
system and its surroundings can be simultaneously
returned to their original states after the process has
been completed.
● Irreversible Processes are processes in which the
system and its surroundings cannot be simultaneously
returned to their initial states after the process has been
completed.
ENTROPY
● When an amount of energy is added to a system by
some reversible process, the change in entropy of the
system is defined as:
○ ΔS = Q [T is constant]
T
○ dS = dQ [non-constant T]
T
○ ΔS = ∫12dS = ⌠2 dQ [A system taken reversibly from
⌡1 T state 1 to 2]
 The total change in entropy of this system
comprising these objects can be represented by:

TH TL
-Q Q
ΔS = ΔSH+ΔSL = TIHF
+ TILF

ΔS = Q ( - )>0
1 1

H L
TILF TIHF

Where TF<TIHF<TH and TL<TILF<TF

TH TL “Energy can flow spontaneously from

a system at a higher temperature to a
system at a lower temperature.

H L Energy does not flow spontaneously

from a lower to higher temperature.”
 The total change in entropy of this system
comprising these objects can be represented by:

TH TL
-Q Q
ΔS = ΔSH+ΔSL = TIHF
+ TILF

ΔS = Q ( - )>0
1 1

H L
TILF TIHF

Where TF<TIHF<TH and TL<TILF<TF

TH TL “The total entropy of any

system and that of the

H L surroundings always increases.”

TAKE NOTE:
● Entropy is a state variable. Hence, it is
pathway-independent.
Sample Problem:
A 5.0 kg piece of metal at 900 K is placed into a
large body of water at 300 K. Assume that the
specific heat of metal is 500 J/kg·K and the body
of water is so large that its temperature does not
change. (A) Calculate the change in entropy of the
metal (ΔSmetal); (B) as well as of the water (ΔSwater).
(A) Given:
mmetal = 5.0 kg
Tmetal = T1 (initial temperature) = 900 K
Twater = T2 (final temperature) = 300 K
cmetal = 500 J/kg·K
ΔSmetal = ?

Solution:

=∫
2 dQ We do not have a value for Q. Since we have a value for
ΔSmetal = ∫12dS mass and specific heat, we will make use of the
1 T calorimetry formula Q = mcΔT, and substitute it to Q.

∫
T2 mcdT
=
T1 T
 ∫
T2
mcdT
= T1 T

∫ ∫
T2
dT du
= mc T1
= ln u + C
T u

T2
= mc (ln T)
T1
M
= mc (ln T2 - ln T 1 ) logb = logbM - logbN
N
T2
= mc ln
T1
Substituting the given values (mmetal = 5.0 kg, T1= 900 K, T2 = 300 K, cmetal = 500 J/kg·K):
300 K
ΔSmetal = (5.0 kg)(500 J/kg·K)ln( ) = -2,747 J/K
900 K
 refers to a process in which
(B) Given: a system
changes—whether it be the
ΔT = 0 indicates an isothermal process pressure, volume and/or
mmetal = 5.0 kg contents—without the
temperature changing
Tmetal = 900 K
Twater = Tconstant = 300 K
cmetal = 500 J/kg·K
ΔSwater = ?

Solution:
Since T is constant, in order to solve for ΔSwater , we will use the formula:
Q Since we don’t have a value for Q yet, we will make use of
ΔSwater = the formula Q = m c ΔT again and solve for Q first.
T metal metal
Solving for Q,
Q = mmetalcmetalΔT
= (5.0 kg)(500 J/kg·K)(900 K - 300 K)
= 1,500 KJ
Finally, solving for ΔSwater ,
Q
ΔSwater =
Tconstant

1,500 KJ 1,000 J 1,500,000 J

ΔSwater = ( )( )= = 5,000 J/K
900 K 1 KJ 900 K Does not
violate the
2nd law of
ΔStotal = ΔSmetal + ΔSwater = -2,747 J/K + 5,000 J/K = 2,253 J/K > 0 thermodynam
ics
 THIRD LAW OF
04 THERMODYNAMICS
Reporter: Galagar, Crizel M.
Third Law of Thermodynamics
● The third law was developed by
Chemist Walther Hermann Nernst
between 1906-1912
● referred as Nernst Theorem

“ The value of entropy of a

completely pure crystalline
substance is zero at absolute
zero temperature”
Absolute Zero Is the coldest possible
Absolute temperature is
the lowest temperature
temperature in the universe known and sets a lower
limit to the Universe’s
temperature range.

Absolute zero in the temperature is :

● 0 Kelvin or

● -273.15 °C

● -459.67 °F
 Temperature
- a measure of available heat
energy
- Collection of kinetic energy
for the system
at absolute zero
everything is in the

Solid phase

● The entropy of any crystalline substance at

absolute zero will be equal to zero
 Mathematical Definition of Entropy by Ludwig Boltzmann:
The entropy of any
crystalline at S = k ln W
absolute zero will
be equal to zero only one microstate is possible

S=0 S= k ln 1

● In light of Boltzmann’s entropy formula, we can make

sense this 3rd law of thermodynamics
● At 0K, all particles are in their energetic ground
state ( W=1, S=0)
Finding S(T) from experimental data
 Formulas to keep in mind :

● To find a change in ● If Cp has been measured

entropy with changing down to temperatures
T (with no phase sufficiently close to 0 K, this
change), integrate equation
using

can be used to calculate the

absolute entropy. This is known
as the “third law method” of
measuring entropy
 Formulas to keep in mind :

● Debye’s Theory at the ● Phase transitions, at

lowest temperature constant pressure
data point

S(T) = Cp(T)/3
 SAMPLE PROBLEM

EXAMPLE 1

It is known that the molar heat capacity of a substance at low

temperature can be approximated by the relation Cp = aT³ ,
where a is a constant. Determine the molar entropy of a metal at
10K if the molar heat capacity at this temperature is 0.45 J/molK.
Given:
Cp =aT³ , a = constant

0
0
 SAMPLE PROBLEM

EXAMPLE 2

Calculate the molar entropy of carbon disulfide at 25.00 °C and 1 bar from the heat capacity data for
the solid in Table and the following data for p = 1 bar. At the melting point,161.11 K, the molar enthalpy
of fusion is 4.38 x10↑³ J/molK. The molar heat capacity of the liquid in the range 161–300 K is described
by Cp,m = a+bT, where the constants have the values a = 74.6J/molK and b = 0.0034J/molK². The area
under the line is 75.5J/molK.
Given:
Cp,m = a+bT
a = 74.6J/molK
b = 0.0034 J/molK²
T = 25.00 °C + 273.15 K = 298.15 K
A = 75.5J/molK
Solutions:
Debye theory extrapolation from 0 K to 15.05 K:
S(T) = Cp(T)/3
S(T) = 6.9 J/molK÷3 = 2.3 J/molK Lowest temperature
THANK YOU
REFERENCES:
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[Video]. YouTube. https://youtu.be/kuGmsnzjbpE
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Private Tutoring (2011) Understanding the Zeroth Law of Thermodynamics
https://www.varsitytutors.com/high_school_physics-help/understanding-the-zeroth-law-of-thermodynamics#:
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