Report - Fundamental Property Relation and Its Usage

BRACT’S Vishwakarma Institute of Technology, Pune-411037
Chemical Engineering Department
Case study
On
Techniques Used For Estimating Earth’s Internal

Temperature
(Home Assignment)
Guide
Prof. Dr. Tanushree Bhattacharjee
Submitted By-
Division-CH-A, GROUP-8
Prasad Godage- 12011290
Shriram Gole - 12010563
Tejas Ingole - 12011187
Ganesh Janrao - 12010498
Sohan Kambale – 12011197
Sanket Khade - 12011161

Introduction :
Relationships which relate all the Fundamental properties are known as

fundamental property relationship.Thermodynamic properties are defined as
characteristic features of a system capable of specifying the system’s state. The
thermodynamic properties of a material are classified in several different ways.The
fundamental thermodynamic relation are four fundamental equations which
demonstrate how four important thermodynamic quantities depend on variables
that can be controlled and measured experimentally.
Fundamental property relations -
In thermodynamics, the fundamental thermodynamic relation are four fundamental

equations which demonstrate how four important thermodynamic quantities depend
on variables that can be controlled and measured experimentally.The first and second
laws of thermodynamics are the most fundamental equations of thermodynamics. First
law of thermodynamics, also known as the law of conservation of energy, states that
energy can neither be created nor destroyed, but it can be changed from one form to
another.
First Law Of Thermodynamics Examples:
● Plants convert the radiant energy of sunlight to chemical energy through
photosynthesis. We eat plants and convert the chemical energy into kinetic
energy while we swim, walk, breathe, and scroll through this page.
● Switching on light may seem to produce energy, but it is electrical energy that
is converted.
Second law of thermodynamics states that the entropy in an isolated system always
increases. Any isolated system spontaneously evolves towards thermal equilibrium,
the state of maximum entropy of the system.
They may be combined into what is known as fundamental thermodynamic relation
which describes all of the changes of thermodynamic state functions of a system of
uniform temperature and pressure.
First Fundamental Relation - The fundamental properties are internal energy u and
entropy s. The differential of energy properties form the basis for the derivation of a
large number of equations relating thermodynamic properties.These properties arrive
from the first and second law of thermodynamics. The first law states that energy is
conserved, and the second law states that entropy of the universe always increases.
According to first law of thermodynamics,
dU = dQ - dW……(1)
Work done,
dW = PdV……(2)
Change in entropy,
dS = dQ / T……(3)
Putting equations (2) and (3) in equation (1) final equation is expressed as,
dU = TdS - PdV
Second Fundamental Relation - Second fundamental relation is obtained from

enthalpy of system. Basically, Enthalpy is the measurement of energy in a
thermodynamic system. It is also the sum of the internal energy and the product of the
pressure and volume of a thermodynamic system.
Enthalpy of system given as,
H = U + PV
After differentiating and putting the necessary values,
The equation obtained is,
dH = TdS + VdP
Third Fundamental Relation - Third fundamental relation is obtained from helmholtz

free energy of the system.Helmholtz free energy is a concept in thermodynamics
where the work of a closed system with constant temperature and volume is measured
using thermodynamic potential. It may be described as the following equation:
A = U - TS
The change in helmholtz free energy is given as,
dA = dU - TdS
The differential of above equation is,
dA = dU - TdS - SdT
The final equation obtained is,
dA = - PdV - SdT
Fourth Fundamental Relation - The fourth fundamental relation is obtained from one
of the thermodynamic quantities i.e gibbs free energy. Gibbs free energy, also known
as the Gibbs function, Gibbs energy, or free enthalpy, is a quantity that is used to
measure the maximum amount of work done in a thermodynamic system when the
temperature and pressure are kept constant.
Gibbs free energy is given as,
G = H - TS
The change in gibbs free energy is given as,
dG = dH - T dS
The differential of above equation is,
dG = dH - T dS - S dT
The final equation obtained is,
dG = VdP - SdT
Maxwell's Relation and Its Application
Maxwell’s equations are helpful in replacing unmeasurable quantities appearing in

thermodynamic equations by measurable quantities. Using these relations, the partial
derivatives of entropy with respect to pressure and volume are expressed as
derivatives possessing easily identifiable physical meaning. Each of the four
Maxwell’s equations is derived from the exact differential equations of the four
energy properties. Consider the exact differential of internal energy. At constant
volume, it becomes
Differentiating with respect to S at constant V

(1)
At constant Entropy the equation reduce to
Differentiating with respect to S at constant V
(2)
Comparing the equation
This is the first of the four Maxwell’s equations. The remaining three equations are
obtained in a similar way starting from Equation. The results are given below.
Application of Maxwell's Equation

● Maxwell’s equations provide the partial derivatives of entropy with
pressure or volume. The partial derivatives of entropy with temperature
are provided by the entropy–heat capacity relationship.
● The usefulness of these relations lies in their quantifying entropy
changes, which are not directly measurable, in terms of measurable
quantities like P , V , T. Maxwell’s equations are used to derive the
relation between Cp and Cv. To deduce the clausius clapeyron equation.
General relations for du,dh,ds,Cv & Cp :
● The state of a simple compressible system is completely specified by two

independent, intensive properties.
● Able to calculate all the properties of a system (U, H, and S) at any state
once two independent, intensive properties are available.
● The calculation of these properties from measurable ones depends on the
availability of simple and accurate relations between the two groups.
● Development of general relations for ΔU, ΔH, ΔS in terms of P, V, T and
CV, CP.
Differential Equation of Entropy

● Entropy as a function of temperature and pressure : S=f(P,T)
1. dS =(∂S/∂P)t dP +(∂S/∂T)p dT
2. dS = Cp/Tdt - (∂V/∂T)pdP
3. dS = Cp/Tdt - R/P dp
● Entropy as a function of temperature and Volume S=f(T,V).
1. dS=(∂S/∂T)v dT +(∂S/∂V)tdV
2. dS=Cv/Tdt +(∂P/∂T)vdV
3. dS=Cv/TdT +R/VdV
● Differential Equation of Internal Energy
1. Internal energy as function of temperature and volume U=f(V,T)
2. dU=(∂u/∂T)v dT +(∂u/∂V)TdV
3. dU=CvdT +[T(dp/dt)v-P]dV
4. dU = CvdT
5. As for ideal gas (du/dv)t = 0 and (du/dp)t = 0 it proves that the
internal energy is not a function of volume and pressure.
● APPLICATIONS OF ENTROPY
1. In finances : Entropy Pricing theory, Portfolio selection
2. Entropy, the measure of a system's thermal energy per unit temperature
that is unavailable for doing useful work
3. In Black holes
Definition of chemical potential

Josiah Willard Gibbs formally introduced the concept of chemical potential
approximately 140 years ago in his foundational article. Gibbs not only established
the mathematical beauty of thermodynamics by formulating the fundamental equation
of thermodynamics of a system but also introduced the concept of chemical potential,
which he originally called the intrinsic potential. The establishment of the
fundamental equation and introduction of chemical potential marked the birth of
chemical thermodynamics and made it possible to apply thermodynamics to materials
science and engineering.
In direct analogy to electrical potential, gravitational potential, thermal potential, and

mechanical potential, the chemical potential of a chemical substance, μ, can be simply
defined as the chemical energy (U c) possessed by 1 mol of the substance
where N is the number of moles of the substance (i.e., the chemical potential of a
chemical substance represents its chemical energy intensity in a given homogeneous
system or at a given location of an inhomogeneous system). The chemical energy U c
is the same as the Gibbs free energy G, and holds for each chemical component of a
homogeneous multicomponent solution as well as for the entire homogeneous solution
Spontaneity
A spontaneous process is one that, once started, continues on its own without input of
energy. A non-spontaneous process needs a continual input of energy.
The application of spontaneity with respect to equilibrium is as follows:
A reaction will never spontaneously move away from equilibrium and will always
move spontaneously towards equilibrium.
Determination of Spontaneity:
Although spontaneous reactions are often exothermic, this is not a criteria for
spontaneity. The best indicator of spontaneity in a reaction is the change in Entropy
(S or DS).The Second Law of Thermodynamics states that for a reaction to be
spontaneous, there must be an increase in entropy.Entropy is often defined as a
measure of the disorder of a system, this is not a very accurate definition. Entropy
change measures the dispersal of energy: how much energy is spread out in a
particular process, or how widely spread out it becomes (at a specific temperature).
This is reflected in the idea that a spontaneous change always results in the dispersal
(spreading out) of energy (and also matter). You see now how hot pans cooling and
chemical reactions belong to the ‘how much' category where energy is being
transferred. Coffee in cream and gas expansion and perfume in air are ‘how widely'
processes where the initial energy of the molecules stay the same but the volume
occupied by the molecules increases. You have probably heard the phrase “the ever
expanding Universe”, although this phrase is often taken to mean our ever increasing
knowledge of our Universe, it also is quite true that our Universe is expanding and
this effect is entropic in nature.
The Third Law of Thermodynamics is usually stated as a definition: the entropy of a

perfect crystal of an element at the absolute zero of temperature is zero. 0 Kelvin or
absolute zero is the temperature at which atoms stop moving. This point is simply
used as a starting point for the measurement of entropy. Entropy is then measured by
determining the energy (heat) required to raise the temperature of a element from
absolute zero to whatever temperature and conditions are prescribed. The change
must be reversible and is calculated as:
DS =qREV/T
Since heat is added to the system, all entropy values are positive at temperatures
above 0K.
Standard entropy values are indicated as S° and are for substances at 1 bar pressure
and 1 molal solution concentration. The units for entropy are in J/K .mol.
What is Helmholtz free energy?
Helmholtz free energy is a concept in thermodynamics where the work of a closed

system with constant temperature and volume is measured using thermodynamic
potential. It may be described as the following equation:
● F = U -TS
● Where,
○ F = Helmholtz free energy in Joules
○ U = Internal energy of the system in Joules
○ T = Absolute temperature of the surroundings in Kelvin
○ S = Entropy of the system in joules per Kelvin
Derivation:
The Helmholtz equation is derived using the law of thermodynamics, so according to
1st law of the thermodynamics
● 𝜹Q = 𝜹W + dU
If the 1st law of thermodynamics is applied to closed systems,
● For the close system

○ 𝜹Q = TdS
○ 𝜹W = PdV
● dU = d(TS) – SdT – PdV
○ Note: d(TS) = SdT – TdS
● dU – d(TS) = – (SdT + PdV)
● dF = – (SdT + PdV)
Application of Helmholtz Free Energy
In equation of state:
The Helmholtz function is used to describe pure fluids with great precision as the sum
of an ideal gas and residual components, such as industrial refrigerants.
Conclusion :
In terms of their natural variables, the differential basic equations explain U, H,
G, and A. Natural variables are important not just for understanding how
thermodynamic quantities are connected to one another, but also for studying
connections between measurable quantities (i.e. P, V, T).
All subsequent assessments of spontaneous and equilibrium processes, such as
equilibrium constants, electrode potentials, and the Nernst equation, gas, liquid,
and solid equilibria, solution processes, and so on, are based on the fundamental
characteristics.
References
[1] Thermodynamic properties and relations. Britannica.

[2] Chemical Engineering Thermodynamics, K. V. Narayana.
[3] Chemical Engineering Thermodynamics, Y V C Rao
[4] Applied Chemical Engineering Thermodynamics, Dimitrios P. Tassios
[5] Chemical Engineering Thermodynamics, Pradeep Ahuja

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BRACT’S Vishwakarma Institute of Technology, Pune-411037

Chemical Engineering Department

Techniques Used For Estimating Earth’s Internal

Prof. Dr. Tanushree Bhattacharjee

Prasad Godage- 12011290

Shriram Gole - 12010563

Tejas Ingole - 12011187

Ganesh Janrao - 12010498

Sohan Kambale – 12011197

Sanket Khade - 12011161

Relationships which relate all the Fundamental properties are known as

Fundamental property relations -

In thermodynamics, the fundamental thermodynamic relation are four fundamental

Second Fundamental Relation - Second fundamental relation is obtained from

Third Fundamental Relation - Third fundamental relation is obtained from helmholtz

Maxwell's Relation and Its Application

Maxwell’s equations are helpful in replacing unmeasurable quantities appearing in

Differentiating with respect to S at constant V

Differentiating with respect to S at constant V

Application of Maxwell's Equation

General relations for du,dh,ds,Cv & Cp :

● The state of a simple compressible system is completely specified by two

Differential Equation of Entropy

Definition of chemical potential

In direct analogy to electrical potential, gravitational potential, thermal potential, and

The application of spontaneity with respect to equilibrium is as follows:

The Third Law of Thermodynamics is usually stated as a definition: the entropy of a

What is Helmholtz free energy?

Helmholtz free energy is a concept in thermodynamics where the work of a closed

If the 1st law of thermodynamics is applied to closed systems,

● For the close system

Application of Helmholtz Free Energy

[1] Thermodynamic properties and relations. Britannica.

[3] Chemical Engineering Thermodynamics, Y V C Rao

[4] Applied Chemical Engineering Thermodynamics, Dimitrios P. Tassios

[5] Chemical Engineering Thermodynamics, Pradeep Ahuja

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