Name: Uman Manzoor

Enroll number: 2022BMME022

Assignment: Thermodynamics (III)

1) Zeroth Law:

When a body, ‘A’, is in thermal equilibrium with another body, ‘b’,

and also separately in thermal equilibrium with a body ‘, C’, then
body, ‘B’ and ‘C’, will also be in thermal equilibrium with each other.
This statement defines the zeroth law of thermodynamics. The law is
based on temperature measurement.
System B= System A, System A= System C
Then, System A= System C

2) First Law of Thermodynamics:

The first law of thermodynamics states that energy can neither be

created nor destroyed, only altered in form. For any system, energy
transfer is associated with mass crossing the control boundary,
 external work, or heat transfer across the boundary. These produce a
change of stored energy within the control volume

It obeys law of conservation of energy

Formula is
△U=Q-W

3) Second Law of Thermodynamics:

The second law of thermodynamics is a physical law based on

universal empirical observation concerning heat and energy
interconversions. A simple statement of the law is that heat always
flows spontaneously from hotter to colder regions of matter (or
'downhill' in terms of the temperature gradient). Another
statement is: "Not all heat can be converted into work in a cyclic
process."

the total entropy of a system either increases or remains

constant in any spontaneous process; it never decreases.

ΔSuniv > 0
Δ S=Δq/ΔT
4) Third Law of Thermodynamics:

when the entropy of each and every element (in their perfectly
crystalline states) is taken as 0 at absolute zero temperature, the
entropy of every substance must have a positive, finite value.
However, the entropy at absolute zero can be equal to zero, as is
the case when a perfect crystal is considered.

S – S0 = 𝑘B ln(1) = 0 [because ln(1) = 0]

When the initial entropy of the system is selected as zero, the

following value of ‘S’ can be obtained:
S–0=0⇒S=0
5) 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.
Formula:

G = H – TS
(or)
G = U + PV – TS

6) 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.

Formula:
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

7) Enthalpy:

Enthalpy is the measurement of energy in a thermodynamic

system. The quantity of enthalpy equals to the total content of
heat of a system, equivalent to the system's internal energy plus
the product of volume and pressure.

Formula:
H=U+PV
(or)
ΔH=ΔU+PΔV
If the pressure and temperature don’t change throughout the
process and the task is limited to pressure and volume

8) Gibbs Duhem Equation:

A combined application of the first and second laws of

thermodynamics yields the equation N dμ = −S dT + V dP,
where N is the number of molecules of the substance, S is the
entropy of the system, and V the volume.
9) Gibbs Helmholtz Equation:

Gibbs-Helmholtz equation is used to determine the change in

Gibbs energy of a system as a function of temperature.
Gibb's Helmholtz equation can be expressed as:

10) Claussius-Clapeyron Equation:

The Clapeyron-Clausius equation is a differential equation giving

the interdependence of the pressure and temperature along the
phase equilibrium curve of a pure substance. This equation was
suggested by B. Clapeyron in 1834 and improved by R. Clausius
in 1850.

Formula:

where
where dP/dT is the slope of the tangent to the coexistence curve
at any point, L is the specific latent heat, T is the temperature, Δ\
Delta v is the specific volume change of the phase transition, and
Δ\Delta s is the specific entropy change of the phase transition.
Clausius–Clapeyron equation:

11) Van't Hoff Equation:

 The Van 't Hoff equation has been widely utilized to explore the
changes in state functions in a thermodynamic system. The Van 't
Hoff plot, which is derived from this equation, is especially
effective in estimating the change in enthalpy and entropy of a
chemical reaction.

Formula:

12) Chemical potential Equation:

In less mathematical terms, the chemical potential of a

component in a mixture at a specific temperature and pressure is
the amount of free energy that can be ascribed to one mole of
that component under the conditions found in the mixture at
that T and p. Alternately it is how much the free energy of the
system, if it were scaled to an infinitely large size, would increase
if you added one mole of that component.

The chemical potential is conceptually useful in that it can

inform you on whether a species in a sample is content to be
where it is located or in the chemical form it is in. For instance, if
the chemical potential of an atom is lower in one chemical form
 than in others, it will prefer to be in the lower-potential form,
thereby driving a reaction to that form. Minimization of the sum
of the chemical potentials of all species (which is just the Gibbs
free energy) drives processes such as chemical reactions (at
constant T and p).

Formula:
μ=μo+RTln(p/po)

13) Faraday's laws of electrolysis in Metallurgy:

The laws state that (1) the amount of chemical change produced
by current at an electrode-electrolyte boundary is proportional
to the quantity of electricity used and (2) the amounts of
chemical changes produced by the same quantity of electricity in
different substances are proportional to their equivalent
weights.

Formula:
14) Raoult's Law:

Raoult’s law has been named after François-Marie Raoult, a

French chemist, who while conducting an experiment, found out
that when substances were mixed in a solution, the vapour
pressure of the solution decreased simultaneously. Raoult’s law
was established in the year 1887 and is also considered as the
law of thermodynamics.

Formula:
Psolution = ΧsolventP0solvent
 Where,
Psolution = vapour pressure of the solution
Χsolvent = mole fraction of the solvent
P0solvent = vapour pressure of the pure solvent

15) Henry’s Law:

Henry’s law is a gas law which states that at the amount of gas
that is dissolved in a liquid is directly proportional to the partial
pressure of that gas above the liquid when the temperature is
kept constant. The constant of proportionality for this
relationship is called Henry’s law constant (usually denoted by
‘kH‘). The mathematical formula of Henry’s law is given by:

P ∝ C (or) P = kH.C

Where,
 ‘P’ denotes the partial pressure of the gas in the atmosphere
above the liquid.
‘C’ denotes the concentration of the dissolved gas.
‘kH’ is the Henry’s law constant of the gas.

16) Non-Ideal solution:

Non-ideal solutions cannot be defined by Raoult's law or by

Henry's law, which are properties specifically unique to ideal
mixtures: Raoult's Law: The vapor pressure of a solvent is
proportional to its mole fraction. (for solutions) Henry's Law:
The partial pressure of a gas is proportional to its mole fraction.
17) Thermodynamic Activity of a Component in a Solution:

In chemical thermodynamics, activity (symbol a) is a measure of

the "effective concentration" of a species in a mixture, in the
sense that the species' chemical potential depends on the
activity of a real solution in the same way that it would depend
on concentration for an ideal solution

Formula:

where μi is the (molar) chemical potential of the species i under the conditions of interest, μo
i is the (molar) chemical potential of that species under some defined set of standard

conditions, R is the gas constant, T is the thermodynamic temperature and e is the

exponential constant.
 Alternatively, this equation can be written as:

18) Regular Solution Model:

In chemistry, a regular solution is a solution whose entropy of mixing is equal to that of an ideal
solution with the same composition, but is non-ideal due to a nonzero enthalpy of mixing.[1][2] Such
a solution is formed by random mixing of components of similar molar volume and without strong
specific interactions,[1][2] and its behavior diverges from that of an ideal solution by showing phase
separation at intermediate compositions and temperatures (a miscibility gap).[3] Its entropy of
mixing is equal to that of an ideal solution with the same composition, due to random mixing
without strong specific interactions.[1][2] For two components

where is the gas constant, the total number of moles, and the mole fraction of each
component. Only the enthalpy of mixing is non-zero, unlike for an ideal solution, while the
volume of the solution equals the sum of volumes of components.

19) Subregular Solution Model:

Abstract. The thermodynamic properties have been examined for

binary solutions whose excess free energy of solution is given by ΔF
= A 1 x 2 y + A 2 xy 2 + RT (x ln x + y ln y) where x and y are the
atomic fractions; the model may be termed a “sub-regular” solution
20) Ellingham Diagram in Metallurgy:

In metallurgy, the Ellingham diagram is used to predict the

equilibrium temperature between a metal, its oxide, and oxygen —
and by extension, reactions of a metal with sulfur, nitrogen, and
other non-metals. The diagrams are useful in predicting the
conditions under which an ore will be reduced to its metal.
Gibbs equation helps us to predict the spontaneity of a reaction on
the basis of enthalpy and entropy values directly. H.G.T Ellingham
proposed the Ellingham diagram to predict the spontaneity of
reduction of various metal oxides. Ellingham diagram was basically
a curve which related the Gibbs energy value with the temperature.
Gibbs energy is given as:

ΔG = ΔH – TΔS

Where ΔH is the change in enthalpy and ΔS is the change in entropy.

With respect to a reaction, Gibbs energy can be related to the

equilibrium constant as:

ΔGo= – RTlnK

Where K is the equilibrium constant.

21) Pourbaix Diagram in Metallurgy:

A simplified Pourbaix diagram indicates regions of "immunity",

"corrosion" and "passivity", instead of the stable species. They thus
give a guide to the stability of a particular metal in a specific
environment. Immunity means that the metal is not attacked, while
corrosion shows that general attack will occur.

The lines in Pourbaix diagrams represent redox and acid-base

reactions, and are the parts of the diagram where two species can
exist in equilibrium. For example, in the Pourbaix diagram for Fe
below, the horizontal line between the Fe3+ and Fe2+ regions
represents the reaction Fe3+(aq)+e−=Fe2+(aq)
 , which has a standard potential of +0.77 V. While we could use
standard potentials for all these lines, in practice Pourbaix
diagrams are usually plotted for lower ion concentrations (often 1
mM) that are more relevant to corrosion and electrochemical
experiments.

Example: Iron Pourbaix diagram

Areas in the Pourbaix diagram mark regions where a single species

(Fe2+(aq), Fe3O4(s), etc.) is stable. More stable species tend to
occupy larger areas.

Lines mark places where two species exist in equilibrium.

Pure redox reactions are horizontal lines - these reactions are not
pH-dependent
Pure acid-base reactions are vertical lines - these do not depend on
potential
Reactions that are both acid-base and redox have a slope of -0.0592
V/pH x # H+⁄# e-)