1.

Potential
1.1 Definition:
It is a field defined in space, from which many important physical properties may be derived.

Fig. 1
Potential generally refers to a currently unrealized ability. The term is used in a wide variety of
fields, from ​physics to the ​social sciences to indicate things that are in a state where they are able
to change in ways ranging from the simple release of energy by objects to the realization of
abilities in people.

1.2 Examples:
● In linguistics, the ​potential mood​.
● In mathematics, the study of potentials is known as ​potential theory​; it is the study of
harmonic functions on ​manifolds​. This mathematical formulation arises from the fact
that, in physics, the scalar potential is irrotational, and thus has a vanishing Laplacian
— the very definition of a harmonic function.
● In physics, a potential may refer to the scalar or to the ​vector potential​. In either case,
it is a field defined in space, from which many important physical properties may be
derived.
● Gravitational ​potential and the ​electric potential​, from which the motion of gravitating
or electrically charged bodies may be obtained.
● Specific forces have associated potentials, including the ​Coulomb potential​, the
Vander Waals potential​, the ​Lenard-Jones potential​ and the ​Yukawa potential​.
● In electrochemistry there are ​Galvani potential​, ​Volta potential​, ​electrode potential​,
and standard electrode potential​.
● In thermodynamics potential refers to ​thermodynamic potential​.
 2. Contact Potential
2.1 Definition:
The contact potential, Δφ (measured in unit of energy, eV), is one of the most important
parameters for understanding tip-induced band bending and tunneling spectroscopy. It is defined
as the work function of the metallic tip, φ​m​, minus that of the semiconducting sample, φ​s​, where
for the sample its work function is given by the electron affinity, χ, plus the difference in energy
between the conduction band maximum and the Fermi-level, E​C​-E​F​.

2.2 Explanation:
For the contact potential used throughout the SEMITIP program, it is assumed that we are taking
the work function of the sample as it would be in the absence of any surface states (intrinsic or
extrinsic). Such surface states can still be included in the program with no problem, but it's just
that the contact potential, as a numerical parameter, corresponds to what would be measured
experimentally on a surface with no surface states.

If, for example, a positive contact potential occurs, then, when a tip is brought towards a sample,
upwards band bending will occur in the sample. The situation for an n-type sample is pictured
below, with the surface region being depleted of electrons. It is clear that a non-zero electrostatic
potential exists in the semiconductor, even though there is not applied voltage bias between the
sample and tip.

Fig.2
A positive contact potential such as this will cause a tunneling spectrum to shift towards higher
(more positive) sample voltages (i.e. towards the right), whereas a negative contact potential will
shift the spectrum towards lower (more negative) sample voltages (towards the left).
In the above diagram, it is clear that the electrostatic potential energy within the probe tip,
relative to a point deep inside the semiconductor, is given simply by Δφ. Application of some
bias voltage Von the sample relative to the tip will further shift the electrostatic potential energy
of the tip by eV (e is the fundamental unit of charge, taken as usual to be positive), so that the
total electrostatic potential energy of the tip is φ​T​=eV+Δφ as defined in Ref. 1. This quantity is
the basic boundary condition used for the electrostatic solution within SEMITIP. In versions 1
and 2 is φ​T itself that was entered as an input parameter. In version 3 and higher, separate
parameters for V and Δφ are entered. (In version 3 these parameters are used simply to compute
the sum eV+Δφ, which is assigned to φ​T​, whereas in versions 4 and higher, where tunnel currents
are computed, the quantities V and Δφ are needed individually for other purposes as well).
Establishment of contact potential:
A difference in electric potentials arising between two bodies that is in contact and in
thermo-dynamic equilibrium. The concept of contact potential is most important for solid
conductors (metals and semiconductors). If two solid conductors are brought into contact, an
exchange of electrons takes place between them; at first the electron transfer will occur
predominantly from the conductor with a lower work function to the conductor with a higher
work function. As a result, the conductors acquire electric charges of opposite sign, which causes
the appearance of an electric field that impedes the flow of electrons. Ultimately a state of
equilibrium is attained; in this state the electron flow in one direction becomes equal to the flow
in the opposite direction, and a contact potential is established between the conductors.

2.3 Value of contact potential:

The value of the contact potential is equal to the difference in work functions divided by the
charge of an electron. The contact potential may attain values of several volts and depends on the
structure of the conductor and the condition of its surface. Therefore, the value of the contact
potential can be changed by treatment of the surface (coatings, adsorption, and so on), by the
introduction of impurities (in the case of semiconductors), and by alloying with other substances
(in the case of metals).

2.3.1 In electric circuits:

In an electric circuit consisting of several conductors, the contact potential between the
conductors at the ends of the circuit is determined solely by their work functions and does not
depend on any of the intermediate components of the circuit (Volta’s rule). Since the work
performed by electric forces arising because of the contact potential in moving charges within a
closed circuit consisting of several conductors is equal to zero.

2.4 Measurement of contact potential:

As, the direct measurement of the contact potential is impossible. But one of the most widely
used methods of measuring the contact potential is the method using Kelvin’s vibrating
capacitor.
2.4.1 Kelvin’s vibrating capacitor:
The distance between the plates of a capacitor made from the pair of conductors being
investigated is changed periodically. The capacitance of the capacitor is thus varied, and an
alternating current caused by the contact potential difference is generated in the circuit. Thus, the
contact potential may be determined by measuring the current. The electric field of the contact
potential is concentrated in the conductors near the boundary surface and in the gap between the
conductors. The linear dimensions of the region are of the order of the screening length, which
increases with decreasing concentration of conduction electrons within the conductor. The
screening length in metals has atomic dimensions (10​−8 to 10​−7 cm); in semiconductors it varies
within wide limits and can attain values of 10​−4 to 10​−5 cm. Two conclusions may be drawn from
this fact:
● Of the two bodies in contact, a greater part of the contact potential occurs on the
conductor having the greater resistance.
● For semiconductors, the density of charge carriers is changed markedly in the region of
concentration of the contact potential.

2.5 Contact potential difference:

2.5.1 Definition​:
● The potential difference that exists across the space between two electrically
connected materials. Also known as contact electromotive force; contact potential;
Volta effect.
● An electrostatic potential that exists between samples of two dissimilar electrically
conductive materials (metals or semiconductors with different electron work
functions) that have been brought into thermal equilibrium with each other, usually
through a physical contact. Although normally measured between two surfaces which
are not in contact, this potential is called the contact potential difference.
Initially it is expected that mobile charge carriers (electrons or holes) will migrate from one
sample to the other. If there is a net flow of electrons from material A to material B (see
illustration), material B will become negatively charged and material A will become
positively charged, assuming that they were originally neutral. This process is self limiting
because a potential difference between the two samples will develop due to the charge
separation and will grow to a value sufficient to stop further motion of the electrons from A
to B.
 Fig. 3

2.6 Development of contact potential difference:

Development of the contact potential difference between different materials have been
performed for the first time using scanning force microscopy. The instrument has a high
resolution for both the contact potential difference of a contact potential as two conductive
materials are brought into thermal equilibrium.
In a metal or a semiconductor, the electrons are distributed in energy such that virtually all of
them exist at or below a level called the Fermi level. When any combination of metals and
semiconductors are put into equilibrium with one another, the Fermi levels in all will coincide.
The contact potential difference between materials is that value necessary to raise or lower the
potential energies of the electrons to produce a common Fermi level. Since they are then at the
same energy, electrons in either material will have no net force on them, that is, no reason to
travel to the other material. Because it causes no net force on the equilibrium distribution of
electrons, contact potential difference cannot be directly measured with an ordinary voltmeter.
Nevertheless, it profoundly affects the behavior of a number of electronic devices.

2.6.1 Triboelectric contact:

If two different ​insulators are touched together, such as when a piece of rubber is touched against
a piece of glass, then the surface of the rubber will acquire an excess negative charge, and the
glass will acquire an equal positive charge. If the surfaces are then pulled apart, a very ​high
voltage is produced. This so-called "tribo" or "rubbing" effect is not well understood. It may be
caused by electron-stealing via ​quantum tunneling​, or by transfer of surface ions. Friction is not
required, although in many situations it greatly increases the phenomenon. Certain phenomena
related to frictionally generated electrostatic charges have been known since antiquity, though of
course the modern theory of electricity was developed after the ​Scientific Revolution​.
2.6.2 Electrolytic-metallic contact:
If a piece of metal is touched against an ​electrolytic material, the metal will spontaneously
become charged, while the electrolyte will acquire an equal and opposite charge. Upon first
contact, a chemical reaction called a '​half-cell reaction​' occurs on the metal surface. As metal
ions are transferred to or from the electrolyte, and as the metal and electrolyte become oppositely
charged, the increasing voltage at the thin insulating ​layer between metal and electrolyte will
oppose the motion of the flowing ions, causing the chemical reaction to come to a stop. If a
second piece of a different type of metal is placed in the same electrolyte bath, it will charge up
and rise to a different voltage. If the first metal piece is touched against the second, the voltage
on the two metal pieces will be forced closer together, and the chemical reactions will run
constantly. In this way the 'contact electrification' becomes continuous. At the same time, an
electric current will appear, with the path forming a closed loop which leads from one metal part
to the other, through the chemical reactions on the first metal surface, through the electrolyte,
then back through the chemical reactions on the second metal surface. In this way, contact
electrification leads to the invention of the ​Galvanic cell​ or ​battery​.

2.6.3 Metallic contact:

If two metals having differing ​work functions​ are touched together, one steals electrons from the
other, and the opposite net charges grow larger and larger; this is the Volta effect. The process is
halted when the difference in ​electric potential​ (electrostatic potential) between the two metals
reaches a particular value, namely the difference in work function values - usually less than one
volt. At this point, the Fermi levels for the two metals are equal, and there is no voltage
difference between them. [If there were a voltage difference between them, then a current would
flow between them: so "zero current" implies "zero voltage difference".

2.6.4 Semiconductor contact:

If a metal touches a semiconductor material, or if two different semiconductors are placed into
contact, one becomes charged slightly positive and the other slightly negative. It is found that if
this junction between semiconductors is connected to a power supply, and if the power supply is
set to a voltage slightly higher than the natural voltage appearing because of contact
electrification, then for one polarity of voltage there will be a current between the two
semiconductor parts, but if the polarity is reversed, the current stops. Thus contact between
materials lead to the invention of the semiconductor ​diode or ​rectifier and triggered the
revolution in ​semiconductor electronics​ and ​physics​.

2.6.4.1 Example:
We know that a PN junction is formed when we connect a p type semiconductor to an n type
semiconductor. The p type layer contains an excess quantity of positive charge carriers. Similarly
the n type layer contains an excess quantity of negative charge carriers. When we bring these two
layers into contact, the free charge carriers on both sides combine with each other and are
neutralized. So the region where the two layers are in contact end up with no free charge carriers
(due to the recombination). This region is called the depletion layer. Now, what do you observe
between the plates of a charged capacitor? You will observe a voltage difference.
So our PN junction behaves like a charged capacitor and the voltage between its terminals is
called the contact potential difference.
In materials with a ​direct band gap​, if bright light is aimed at one part of the contact area between
the two semiconductors, the voltage at that spot will rise, and an electric current will appear.
When light meets contact electrification, the light energy is changed directly into electrical
energy, allowing creation of ​solar cells​. Later it was found that the same process can be reversed,
and if a current is forced backwards across the contact region between the semiconductors,
sometimes light will be emitted, allowing creation of the ​light-emitting diode​ (LED).

2.7 Measurement of contact potential difference:

Measurements of the contact potential difference between different materials have been
performed for the first time using scanning force microscopy. The instrument has a high
resolution for both the contact potential difference (better than 0.1 mV) and the lateral dimension
(<50 nm) and allows the simultaneous imaging of topography and contact potential difference.
Images of gold, platinum, and palladium surfaces, taken in air, show a large contrast in the
contact potential difference and demonstrate the basic concept.

2.8 Applications:
The contact potential plays an important role in solid-state physics and its applications are:
▪ It significantly affects the operation of electro vacuum instruments.
▪ In electron tubes the contact potential difference between electrodes is added to the
applied external voltages and influences the shape of the current-voltage characteristic
curve.
▪ In thermionic generators the contact potential is used for direct conversion of thermal
energy to electric power. Electrons are “evaporated” from a hot cathode that has a high
work function and are “condensed” on an anode with a low work function. The difference
in the potential energy of electrons is converted into work, which is performed in the
external electric circuit.
 3. Chemical potential
3.1 History:
Chemical potential was first described by the American engineer, chemist and
mathematical physicist ​Josiah Willard Gibbs​.​ He defined it as follows:

“If to any ​homogeneous​ mass in a ​state​ of ​hydrostatic stress​ we suppose an

infinitesimal quantity of any substance to be added, the mass remaining homogeneous and
its ​entropy​ and ​volume​ remaining unchanged, the increase of the ​energy​ of the mass divided by
the quantity of the substance added is the ​potential​ for that substance in the mass considered.”

Fig. 2
Gibbs later noted also that for the purposes of this definition, any ​chemical element​ or
combination of elements in given proportions may be considered a substance, whether capable or
not of existing by itself as a homogeneous body. This freedom to choose the boundary of the
system allows chemical potential to be applied to a huge range of systems. The term can be used
in ​thermodynamics​ and ​physics​ for any system undergoing change. Chemical potential is also
referred to as ​partial molar Gibbs energy​ (see also ​partial molar property​). Chemical potential
is measured in units of energy/particle or, equivalently, energy/​mole​.

3.2 Overview:
Particles tend to move from higher chemical potential to lower chemical potential. In this way,
chemical potential is a generalization of ​"potentials" in physics​ such as ​gravitational potential​.
When a ball rolls down a hill, it is moving from a higher gravitational potential (higher internal
energy thus higher potential for work) to a lower gravitational potential (lower internal energy).
In the same way, as molecules move, react, dissolve, melt, etc., they will always tend naturally to
go from a higher chemical potential to a lower one, changing the ​particle number​, which
is ​conjugate variable​ to chemical potential. A simple example is a system of dilute
molecules ​diffusing​ in a homogeneous environment. In this system, the molecules tend to move
from areas with high ​concentration​ to low concentration, until eventually the concentration is the
same everywhere.
The microscopic explanation for this is based in ​kinetic theory​ and the random motion of
molecules. However, it is simpler to describe the process in terms of chemical potentials: For a
given temperature, a molecule has a higher chemical potential in a higher-concentration area, and
a lower chemical potential in a low concentration area. Movement of molecules from higher
chemical potential to lower chemical potential is accompanied by a release of free energy.
Therefore, it is a ​spontaneous process​.

3.3 Understanding the concept of chemical potential:

For many systems we are interested in, the number of particles is not constant: for a crystal
growing, for ice melting, for chemical reactions, the number of particles are not constant. How
can we extend the methods we have developed to handle non-constant particle numbers?
We have seen that:
● If two systems have the same temperature there is no net energy between them.
● If two systems have the same pressure, there is no net change of volumes
● If two systems have the same X, there is no net flow of particles.
What is this X? We call it the chemical potential: If two systems are at the same temperature and
only have a single chemical species and the same value of the chemical potential, there is no net
flux of particles from one side to another. But if the chemical potential is different, there will be
a net flux.

3.4 Statement:
Chemical potential, also known as partial molar free energy is a form of ​potential energy​ that can
be absorbed or released during a chemical reaction or ​phase transition​. The chemical potential of
a species in a mixture is defined as:
“​The rate of change of a ​free energy​ of a ​thermodynamic system​ with respect to the change in
the number of atoms or molecules of the species that are added to the system​.”
Thus, it is the ​partial derivative​ of the free energy with respect to the amount of the species, all
other species' concentrations in the mixture remaining constant. When both temperature and
pressure are held constant, chemical potential is the partial molar ​Gibbs free energy
● At chemical equilibrium:
 At ​chemical equilibrium​ or in ​phase equilibrium​ the total sum of chemical potentials is
zero, as the free energy is at a minimum
● Fermi energy:
In ​semiconductor​ physics, the chemical potential of a system of electrons at a temperature
of zero Kelvin is known as the ​Fermi energy​.

3.4.1 Examples:
● Chemical potential energy is the energy stored in the chemical bonds of a substance. The
various chemicals that make up gasoline contain a large amount of chemical
potential energy that is released when the gasoline is burned in a controlled way in the
engine of the car.

Fig. 3
● An example is illustrated by the chemical reaction of ​dissociation​ of a ​weak acid​, such
as ​acetic acid​, HA, where A=CH​3​COO​−​.
HA ​⇌​ H​+​ + A​−
Vinegar​ contains acetic acid. When acid molecules dissociate, the concentration of the
undissociated acid molecules (HA) decreases and the concentrations of the product ions
(H​+​ and A​−​) increase. Thus the chemical potential of HA decreases and the sum of the
chemical potentials of H​+​ and A​−​ increases. When the sums of chemical potential of reactants
and products are equal the system is at equilibrium and there is no tendency for the reaction
to proceed in either the forward or backward direction. This explains why vinegar is acidic,
because acetic acid dissociates to some extent, releasing ​hydrogen ions​ into the solution.
3.5 Chemical potential and Gibbs free energy:
The energy associated with a chemical reaction that can be used to do work. The free energy of a
system is the sum of its enthalpy (H) plus the product of the temperature (Kelvin) and the
entropy (S) of the system.
 Fig. 4
Chemical potential of the ith-component of the system is the derivative of any thermodynamic
potential divided by the quantity (or number of molecules) of this component when the values of
the other thermodynamic variables, given a thermodynamic potential, are constant, e.g., μ​i​ =
(G/n​i​)​T,p,nj​, where G is the Gibbs energy of the phase; ni the number of moles of the i-component
of the phase; T, the absolute temperature; p, pressure, and n​j​, the number of moles of all other
components (j = i). It is obvious that chemical potential (μ​i​) is a partial molar Gibbs energy. The
sum ∑μ​i​dn​i​, which enters into the expression for the total differential of all thermodynamic
potentials, has been called the fundamental Gibbs equation, e.g.

where S is the entropy and V the volume.

3.6 Chemical potential and fugacity:

● Like there is gravitational potential or electrostatic potential there is chemical
potential. It is basically change in the internal energy of the system by addition of a
new particle at constant volume and entropy. In terms of free energy, the changes in
Gibbs free energy of a system by addition of a particle at constant temperature and
pressure. So basically it tells you about the reactivity of a component in a phase.
Transfer of molecule will always occur from high potential to low potential.
● Fugacity is escapability that is tendency of a particle to prefer one phase over other.
The particle will be present in the phase having low fugacity (where the escapability
is least). In terms of chemical potential it is the measure of how much the chemical
potential of a component in a phase differs from the chemical potential in standard
state, due to change in Pressure or mol fr of component. Fugacity is analogous to
partial pressure when applying thermodynamics to any non ideal system for any
component. For pure ideal gases fugacity --> partial pressure

3.7 Applications:
Chemical potential has various applications for finding slope:
● Chemical potentials can be used to explain the slopes of lines on a ​phase diagram​ by
 using the ​Clapeyron equation​, which in turn can be derive from the Gibbs–Duhem
equation They are used to explain ​colligative properties​ such as ​melting-point
depression​ by the application of pressure.

Fig. 5
● Both ​Raoult's law​ and ​Henry's law​ can be derived in a simple manner using chemical
potentials.
● As a driving force: ​Chemical potential is the main driving force for any mass transfer
operation to be occurred and is very closely related with concentration of that
corresponding species therefore we generally take concentration term instead of
chemical potential while for very high pressures we generally calculate fugacity instead
of pressures.
● To calculate free energy.
● Chemical potential is 1 type of force to turn a reaction in equilibrium. Chemical potential
is comparable to escaping tendency or fugacity, its means the tendency of reaction flow
to equilibrium point. If chemical potential is high escaping tendency will high.
● Chemical potential of photons: ​The most common example of a photon gas in
equilibrium is black body radiation. A massive ideal gas with only one type of particle is
uniquely described by three state functions such as the temperature, volume, and the
number of particles. As a result, the chemical potential of the black body photon gas
is zero.

3.8 Can chemical potential be negative?

This is clear from the fact that for a classical gas of fermions, or any gas of bosons, the chemical
potential is negative. (That is, it is lower than the lowest possible energy that a particle can have
in the system).

3.9 Table:
 Fig. 6

4. Thermodynamic Potential
Four quantities called "​thermodynamic potentials​" are useful in the
chemical thermodynamics of reactions and non-cyclic processes. They
are ​internal energy​, the ​enthalpy​, the Helmholtz free energy and the ​Gibbs
free energy​.

The four thermodynamic potentials are related by offsets of the "energy

from the environment" term TS and the "expansion work" term PV. A
mnemonic diagram suggested by Schroeder can help you keep track of the
relationships between the four thermodynamic potentials​.

4.1 Definition:
A thermodynamic potential is a ​scalar​ quantity used to represent the ​thermodynamic state​ of
a ​system​.

4.2 History:
The concept of thermodynamic potentials was introduced by ​Pierre Duhem​ in 1886. ​Josiah
Willard Gibbs​ in his papers used the term fundamental ​functions​. One main thermodynamic
potential that has a physical interpretation is the ​internal energy​ U. It is the energy of
configuration of a given system of ​conservative forces​ (that is why it is a potential) and only has
meaning with respect to a defined set of references (or data). Expressions for all other
thermodynamic energy potentials are derivable via ​Legendre transforms​ from an expression
for U. In ​thermodynamics​, certain forces, such as ​gravity​, are typically disregarded when
formulating expressions for potentials. For example, while all the ​working fluid​ in a ​steam
engine​ may have higher energy due to gravity while sitting on top of ​Mount Everest​ than it
would at the bottom of the ​Mariana Trench​, the ​gravitational potential energy​ term in the
formula for the internal energy would usually be ignored because changes in gravitational
potential within the engine during operation would be negligible.

Fig .1 (Pierre Duhem and Josiah Willard Gibbs)

4.3 Description and Interpretation:

Five common thermodynamic potentials are:
Name Symbol Formula Natural variables

Internal energy U ∫(T dS − pdV + ∑ μi dN i S,V, {N i }

i

Helmholtz free energy F U-TS T,V,{ N i }

Enthalpy H U+pV S,p,{ N i }

Gibbs free energy G U+pV-TS T,p,{ N i }

Landau Potential (Grand potential) Ω U-TS- ∑ μi N i T,V,{ μi }

i

where
T = Temperature
 P = Pressure
V = Volume
S = Entropy
The Helmholtz free energy is often denoted by the symbol F, but the use of A is preferred
by ​IUPAC​, ​ISO​ and ​IEC​. N​i​ is the number of particles of type i in the system and μ​i​ is
the ​chemical potential​ for an i-type particle. For the sake of completeness, the set of all N​i​ are
also included as natural variables, although they are sometimes ignored.
These five common potentials are all energy potentials, but there are also ​entropy potentials​.
The ​thermodynamic square​ can be used as a tool to recall and derive some of the potentials.
Just as in ​mechanics​, where ​potential energy​ is defined as capacity to do work, similarly different
potentials have different meanings:
● Internal energy​ (U) is the capacity to do work plus the capacity to release heat.

● Gibbs energy​ (G) is the capacity to do non-mechanical work.

● Enthalpy​ (H) is the capacity to do non-mechanical work plus the capacity to release heat.

● Helmholtz free energy​ (F) is the capacity to do mechanical plus non-mechanical work.
From these definitions we can say that ΔU is the energy added to the system, ΔF is the total work
done on it, ΔG is the non-mechanical work done on it, and ΔH is the sum of non-mechanical
work done on the system and the heat given to it. Thermodynamic potentials are very useful
when calculating the ​equilibrium results of a chemical reaction​, or when measuring the
properties of materials in a chemical reaction. The chemical reactions usually take place under
some simple constraints such as constant pressure and temperature, or constant entropy and
volume, and when this is true, there is a corresponding thermodynamic potential that comes into
play. Just as in mechanics, the system will tend towards lower values of potential and at
equilibrium, under these constraints, the potential will take on an unchanging minimum value.
The thermodynamic potentials can also be used to estimate the total amount of energy available
from a thermodynamic system under the appropriate constraint.
● When the entropy (S ) and "external parameters" (e.g. volume) of a ​closed system​ are held
constant, the internal energy (U ) decreases and reaches a minimum value at equilibrium.
This follows from the first and second laws of thermodynamics and is called the principle of
minimum energy. The following three statements are directly derivable from this principle.

● When the temperature (T ) and external parameters of a closed system are held constant, the
Helmholtz free energy (F ) decreases and reaches a minimum value at equilibrium.

● When the pressure (p) and external parameters of a closed system are held constant, the
enthalpy (H ) decreases and reaches a minimum value at equilibrium.

● When the temperature (T ), pressure (p) and external parameters of a closed system are held
constant, the Gibbs free energy (G ) decreases and reaches a minimum value at equilibrium.
4.4 Fundamental Equations:
The definitions of the thermodynamic potentials may be differentiated and, along with the first
and second laws of thermodynamics, a set of differential equations known as the fundamental
equations follow.(Actually they are all expressions of the same fundamental thermodynamic
relation, but are expressed in different variables.) By the ​first law of thermodynamics​, any
differential change in the internal energy U of a system can be written as the sum of heat flowing
into the system and work done by the system on the environment, along with any change due to
the addition of new particles to the system:
dU = δQ − δW + ∑ μi dN i
i

where δQ is the ​infinitesimal​ heat flow into the system, and δW is the infinitesimal work done by
the system, μ​i​ is the ​chemical potential​ of particle type i and N​i​ is the number of type i particles.
(Note that neither δQ nor δW are ​exact differentials​. Small changes in these variables are,
therefore, represented with δ rather than d.)
By the ​second law of thermodynamics​, we can express the internal energy change in terms of
state functions and their differentials. In case of reversible changes we have:
δQ = T dS

δW = pdV

where
T is ​temperature​,
S is ​entropy​,
p is ​pressure​,
and V is ​volume​, and the equality holds for reversible processes.
This leads to the standard differential form of the internal energy in case of a quasistatic
reversible change:

dU = T dS − pdV + ∑ μi dN i
i

Since U, S and V are thermodynamic functions of state, the above relation holds also for
arbitrary non-reversible changes. If the system has more external variables than just the volume
that can change, the fundamental thermodynamic relation generalizes to:

dU = T dS − ∑ X i dxi + ∑ μj dN j
i j

Here the X​i​ are the ​generalized forces​ corresponding to the external variables x​i​.
Applying ​Legendre transforms​ repeatedly, the following differential relations hold for the four
potentials:
 dU = T dS − pdV + ∑ μi dN i
i

dF =− S dT − pdV + ∑ μi dN i
i

dH = T dS + V dp + ∑ μi dN i
i

dG =− S dT + V dp + ∑ μi dN i
i

Note that the infinitesimals on the right-hand side of each of the above equations are of the
natural variables of the potential on the left-hand side. Similar equations can be developed for all
of the other thermodynamic potentials of the system. There will be one fundamental equation for
each thermodynamic potential, resulting in a total of 2​D​ fundamental equations.
The differences between the four thermodynamic potentials can be summarized as follows:
dpV = dH − dU = dG − dF

dT S = dU − dF = dH − dG

5. Gibbs free energy

5.1 Definition:
Gibbs free energy is a measure of the potential for reversible or maximum work that may be
done by a system at constant temperature and pressure.
It is a thermodynamic property that was defined in 1876 by Josiah Willard Gibbs to predict
whether a process will occur spontaneously at constant temperature and pressure. Gibbs free
energy G is defined as G = H - TS where H, T and S are the enthalpy, temperature, and entropy.

5.2 SI Unit:
The SI unit for Gibbs energy is the kilo joule (kJ).

5.3 Change in Gibbs free energy:

Changes in the Gibbs free energy G correspond to changes in free energy for processes at
constant temperature and pressure. The change in Gibbs free energy change is the maximum no
expansion work obtainable under these conditions in a closed system. ΔG is negative for
spontaneous processes, positive for non-spontaneous processes and zero for processes at
equilibrium.

5.4 Synonyms:
Also Known As: (G), Gibbs' free energy, Gibbs energy, or Gibbs function. Sometimes the term
"free enthalpy" is used to distinguish it from Helmholtz free energy. The terminology
recommended by the IUPAC ​is Gibbs energy or Gibbs function.

5.5 Example:
When you pull a rock using a rope and a pulley, you raise the height of the rock. In mechanics,
we would say that we increased the potential energy of the rock. This is because if we release it,
the rock will gain speed as it falls. If the rock hits a nail that is partly inserted on the floor, the
nail will penetrate the floor further. We would say that the rock did work on the nail because the
original potential energy of the rock was used to insert the nail in the floor.
Similarly, the Gibbs free energy is the energy available in a substance to do work. However, this
work does not involve mechanical work, meaning the substance does not expand or contract to
push on something. It refers to the 'chemical work' involved in chemical reactions. One could
think of chemical work as the energy involved in transforming one chemical into another. The
Gibbs free energy is a chemical potential energy in a substance. It is defined by the equation

G= H-TS
Where G is the Gibbs free energy, H is the enthalpy, T is the temperature and S is the entropy.
Enthalpy and entropy are thermodynamic properties of a system related to the system's internal
energy and its degree of disorder.

5.6 Spontaneity of Chemical Reactions:

The mechanical potential energy of the rock is measured by the rock's height above the ground.
On the ground, the rock has no potential energy. Similarly, the Gibbs free energy of a chemical is
measured in reference to another chemical state that is assigned a Gibbs free energy of zero. Two
different substances may have different Gibbs free energies. Also, the state of a substance may
have higher Gibbs free energy than another state of the same substance.
On Earth, objects always want to fall and reduce their potential energy. In the world of chemical
transformations, chemicals always want to minimize their Gibbs free energy. What this means is
that chemicals will tend to transform to other states ​or chemicals that have less Gibbs free energy.
The rock, if not supported by the rope, will always want to fall to the ground where it has less
potential energy. A chemical with higher Gibbs free energy will always want to transform to a
chemical with lower Gibbs free energy. These types of chemical reactions are called spontaneous
reactions because they happen without the need of any input energy, just like the rock falls
without us doing anything. Ice will always convert to water when the temperature is above 0
degrees Celsius. At these temperatures, we never see water converting to ice. We would say that
the conversion of ice to water occurs spontaneously. If we wanted to convert water to ice, we
would need to extract heat. If we wanted to place the rock above the ground again, we would
have to pull strongly on the rope. In this case, we would say that the conversion of water to ice
and increasing the rock's height do not occur spontaneously.

5.7 Using free energy to determine spontaneity:

For a process that occurs at constant temperature and pressure, spontaneity can be determined
using the change in Gibbs free energy, which is given by:
∆G = ∆H − T ∆S

where the sign of ΔG depends on the signs of the changes in enthalpy (ΔH) and entropy (ΔS).
The sign of ΔG will change from positive to negative (or vice versa) where T = ΔH/ΔS.
In cases where ΔG is:
● negative, the process is spontaneous and may proceed in the forward direction as written.
● positive, the process is non-spontaneous as written, but it may proceed spontaneously in
the reverse direction.
● zero, the process is at equilibrium, with no net change taking place over time.
This set of rules can be used to determine four distinct cases by examining the signs of the ΔS
and ΔH.
● When ΔS > 0 and ΔH < 0, the process is always spontaneous as written.
● When ΔS < 0 and ΔH > 0, the process is never spontaneous, but the reverse process is
always spontaneous.
● When ΔS > 0 and ΔH > 0, the process will be spontaneous at high temperatures and
non-spontaneous at low temperatures.
● When ΔS < 0 and ΔH < 0, the process will be spontaneous at low temperatures and
non-spontaneous at high temperatures.
For the latter two cases, the temperature at which the spontaneity changes will be determined by
the relative magnitudes of ΔS and ΔH.

5.8 Gibbs energy and Chemical change:

ΔG determines the direction and extent of chemical change. ΔG is meaningful only for changes
in which the temperature and pressure remain constant. These are the conditions under which
most reactions are carried out in the laboratory; the system is usually open to the atmosphere
(constant pressure) and we begin and end the process at room temperature (after any heat we
have added or which is liberated by the reaction has dissipated.)
The importance of the Gibbs function can hardly be over-stated: it serves as the single master
variable that determines whether a given chemical change is thermodynamically possible. Thus
if the free energy of the reactants is greater than that of the products, the entropy of the world
will increase when the reaction takes place as written, and so the reaction will tend to take place
spontaneously. Conversely, if the free energy of the products exceeds that of the reactants, then
the reaction will not take place in the direction written, but it will tend to proceed in the reverse
direction.
In a spontaneous change, Gibbs energy always decreases and never increases. This of course
reflects the fact that the entropy of the world behaves in the exact opposite way (owing to the
negative sign in the TΔS term). Recalling the example of the freezing of water we presented in
the previous lesson
H 2 O (liquid) →H 2 O(ice)

water below its freezing point undergoes a decrease in its entropy, but the heat released into the
surroundings more than compensates for this, so the entropy of the world increases, the free
energy of the H2O diminishes, and the process proceeds spontaneously.
An important consequence of the one-way downward path of the free energy is that once it
reaches its minimum possible value, net change comes to a halt. This, of course, represents the
state of chemical equilibrium.
These relations are nicely summarized as follows:
● ΔG < 0reaction can spontaneously proceed to the right: A → B
● ΔG > 0reaction can spontaneously proceed to the left: A ← B
● ΔG = 0the reaction is at equilibrium; the quantities of A and B will not change.

5.9 Important role of temperature:

Recalling the condition for spontaneous change
ΔG = ΔH – TΔS < 0
it is apparent that the temperature dependence of ΔG depends almost entirely on the entropy
change associated with the process. (We say "almost" because the values of ΔH and ΔS are
themselves slightly temperature dependent; both gradually increase with temperature). In
particular, notice that in the above equation the sign of the entropy change determines whether
the reaction becomes more or less spontaneous as the temperature is raised.
For any given reaction, the sign of ΔH can also be positive or negative. This means that there are
four possibilities for the influence that temperature can have on the spontaneity of a process:
Case 1: ΔH < 0 and ΔS > 0
Under these conditions, both the ΔH and TΔS terms will be negative, so ΔG will be negative
regardless of the temperature. An exothermic reaction whose entropy increases will be
spontaneous at all temperatures.
Case 2: ΔH < 0 and ΔS < 0
If the reaction is sufficiently exothermic it can force ΔG negative only at temperatures below
which |TΔS| < |ΔH|. This means that there is a temperature T = ΔH / ΔS at which the reaction is
at equilibrium; the reaction will only proceed spontaneously below this temperature. The
freezing of a liquid or the condensation of a gas is the most common examples of this condition.
Case 3: ΔH > 0 and ΔS > 0
This is the reverse of the previous case; the entropy increase must overcome the handicap of an
endothermic process so that TΔS > ΔH. Since the effect of the temperature is to "magnify" the
influence of a positive ΔS, the process will be spontaneous at temperatures above T = ΔH / ΔS.
(Think of melting and boiling.)
Case 4: ΔH > 0 and ΔS < 0
With both ΔH and ΔS working against it, this kind of process will not proceed spontaneously at
any temperature. Substance A always has a greater number of accessible energy states, and is
therefore always the preferred form.

5.10 Significance:
● The Gibbs [free] energy is a state function defined as G = H – TS .
● The Gibbs energy is the maximum useful work that a system can do on the surroundings
when the process occurs reversibly at constant temperature and pressure.
● The practical utility of the Gibbs function is that ΔG for any process is negative if it leads
to an increase in the entropy of the world. Thus spontaneous change at a given
temperature and pressure can only occurs when it would lead to a decrease in G.
● The sign of the standard free energy change ΔG° of a chemical reaction determines
whether the reaction will tend to proceed in the forward or reverse direction.
● Similarly, the relative signs of ΔG° and ΔS° determine whether the spontaneity of a
chemical reaction will be affected by the temperature, and if so, in what way.
● The existence of sharp melting and boiling points reflects the differing temperature
dependencies of the free energies of the solid, liquid, and vapor phases of a pure
substance, which are in turn, reflect their differing entropies.
 6. Helmholtz free energy
6.1 Preamble:
The Helmholtz free energy was developed by ​Hermann von Helmholtz​, a German physician and
physicist, and is usually denoted by the letter A (from the German “Arbeit” or work), or the
letter F. The ​IUPAC​ recommends the letter A as well as the use of name Helmholtz energy. In
physics, the letter F can also be used to denote the Helmholtz energy, as
Helmholtz energy is sometimes referred to as the Helmholtz
function, Helmholtz free energy, or simply free energy (not to be confused
with​ ​Gibbs free energy​ or free enthalpy​).
6.2 Definition:
“A measure of the useful ​work​ obtainable from a constant ​temperature​,
constant ​volume​ ​thermodynamic​ system; more precisely, the difference between internal energy
(of a system) and the product of its ​absolute temperature​ and ​entropy​.”

6.3 Helmholtz function:

The thermodynamic function of a system that is equal to its internal energy minus the product of
its absolute temperature and entropy: A decrease in the function is equal to the maximum amount
of work available during a reversible isothermal process.

6.4 Description:
In thermodynamics, the Helmholtz free energy is a thermodynamic potential that measures the
“useful” work obtainable from a closed thermodynamic system at a constant temperature and
volume. For a system at constant temperature and volume, the Helmholtz energy is minimized at
equilibrium.
Since in this case no work is performed on the environment, the drop in the Helmholtz energy is
equal to the maximum amount of useful work that can be extracted from the system. For a
system at constant temperature and volume, the Helmholtz energy is minimized at equilibrium.
When Helmholtz is positive the process is not spontaneous.
6.5 Mathematical Expression:

Fig .2
The Helmholtz free energy is defined as:

● A is the Helmholtz free energy (​SI​: ​joules​, ​CGS​: ​ergs​),

● U is the ​internal energy​ of the system (SI: joules, CGS: ergs),

● T is the absolute temperature (​Kelvin​) of the surroundings, modeled as a heat bath,

● S is the ​entropy​ of the system (SI: joules per Kelvin, CGS: ergs per Kelvin).

6.6 Free energy:

“The free energy is the internal energy of a system minus the amount of energy that cannot be
used to perform work.”

6.6.1 Note:
If a more disordered (higher entropy) final state is created, less work is required to create the
system. The Helmholtz free energy is then a measure of the amount of energy you have to put in
to create a system once the spontaneous energy transfer to the system from the environment is
 accounted for.

6.7 Derivation​:
Let us consider a system that is in thermal equilibrium with its surroundings at a temperature T.
When there is a change in system and there is a
transfer of heat energy between system and
surroundings, the Clausius inequality can be
arranged in the form;
dS - δ q/T ≥0
We can examine this inequality for either a
constant volume process or a constant pressure
process.

From the​ ​first law of thermodynamics​ in a closed system we have

dU = δ q+ δ W​-------------------------(1)
where U is the internal energy, δ q is the energy added as heat and δ W​ is the work done on the
system.
Where at constant volume dV = 0 so PdV is zero and so work done is zero.
dU = δ q
This equation is important because it now express the criterion for a spontaneous change solely
in terms of the state function of the system.
From the ​second law of thermodynamics​,
dS ≤δ q/T
for a ​reversible process​ we may say that δ q ≥ TdS​. Also, in case of a
reversible change, the work done can be expressed as δ W= - PdV​ (ignoring electrical and other
non-PV work). Hence; eq(1) becomes
dU ≤ TdS –PdV -------------------------(2)

Now as temperature is also constant so dT = 0 and also Sd=0. Adding this value of temperature
change with TdS, the equation (2) becomes,
dU ≤ TdS+SdT(constant Temp. and Volume)
Here by product rule;
dU ≤ d(TS)
dU – d(TS) ≤ 0
d(U-TS) ≤ 0
U-TS = A (Helmholtz free energy)
dA ≤ 0

6.8 Conclusion:
Helmholtz free energy must stay the same(reversible) or decrease (irreversible) for closed system
at constant volume and temperature.
“The change in a system at constant temperature and volume is spontaneous if the Helmholtz
energy is less than or equal to zero.”
In other words the change under these conditions is spontaneous if it leads to a decrease in
Helmholtz energy.
Therefore t equilibrium the change for both forward and reverse process should be zero.
d Aeq =0

6.9 Valuing of dA:

A = U-TS
dA=dU-TdS​≤0

6.9.1 Negative value of dA:

A negative value of dA is favored by negative value of dU and positive value of TdS.
This suggests that tendency of the system is due to its tendency to move towards states of lower
internal energy and higher entropy.
Therefore the tendency of a system to lower A is only due to increase in total entropy.
Positive value of dA:
A positive value of dA is favored by positive value of dU and negative value of TdS.

6.10 Maximum Work:

“The change in the Helmholtz energy is equal to the maximum work accompanying a process at
constant temperature and constant volume.”
Thus A is sometimes referred to as “maximum work function”or “work function”
A = U-TS
dA=dU-TdS​≤0

Change in internal energy = reversible heat + reversible work done

dU = q + W
andTdS = T(q/T) = q
dA = W (max. reversible work done)
heredA = q+W – q
6.10.1 Note:
Hence the symbol A (used for Helmholtz free energy) is taken from the Greek word
‘Arbeit’meaning ‘Work’ which also shows that the change in the Helmholtz energy is equal to
the maximum work at constant temperature.

6.11 Heat transfer effect on work:

When a macroscopic isothermal changes takes place;
dA = W max.
where
dA=dU-TdS
Work is the energy transferred to the surroundings as uniform motion of atoms.Because the
energy stored is random thermal motion (TS) cannot be used to achieve uniform motion in the
surroundings, only the part of U that is not stored in that way (the U-TS) can be converted into
work.

6.11.1 Outside flow of Heat:

The transfer of heat outside decreases the disorder-ness of the system and hence there is less
amount of work done than the internal energy of the system.

6.11.2 Inside flow of heat:

The transfer of heat inside increases the disorder-ness of the system and hence there is larger
amount of work done than the internal energy of the system.