Thermodynamic functions: Energy, entropy and free energy

(Internal energy, Helmholtz free energy, Enthalpy, Gibb’s free energy- definition, expression and
explanation)

Importants Terms and Types of thermodynamic Systems

Thermodynamics: Thermodynamics is the branch of science or physics that studies

various forms of energies and their conversion from one form to the other like electrical
energy to mechanical energy, heat to electrical, chemical to mechanical, wind to electrical
etc. The study of thermodynamics is comprised of important laws of thermodynamics
namely first law of thermodynamics, second law of thermodynamics, third law of
thermodynamics and Zeroth law of thermodynamics. Thermodynamics is an important
subject area studied under Mechanical Engineering.

System: A quantity of the matter or part of the space which is under thermodynamic study
is called as system. There are three types of system: closed system, open system and
isolated system.

Surroundings or environment: Everything external to the matter or space, which is

under thermodynamic study is called surroundings or environment.

Boundary: The boundary that separates the system and surrounding is called as system
boundary. The system boundary may be fixed or moving.

Closed system: The system of fixed mass across the boundary of which no mass transfer
can take place is called as closed system. However, across the closed system the energy
transfer may take place. An example is fluid being compressed by the piston in cylinder.

Open system: The system across the boundary of which transfer of both mass as well
as energy can take place across the boundary is called as open system. An example is
an air compressor.

Isolated system: The system in which both the mass as well as energy content remains
constant is called an isolated system. In this system no mass or energy transfer takes
place across the boundary.

State of the system: The present status of the system described in terms of properties
such as pressure, temperature, and volume is called the state of system.

Properties of the system: The characteristics by which the physical condition of the
system is described are called as properties of system. Some examples of these
characteristics are: temperature, pressure, volume etc and are called as properties of
system. The system properties are of two types: extensive and intensive properties.
Extensive properties of system: The properties of the system that depend on the mass
or quantity of the system are called extensive properties. Some examples of extensive
properties are: mass, volume, enthalpy, internal energy, entropy etc.

Intensive properties of the system: These properties do not depend on the quantity of
matter of the system. Some of the examples of intensive properties are: freezing point
temperature, boiling point, temperature of the system, density, specific volume etc.

Change of state of system: When one or more properties of the system like pressure,
temperature, volume changes, the state of system changes.

Path of change of state: The succession of states through which the system undergoes
change to reach the final state is called as the path of change of state of the system.
Homogeneous system: The system that has single or uniform phase such as like solid
or liquid or gaseous is called as homogeneous system.

Heterogeneous system: The system that has more than one phase i.e. the combination
of solid, liquid and gaseous state is called as heterogeneous system.

Thermodynamics process: When the system changes from one thermodynamic state
to the final thermodynamic state due to change in pressure, temperature, volume etc, the
system is said to have undergone thermodynamic process. The various types of
thermodynamic processes are: isothermal process, adiabatic process, isochoric process,
isobaric process and reversible process.

Cyclic process: When the system undergoes a number of changes in states and returns
back to the initial state, the system is said to have undergone cyclic process. (ΔUcyclic = 0
and ΔHcyclic = 0).

Isothermal process: The process during which the temperature of the system remains
constant is called as isothermal process. (ΔT = 0 and ΔU = 0).

Adiabatic process: The process during which the heat content of the system remains
constant i.e. no flow of heat takes place across the boundaries of system, the process is
called as adiabatic process. (Δq = 0).

Isochoric process: In this process the volume of system remains constant. (ΔV = 0).

Isobaric process: The process during which the pressure of the system remains
constant, is called as isobaric process. (ΔP = 0).
Reversible process: When the system undergoes changes infinitesimally slowly the
changes can be reversed back, such a process is called as reversible process. During
reversible process the system remains in equilibrium during the change of state of the
system.
Entropy of the system: It is the total energy inside the system, which is not available for
work during thermodynamic process. It depends on the movement of the molecules inside
the system. As the temperature of the system reduces its entropy also reduces. Entropy
of the system is never negative.

Internal energy (E/U)

 Internal energy is defined as the energy associated with the random, disordered
motion of molecules. It is total energy within the substance and is sum of all the
microscopic energies such as (1) translational kinetic energy (2) vibrational and
rotational kinetic energy (3) potential energy from intermolecular forces etc.
 It is separated in scale from the macroscopic ordered energy associated with moving
objects; it refers to the invisible microscopic energy on the atomic and molecular scale.
 For example, a room temperature glass of water sitting on a table has no apparent
energy, either potential or kinetic. But on the microscopic scale it is a seething mass
of high speed molecules traveling at hundreds of meters per second. (see below)
 U is the most common symbol used for internal energy.
 It is an extensive property and a state function.
 Its absolute value cannot be determined but change in internal energy can be
determined by ΔU = U2 – U1 or ΣUproducts - ΣUreactants
 For exothermic process (process in which heat is evolved) ΔU is –ve whereas for
endothermic process (process in which heat is absorbed, ΔU is +ve).
 Internal energy depends on temperature, pressure, volume and quantity of matter.

Enthalpy of the system (H):

 The total heat content of the system is called as enthalpy of the system. The units of
enthalpy are same as heat viz. Joules and Calories.
 It is sum of internal energy and PV energy of the system, defined as H = U + PV.
 It is a state function and an extensive property.
 Like U, absolute value of H cannot be known but ΔH for a chemical reaction can be
determined experimentally by ΔH = H2 – H1 or ΣHproducts - ΣHreactants
 For exothermic process (process in which heat is evolved) ΔH is –ve whereas for
endothermic process (process in which heat is absorbed, ΔH is +ve).
 Enthalpy of a reaction is change in enthalpy that accompanies a chemical reaction
represented by a balanced chemical equation i.e. ΔH(r) = ΣHproducts - ΣHreactants
e.g. (1) Enthalpy of formation: it is enthalpy change when one mole of a compound is
obtained from its constituent elements.
H2(g) + ½ O2(g) → H2O(l) ……….. ΔH(f) = -68 kcal
(2) Enthalpy of combustion: it is enthalpy change taking place when one mole of a
compound undergoes complete combustion in presence of O2.
C + O2 → CO2………… ΔH(c) = + 95.5 kcal

Entropy (S):

 Entropy, the measure of a system’s thermal energy per unit temperature that is
unavailable for conversion into mechanical work (doing useful work).
i.e. Entropy = unavailable energy/temperature
 For a reversible process at constant temperature T, change in entropy is equal to heat
absorbed or heat evolved divided by the constant temperature in kelvin. i.e.
ΔS = qrev/T, where q is the heat absorbed. Unit of entropy is JK/mol
ΔS is +ve if heat is absorbed
ΔS is -ve if heat is evolved.
 Because work is obtained from ordered molecular motion, the amount of entropy is
also a measure of the molecular disorder, or randomness, of a system.
 The concept of entropy provides deep insight into the direction of spontaneous change
for many everyday phenomena. It is the quantity that tells whether a chemical reaction
or a physical change can occur spontaneously in an isolated system or not.
 It is an extensive property and a state function
 Its value depends on mass of substance present in system
 ΔS = Sfinal – Sinitial
 At equilibrium ΔS = 0
 For cyclic process, ΔS = 0
 For natural process ΔS > 0, i.e. increasing
 For adiabatic process ΔS = 0.
 The entropy of a system and surrounding taken together increases (ΔS > 0) in a
thermodynamically irreversible/natural process, but it remains constant in a
thermodynamically reversible process (ΔS = 0).

ΔSsystem + ΔSsurrounding = 0 (for reversible process)

ΔSsystem + ΔSsurrounding > 0 (for irreversible process)

Physical significance of entropy

 First Law of Thermodynamics
 The first law of thermodynamics, also known as Law of Conservation of Energy, states
that energy can neither be created nor destroyed; energy can only be transferred or
changed from one form to another. For example, turning on a light would seem to
produce energy; however, it is electrical energy that is converted.
 A way of expressing the first law of thermodynamics is that any change in the internal
energy (∆E) of a system is given by the sum of the heat (q) that flows across its
boundaries and the work (w) done on the system by the surroundings:
 The first law of thermodynamics states that the change in internal energy of a
system ∆E, equals the net heat transfer into the system Q, plus the net work done on
the system W. In equation form, the first law of thermodynamics is,
ΔE (change in internal energy) = q (heat added to the system)
+ w (work done on the system)
OR
ΔE = q + p ΔV (since w = p ΔV, where P = pressure, ΔV = change in volume)

 This law says that there are two kinds of processes, heat and work, that can lead to a
change in the internal energy of a system. Since both heat and work can be measured
 and quantified, this is the same as saying that any change in the energy of a system
must result in a corresponding change in the energy of the surroundings outside the
system. In other words, energy cannot be created or destroyed. If heat flows into a
system or the surroundings do work on it, the internal energy increases and the sign
of q and w are positive. Conversely, heat flow out of the system or work done by the
system (on the surroundings) will be at the expense of the internal energy, and q and
w will therefore be negative.

q is +ve if heat absorbed by system

q is –ve if heat evolved by the system
w is +ve if work done on the system
w is –ve if work done by the system

So positive heat q adds energy to the system and positive work W adds energy to the
system. This is why the first law takes the form it does, ΔE=q+W. It simply says that
you can add to the internal energy by heating a system, or doing work on the
system.
Thus for adiabatic process, q = 0 therefore w = ΔE
for isothermal, cyclic process, ΔE = 0, therefore q = - w
for isochoric process, ΔV = 0, therefore q = ΔE

 Example: If the gas is heated, it will expand and push the piston up, thereby doing
work on the piston. If the piston is pushed down, on the other hand, the piston does
work on the gas and the gas does negative work on the piston. This is an example of
how work is done by a thermodynamic system. An example with numbers might make
this clearer.
 Limitations of first law of thermodynamics
1. No restriction on the direction of the flow of heat: the first law establishes definite
relationship between the heat absorbed and the work performed by a system. The first
law does not indicate whether heat can flow from a cold end to a hot end or not. For
example: we cannot extract heat from the ice by cooling it to a low temperature. Some
external work has to be done.
 2. Does not specify the feasibility of the reaction: first law does not specify that process is
feasible or not for example: when a rod is heated at one end then equilibrium has to be
obtained which is possible only by some expenditure of energy.
3. Practically it is not possible to convert the heat energy into an equivalent amount of
work. The law does not explain why heat cannot be completely converted into work.
To overcome these limitations, another law is needed which is known as second law of
thermodynamics.

Second Law of Thermodynamics

 The second law of thermodynamics says that the entropy of any isolated system
always increases. Isolated systems spontaneously evolve towards thermal
equilibrium—the state of maximum entropy of the system. More simply put: the
entropy of the universe (the ultimate isolated system) only increases and never
decreases (ΔS > 0).
 In other words, “whenever a spontaneous process takes place, it is accompanied by
an increase in the total entropy of the universe”. More specifically, the term universe
means system and surrounding. Thus,
ΔSuniverse = ΔSsystem + ΔSsurrounding
The law tells that when an irreversible spontaneous process occurs the entropy of the
system and the surrounding increases. i.e. ΔS > 0. When reversible process occurs,
entropy of system remains constant ΔS = 0.
 “Entropy of universe is constantly increasing”
 A simple way to think of the second law of thermodynamics is that a room, if not
cleaned and tidied, will invariably become more messy and disorderly with time –
regardless of how careful one is to keep it clean. When the room is cleaned, its entropy
decreases, but the effort to clean it has resulted in an increase in entropy outside the
room that exceeds the entropy lost.

Helmholtz free energy and Gibb’s Free energy

 Entropy gives a maximal principle but for the entire universe. It would be useful to find
other functions that have similar external properties but for a subsystem of the
universe. e.g. One doesn’t usually states that ice will freeze at particular temperature,
pressure because the entropy of ice plus the freezer plus wires that run to power station
plus etc. have total sum entropy that increases.
 Rather it is decidedly more useful to have some other quantity that applies to the
water/ice itself as a function of temperature and pressure of its environment.
 Two such quantities are Helmholtz free energy and Gibb’s Free energy.
 Helmholtz free energy (ΔA): is the maximum amount of work a system can do at
constant volume and temperature.
 Gibbs free energy (ΔG): is the maximum amount of work a system can do at constant
pressure and temperature
Work function/Helmhotlz function/Helmholtz free energy (ΔA)
Free enerty function/Gibb’s function/Gibb’s free energy (ΔG)
Estimation of Entropy and free energy (Gibb’s Helmholtz equation of free
energy and its application)

Gibbs-Helmholtz Equation
Application of Gibbs-Helmholtz Equation/Relation between emf and Gibbs energy
Free energy and EMF of cell (electrochemical cell, galvanic cell, cell
representation, cell potential and free energy, Nernst equation and applications)

Electrochemical cell: An electrochemical cell is a device capable of either

generating electrical energy from chemical reactions or using electrical energy to cause
chemical reactions. The electrochemical cells which generate an electric current are
called voltaic cells or galvanic cells and those that generate chemical reactions,
via electrolysis for example, are called electrolytic cells. A common example of a
galvanic cell is a standard 1.5 volt cell meant for consumer use.
 An electrolytic is an electrochemical cell that drives a non-spontaneous redox reaction
through the application of electrical energy. They are often used to decompose chemical
compounds, in a process called electrolysis—the Greek word lysis means to break up.

Example: Daniel Cell

Cell notation or line notation in chemistry is a shorthand way of expressing a certain

reaction in an electrochemical cell. The cell anode and cathode (half-cells) are separated
by two bars or slashes representing a salt bridge, with the anode on the left and cathode
on the right. Individual solid, liquid or aqueous phases within each half-cell are separated
by a single bar. Concentrations of dissolved species, in each phase written in parentheses
and the state of each phase (usually s (solid), l (liquid), g (gas) or aq. (aqueous solution))
is included in a subscript after the species name.
Some examples of this notation are:
Zn°|Zn2+||Cl−|AgCl|Ag°
This means that the left electrode (anode) is made of zinc, while the other one (right,
cathode) is composed of a silver wire covered by a silver chloride layer which is not
soluble. Both of the electrodes are immersed into aqueous media where zinc and chloride
ions are present.
Zn°|Zn2+, SO42−||SO42−,Cu2+|Cu°
This cell is very famous: the Daniell cell. If the electrodes are connected, a
spontaneous reaction takes place. Zinc is oxidized, and copper ions are reduced.
Sometimes the state of each species into the cell is written. For example, in
the zinc cell (shown above), we can write that zinc, silver and silver chloride are solids,
while zinc cation and chloride anion are in aqueous medium. So, the new notation will
be:
Zn°(s)|Zn2+(aq), SO42−(aq) || SO42−(aq) Cu2+ (aq) | Cu° (s)
It is possible to express the ion concentration too. For example, in the Galvanic cell:
 Zn°(s)|Zn2+(aq,1mol/L),SO42−(aq,1mol/L)||SO42−(aq,1mol/L)|Cu2+(aq,1mol/L)|Cu°(s)
In this case, all ions (sulfate, zinc and copper) are in a concentration equal to 1
mol/L.
Nernst equation and applications: (derivation, acid- base titraion, redox
titration, solubility product)
Corrosion: (Definition, types and mechanism for -dry, wet, hydrogen evolution and
oxygen absorption)
 Corrosion (Pourbaix diagram for iron)
Pourbaix Diagram

What does Pourbaix Diagram mean?

• A Pourbaix diagram provides information about the stability of a metal as a function of pH and
potential.
• These diagrams are available for over 70 different metals.
• Pourbaix diagrams have several uses, including in corrosion studies.
• A Pourbaix diagram is also known as a potential/pH diagram, equilibrium diagram, EH-pH diagram, a
pE/pH diagram on an E-pH diagram.
• Pourbaix diagrams are plotted by using the Nernst equation (an equation used to calculate electrode
potential).
• As the Nernst equation is derived entirely from thermodynamics, the Pourbaix diagram can be used
to determine which species (metals or alloys) is thermodynamically stable at a given electrode
potential (E) and pH.
• Nernst equation: E = E0 - (0.059/n) × ln (Cion)
• Where: E = electrode potential V; E0 = standard electrode potential, V; n = number of electrons
transferred; Cion = molar activity (concentration) of ions
 The diagram defines the following zones of the equilibrium states:

below the line a-b-j: Solid iron (immunity zone). The electrochemical reactions in this zone proceed in
the direction of reduction of iron ions. No corrosion occurs in this zone.
a-b-n-c-d-e: Aqueous solution of ion Fe2+ (corrosion zone). Metallic iron oxidizes in this zone.
e-d-f-g-k: Aqueous solution of ion Fe3+ (corrosion zone). Metallic iron oxidizes (corrodes) in this zone.
h-f-g-m: Aqueous solution of ion FeO42- (corrosion zone).
c-d-f-h-i: Solid ferrous oxide Fe2O3 (passivation zone). Iron oxidizes (corrodes) in this zone however the
resulted oxide film depresses the oxidation process causing passivation (corrosion protection of the
metal due to formation of a film of a solid product of the oxidation reaction).
n-c-i-p: Solid oxide Fe3O4 (Fe2O3*FeO) (passivation zone). The oxide film causes passivation.
b-n-p-j: Solid hydroxide (II) Fe(OH)2 / FeO*nH2O / green rust (passivation zone).
 MCQ

1. If an alloy of Au and Zn is immersed in HCl, which among the following will be

feasible?
(a) H2 evolution
(b) Zn dissolution
(c) Formation of nanoporus Au
(d) All of the above

2. Which of the following statements is not true for Pourbaix diagram?

(a)It represents the stability of a metal as a function of potential and pH
 (b)The horizontal lines represent electron transfer reactions and are pH
independent
(c) The vertical lines are potential independent
(d)It considers both thermodynamic and kinetic parameters

3. Which of the following reactions is only pH dependent?

(a)Al3+ + 3e- = Al
(b)Zn + 2H2O = Zn(OH)2 + 2H+ + 2e-
(c) Zn2+ + 2H2O = Zn(OH)2 + 2H+
(c) H2CO3 = H2O + CO2

4. Dry corrosion is also called as _________

a) Chemical corrosion
b) Electrochemical corrosion
c) Wet corrosion
d) Oxidation corrosion
5. Anhydrous inorganic liquid metal surface in absence of moisture
undergoes ___________
a) Wet corrosion
b) Dry corrosion
c) Galvanic corrosion
d) Pitting corrosion
6. The rusting iron is the __________
a) Oxidation corrosion
b) Liquid metal corrosion
c) Wet corrosion
d) Corrosion by other gases
7. Corrosion between the dissimilar metals is called as __________
a) Galvanic corrosion
b) Dry corrosion
c) Oxidation corrosion
d) Concentration cell corrosion
8. Wet corrosion is also called as ____________
a) Chemical cell
b) Electro chemical cell
c) Oxidation reaction
d) Liquid metal corrosion
9. Corrosion due to the formation of cavities around the metal is called as the
___________
a) Pitting corrosion
b) Soil corrosion
c) Water line corrosion
d) Galvanic corrosion
10. Corrosion due to the flow of the _________ between the cathodic and anodic
areas is called as the electro chemical corrosion by evolution of hydrogen ad
absorption of oxygen.
a) Electron current
b) Proton current
c) Ion current
d) Neutron current
11. Corrosion due to difference in water level is __________
a) Soil corrosion
b) Oxidation corrosion
c) Pitting corrosion
d) Water line corrosion
12. Corrosion is uniform in __________
a) Dry corrosion
b) Wet corrosion
c) Pitting corrosion
d) Water line corrosion
13. Dry corrosion takes place in __________
a) Homogeneous solutions
b) Heterogeneous solutions
c) Neither homogeneous nor heterogeneous
d) Both homogeneous and heterogeneous solutions

14. Concentration cell corrosion occurs when a metallic surface is partially

immersed in an electrolyte and partially exposed to air.
a) True
b) False

15. Poorly oxygenated part becomes cathode whereas well oxygenated part
becomes anode in the differential aeration corrosion.
a) True
b) False