STATE FUNCTIONS

  Quantities that depends on the conditions reached by a system

 Examples of these properties are pressure, temperature, volume, enthalpy, and
internal energy
 On thermodynamic charts (such as PV diagrams), state functions are represented by
points.
 Infinitesimal changes in state functions are represented by exact differentials.
Integration of these exact differentials result to finite changes in the value of the
state function.
PATH FUNCTIONS

 Movement
  of a system’s conditions from one state to another is called a process.
Quantities that depend on the path taken by the system during a process are called
path functions.
 Examples of path functions are work and heat.
 On thermodynamic charts (such as the PV diagram), path functions are represented
by areas under the curve.
 Infinitesimal quantities of path functions are represented by inexact differentials.
Integration of these inexact differentials correspond to finite values of the path
function.
STATE FUNCTIONS AND PATH FUNCTIONS
CYCLIC PROCESSES

 A cyclic process refers to any sequence of

thermodynamic processes that eventually
returns the system to its initial state.

 For any cyclic process, changes in the state

variables of a system are all equal to zero.
 LECTURE 6.
ENTROPY AND THE SECOND LAW OF
THERMODYNAMICS
SPONTANEITY

 Spontaneity refers to the natural occurrence of

processes.
 A spontaneous process does not require work to be
done to be brought about.
 All naturally occurring process always tend to change
spontaneously in a direction which will lead to
thermodynamic equilibrium.
 What determine the direction of spontaneous change?
FIRST LAW OF THERMODYNAMICS

 

 The first law of thermodynamics allows for calculation of heat, work, and energy
changes for any particular process.

 The first law of thermodynamics however doesn’t give any insight on the direction
at which processes proceed spontaneously.
DISPERSAL OF ENERGY

 The direction of spontaneous change tend to be in the

direction that leads to dispersal of the total energy of a
system.
SECOND LAW OF THERMODYNAMICS

 Kelvin-Planck Statement
No apparatus can operate in such a way that the only effect is to convert heat
absorbed by a system completely into work done by the system.

 Clausius Statement
No process is possible which consists solely in the transfer of heat from one
temperature to a higher one.
HEAT ENGINE
A heat engine is a device or machine that produces work from heat in a cyclic process
Example: steam power plant

1. Pumping of liquid water to high pressure in the boiler

2. Conversion of liquid water to superheated steam at
high pressure in the boiler using heat from fuel
combustion
3. Expansion of steam to a low pressure and temperature
in a turbine converting energy to shaft work
4. Condensation of exhaust steam from the turbine is by
transfer of heat to the surroundings
 HEAT ENGINE: THEORETICAL TREATMENT

net
  work=|W |=|W t|−∨W p ∨¿

Heat reservoirs
TH
- capable of accepting/rejecting infinite
amounts of heat without undergoing
temperature change
Ex. Furnace at TH, surrounding
atmosphere/rive at Tc
TC
HEAT ENGINE: THEORETICAL STATEMENT

 
HEAT ENGINE

 

 Kelvin-Planck Statement
No apparatus can operate in such a way that the only effect is to convert heat
absorbed by a system completely into work done by the system.

What is the maximum possible value for the efficiency of a heat engine?
PROCESS REVERSIBILITY
Irreversible process
PROCESS REVERSIBILITY

Internal reversibility
 No irreversibility occurs within the boundaries of the system during the process
 System passes through a series of equilibrium states in both the forward and
reverse process
External reversibility
 No irreversibility occurs outside the system boundaries during the process
 Ex. Heat transfer between a reservoir and a system if the outer surface of the
system is at the temperature of the reservoir.
A process is totally reversible if it involves no irreversibilities within the system
or its surroundings.
PROCESS REVERSIBILITY
CARNOT ENGINE

(a – b) Reversible adiabatic process:

increase of T from TC to TH
(b – c) Reversible isothermal process: |
QH| is absorbed from hot reservoir
(c – d) Reversible adiabatic process:
decrease of T from TH to TC
(d – a) Reversible isothermal process: |
QC| is rejected from cold reservoir
CARNOT ENGINE
CARNOT ENGINE

  For a  b
CARNOT ENGINE

  For c  d
CARNOT ENGINE
 

Therefore
CARNOT ENGINE

  For b  c

 For d  a
CARNOT ENGINE

 The
  efficiency of an engine can be
calculated by:

 Substituting
and
CARNOT ENGINE

 

Since

Then, the efficiency of a Carnot engine is

given by:
CARNOT ENGINE

 Carnot theorem
For two given heat reservoirs no engine
can have a thermal efficiency higher than
that of a Carnot engine.
EXAMPLE

A chemical engineer wants to extract energy from a geothermal well. At the top of the
reservoir, the temperature of the water is 50oC, and as the water goes out of the coils, the
temperature is 20oC. What is the maximum amount of energy that can be extracted from 1000
kg of water in the reservoir? Assume the specific heat capacity of water is constant at 4.186
kJ/kg-K.
CARNOT CYCLE

In  a Carnot engine

For the working fluid undergoing a reversible Carnot cycle:

REVERSIBLE CYCLE
Internally
  reversible cycle divided into
differential segments each representing a
Carnot cycle

For each Carnot cycle:

For the entire cycle:

ENTROPY

   the entire cycle:

For

Defining the term inside the integral to be

entropy:
ENTROPY

 Entropy is a state function that measures how much of a system’s

energy is dispersed during a process.

 A change in entropy occurs as a result of a physical or chemical

change in a system, this change measures the extent to which
energy is dispersed in a disorderly manner
ENTROPY CHANGES FOR VARIOUS
PROCESSES
 Since
  entropy is a state function, for any process, the entropy change of a system is
given by:

 For a totally reversible process, the change in entropy can be obtained by the integral:

 The entropy change due to heat transfer to a heat reservoir is given by:

 An isentropic process is any process that is both reversible and adiabatic. The
entropy change due to an isentropic process is zero.
ENTROPY CHANGES FOR VARIOUS
PROCESSES
Isothermal
  expansion/compression

For an ideal gas

ENTROPY CHANGES FOR VARIOUS
PROCESSES
  Isobaric processes
ENTROPY CHANGES FOR VARIOUS
PROCESSES
  Isochoric process
ENTROPY CHANGES FOR VARIOUS
PROCESSES
  For any reversible process occurring in a system:

For an ideal gas undergoing a reversible process:

For an ideal gas undergoing any process (reversible or not):

If Cp is constant:
ENTROPY CHANGES FOR VARIOUS
PROCESSES
  For any reversible process occurring in a system:

For an ideal gas undergoing a reversible process:

For an ideal gas undergoing any process (reversible or not):

If CV is constant:
EXAMPLE

  A piston-cylinder assembly contains 2.00 mol CO2 gas expanding at 273 K from 5.0
L to 6.5 L. Calculate the entropy change associated with the expansion.
a) Assuming CO2 is ideal.
b) Assuming CO2 follows the virial equation truncated to two terms

where B = -149.7 cm3 mol-1

EXAMPLE

The
  following empirical model shows the temperature dependence of Cp of N2.

where T is in K.
Calculate the change in entropy associated when 2.50 mol N2 is heated from 298 K to
373 K at 1 bar.
EXAMPLE

Assuming the following gases are ideal and have constant molar heat capacities.
Calculate the entropy change associated when 1.50 mol of the following gas are
cooled from 80oC to 25oC at constant volume.
a) Ar
b) N2
c) CO2
EXAMPLE

Calculate the entropy change when argon at 25oC and 1.00 bar in a container
of 0.500 L is allowed to expand to 1.000 L and is simultaneously heated to
100oC. Assume that argon is ideal gas and has constant molar heat capacity.
ENTROPY CHANGES FOR VARIOUS
PROCESSES
For
  phase changes:
EXAMPLE

Calculate
  the entropy change associated with transforming 25.0 g of ice at -5.00 oC to steam at 105oC.
For H2O:

Assume constant heat capacities:

 ENTROPY CHANGES FOR VARIOUS
PROCESSES
  Isothermal mixing of gases
 ENTROPY CHANGES FOR VARIOUS
PROCESSES
  Isothermal mixing of gases

If
 ENTROPY CHANGES FOR VARIOUS
PROCESSES
  Isothermal mixing of gases (at constant P)
EXAMPLE

A 250-L tank contains 10 moles of air (79% N2 and 21% O2) at 1 bar. Another 250-L
container tank contains 10 moles of O2 at 1 bar. The contents of these two tanks are
mixed isothermally. What is the entropy change associated with the described
process?
MEASUREMENT OF ENTROPY

 The
  entropy of a system at a temperature T is related to its entropy at T = 0 by
accounting the entropy change in heating the system to a final temperature T and
accounting the entropy change due to phase transitions between T = 0 and the
temperature T.
 For pure substance that melts at Tf and boils at Tb, the entropy of the substance at a
temperature T above Tb is given by:
 MEASUREMENT OF ENTROPY
 

 All properties in this equation, except S(0), can be measured by

calorimetry and integrals can be evaluated graphically or by polynomial
fitting.
MEASUREMENT OF ENTROPY
 
 Measuring heat capacities near T = 0 can be difficult. Debye extrapolation
allows for measurement of Cp at near T = 0 () temperatures by assuming
that Cp is proportional to T3 .

 Values of Cp is measured down to the lowest possible temperature and the

equation Cp = aT3 is fitted to the data.
THIRD LAW OF THERMODYNAMICS

 At T = 0, the motion of all the molecules in a system ceases.

 In a perfect crystal, all the atoms or ions are arranged in a regular, uniform
array. At T = 0, the localization of matter and absence of molecular motion
suggests that the entropy of perfect crystal at T = 0 is zero.
 The Nernst heat theorem provides an experimental insight to the zero entropy
of perfect crystals at T = 0.
“ The entropy change accompanying any physical or chemical transformation
approaches zero as the temperature approaches zero: ΔS  0 as ΔT  0 provided
all the substances involved are perfectly crystalline.”
THIRD LAW OF THERMODYNAMICS

 It follows from Nernst theorem that if S = 0 is arbitrarily assigned to the entropy of

elements in their perfectly crystalline form at T = 0, then all perfect crystalline
compounds have S = 0 at T = 0. And thus concludes the Third Law of
Thermodynamics.
“The entropy of all perfectly crystalline substances at T = 0.”

 For a general system (which may or may not consists of perfect crystals), this implies
that:
“The entropy of a system approaches a constant value as T approaches 0.”
ABSOLUTE ENTROPY

 The
  entropy of a substance at T = 0 is called its absolute entropy or Third-Law
entropy.
 When the substance is in its standard state, the standard entropy at temperature T is
denoted by . Values of standard entropy are usually listed at 298 K.
 The standard entropy change of a reaction at temperature T is determined from the
balanced chemical equation and the standard entropies of the reactants and products.
 STANDARD MOLAR ENTROPY AT 298 K

Atkins 8th Ed. – Appendix Table 2.5: 5th column – lists down standard molar entropy at 298 K of various
organic substances in J/K-mol
Atkins 8th Ed. – Appendix Table 2.7 5th column – lists down molar entropy at 298 K of various inorganic
substances in J/K-mol
EXAMPLE

Calculate the standard entropy change at 298 K for the following reactions.
(1) H2O (g)  H2O (l)

(2) N2 (g) + 3 H2 (g)  2 NH3 (g)

(3) NaCl (s)  Na+(aq) + Cl- (aq)

(4) CH4 (g) + 2 O2 (g)  CO2 (g) + 2 H2O (l)

 EXAMPLE

 The molar heat capacity of lead varies with temperature as follows:

T (K) 10 15 20 25 30 50

Cp (J/mol-K) 2.8 7.0 10.8 14.1 16.5 21.4

T (K) 70 100 150 200 250 298

Cp (J/mol-K) 23.3 24.5 25.3 25.8 26.2 26.6

Calculate the standard absolute entropy of lead at 25oC.

   Debye extrapolation at
By
 
Evaluate the equation:
MATHEMATICAL STATEMENT OF THE SECOND
LAW  

𝑇
 

𝐻
Q

𝑇𝐶
 

 For any irreversible process:

As the process approaches reversibility:

MATHEMATICAL STATEMENT OF THE SECOND
LAW
 

Every process proceeds in such a direction that the total entropy change
associated with it is positive, the limiting value of zero being attained only by
a reversible process.
No process is possible for which the total entropy decreases.
EXAMPLE

An inventor has devised a complicated non-flow process in which 1 mole of air is

the working fluid. The net effects of the process are claimed to be:
A change in state of the air from 250oC and 3 bar to 80oC and 1 bar
The production of 1,800 J of work
The transfer of an undisclosed amount of heat to a heat reservoir at 30oC
Determine whether the claimed performance of the process is consistent with the
second law. Assume air is an ideal gas for which Cp = (7/2)R.
 SOLUTION

Given:
  P1 = 3 bar, P2 = 1 bar, T1 = 523.15 K (250oC), T2 = 353.15 K (80oC)
n = 1 mol, W = -1800 J, Tsurr = 303.15 K (30oC)

The amount of heat emitted by air in the system to the surrounding is given by:

The entropy change of the surrounding is given by:

 SOLUTION

 
The entropy change of the system is given by:

The total entropy change due to the process is given by:

The process is therefore possible.

CLAUSIUS INEQUALITY

 The
  maximum amount work done by a system by a process occurs when the process is
reversible. It can be written that:

 Since the internal energy is a state function, its change is the same regardless whether the
path taken by the process is reversible or irreversible.

 Therefore, we can write:

CLAUSIUS INEQUALITY

 
 Rearranging this expression and dividing both sides by T

 Substituting the definition dS = dQrev/T

 This expression is called the Clausius inequality.

CLAUSIUS INEQUALITY

 

 Consider an isolated system, so that dQ = 0. The Clausius inequality implies that for
an isolated system:

 This expression shows that the entropy of an isolated system cannot decrease due to a
spontaneous process. This statement captures the Second Law of Thermodynamics.
CLAUSIUS INEQUALITY

 

 Any spontaneous process occurring in an isolated

system will increase the system’s entropy until the
system’s entropy is maximized. At maximum
entropy, the system has reached thermodynamic
equilibrium.