FEB 421 THERMODYNAMICS IV

Course Outline
1. Generalized Thermodynamic Relations
 Essential Mathematics
 Thermodynamics of state and Maxwell Relations
 Differential Equation of State
 Relations for Internal Energy, Enthalpy and Entropy
 Specific heat relations
 Clausius-Clapeyron equation
 Physical Coefficients
 Joules’ Thompson Coefficient
2. Mixtures
3. Fuels and Combustion
4. Internal Combustion Engines

References
1. Applied Thermodynamics for Engineering Technologists. Fifth Edition T.D Eastop and A. Mc
Conkey
2. Scilab Textbook Companion for Applied Thermodynamics and Engineering by T.D. Eastop
and A. Mc Conkey

Course Assessment
1. Assignments, Practicals and CATs = 30 %
2. End of Semester Exam = 70 %
Course Lecturer
GE. Amos Kola
Cellphone: 0720122635
Email address: kolaamos@gmail.com
Course Objectives
1. Write balanced equations of mixtures and their thermodynamic relations between the mixtures

2. Learn about the chemistry of fuels and their applications to IC engines

3. Learn about the types of IC engines

GENERALIZED THERMODYNAMIC RELATIONS

Relationships between various properties (any characteristic of a system which can be measured or
calculated. Temperature and pressure are examples of properties that can be measured. Internal energy,
enthalpy and entropy are examples of properties that can be calculated), can be derived
mathematically.

These can then be applied to gases, liquids and solids, the main purpose being to demonstrate
how first and second laws are used experimentally or theoretically to determine the values of
internal properties such as internal energy and entropy which are not directly measurable in
terms of measurable properties such as temperature, pressure and volume.

Essential Mathematical Relations

Euler Theorem

If a quantity z is a function of x and y we can say mathematically that there is a functional

relationship which may be expressed as:

**

Where x and y are independent variables.

The general function for n variables will be;

Upon differentiation of equation (**) a differential change in z results in:

Where x and y are suffix of partial differential coefficients.

The infinitesimal quantity dz is a complete (exact differential) since the integral

And depends only on the end states 1 and 2 and is independent of the path.

Equation [1] is general and applies to any infinitesimal change of state.

Suppose an infinitesimal change is such a way that z is constant then dz = 0 and if dz = 0 then
equation [1] becomes:

Dividing equation [2] by dy we get

 ( )

Suppose there exists a relation between the variables of the form

x = f (y, z), then

( )

Since dz = 0 (i.e. z = constant)

Then

Or

Substituting equation [6] in equation [3] for we get

Multiplying both sides of [7] by leads to

The above is a cyclic relation.

In thermodynamics equations frequently arise of the form:

Comparing equation [9] with [1], the infinitesimal quantity dz in equation [9] represents a
complete differential only if;

I.e. equations [9] and [1] are identical only if and

Differentiating equation [10] we have:

And

i.e. if z = f (x, y), the magnitude of the second derivative of z with respect to x and y is
independent of the order of differentiation and hence;

This is the Euler Criterion or Euler Theorem.

It applies only to point functions.

It follows that in equation [13] satisfied then equation [9] and [1] are identical and the quantity z
in [9] must be capable of being expressed as a function of x and y.

dz is then referred to an exact or perfect differential.

Conversely, if the quantity z is known to be a property, equation [13] must be satisfied.

Maxwell was the first to apply relation [13] in thermodynamics.

He recognized that this criterion must apply to such state properties as and but that it
cannot apply to work and heat since those are not state functions of the system.

Another useful relation can be derived as follows:

If

And

Then the function w can be expressed as follows:

And its complete differential can be expressed as

Differentiating equation [17] while y is constant we get

x
z

Thermodynamic of State and Maxwell Relations

For single compressible substance, Maxwell relations are 4 equations which involve and .

Since the entropy, S is not directly measurable, the relations provide us with means of
calculating entropy.

For derivation of Maxwell relations an understanding of thermodynamic potentials is required.

Thermodynamic Potentials

Thermodynamic potentials are energy terms mathematically formed by combining basic

coordinates and in various ways.

Internal energy, U

U is a function of and and is mathematically given by the Gibb’s function as

Physically, du is the increment in the internal energy of a system.

Enthalpy, h

It is defined as the total energy function of the system.

Equation [2] defines in terms of and . However, we would like to define h in terms of 4
basic coordinates i.e. we get rid of u from [2].

To do this we make infinitesimal changes in u and v in equation [2] to get

Substituting for du from [1] we get

Or

I.e. h in terms of 4 basic coordinates and .

Look at a physically isothermal process which is always reversible.

The principle of increase of entropy of entropy states that the entropy remains constant during a
reversible process and increases during irreversible process i.e. entropy never decreases.

Thus we can write:

Or

Or

Putting the above inequality in the first law equation i.e. dq = du + pdv we get

Or

Case 1

If an infinitesimal process is going on with a constant volume i.e. dv = 0 in the inequality [6]
leads to;

Or

Thus we have a physical quantity [u – Ts] in energy units which never increases during an
isothermal isometric (isochoric) (constant temperature constant volume)

This is called the Helmholtz free energy or Helmholtz function and is expressed as
This is the third thermodynamic potential.

In order to represent Helmholtz, free energy in terms of 4 basic properties, and we give a
small change to u, T and S in equation [9] or differentiating equation [9] to get;

Using equation [1] to eliminate we get;

.i.e. in terms of the 4 basic coordinates.

Case 2

If the isothermal process is going on at a constant pressure i.e. = 0, the inequality in [6] leads
to – ) and since p = constant, and since

– , thus we have a physical quantity in energy units – which

never increases during an isothermal isobaric process (constant temperature, constant pressure).

This is another thermodynamic potential referred to as the Gibbs free energy or Gibbs
function, g.

In order to represent the Gibbs function, g in terms of basic coordinates , differentiate equation
[11] i.e. gives small changes, and in equation [11]. i.e.

– –

Using equation [1] to eliminate du, we get

Giving g in terms of 4 basic coordinates

and represent extensive values of the Helmholtz and Gibbs functions and and represent
specific values.

Maxwell Relations as Got from Thermodynamic Potentials

The first potential is the internal energy, and is given as

–
Comparing this equation with equation [9]

Where,

and

It is right to say that

And

u is an exact (perfect) differential thus we must have

Differentiating equation [13a] with respect to v and holding s constant we get

Differentiating [13b] with respect to s holding v constant, we get

Thus it right to say

This is the First Maxwell Relation

The second thermodynamic potential is defined as

From the above equation we will have

And

Differentiating equation [14a] with respect to , holding s constant and differentiating equation
[14b] with respect to s holding v constant and with the fact that h is an exact differential, the
second derivative should be equal.

This leads

This is the second Maxwell Relation

The third thermodynamic potential is the Helmholtz relation which is defined as – and in
terms of 4 basic coordinates it is given as

Which comparing with equation [9] we have

Differentiating [16a] with respect to T holding v constant and differentiating [16b] with respect v
holding T constant, f being an exact differential will get

This implies that

This is the third Maxwell relation

The fourth thermodynamic potential is the Gibbs function which is defined as

And in basic coordinates, g is given by

Comparing the above with equation [9] we get

g being an exact differential therefore

Differentiating equation [18a] with respect to T holding p constant and equation [18b] with
respect to p holding T constant, this yields

This being the fourth Maxwell relation

NB//

 The Maxwell equations do not refer to processes but simply express relations between
properties which must be satisfied when any system is in a state of equilibrium.
 Each partial differential coefficient can itself be regarded as a property of a state.
 Since entropy is not measurable then Maxwell relations in terms of and provide a
means of measuring entropy.

EQUATION OF STATE (CHARACTERISTIC EQUATIONS)

From the differentials of the thermodynamic equations we obtain equations [13], [14], [16] and
[18] implying that
These equations [20] – [23] provide the thermodynamic definitions of and for a simple
compressible substance. E.g. Temperature is the rate of change of internal energy with entropy at
constant volume while the pressure is the rate of change of internal energy with volume under
isentropic conditions.

These equations are referred to as equation of state.

They provide relationships between the intensive thermodynamic coordinates under equilibrium
conditions and enable determination of all other properties.

The perfect gas equation Pv = RT is an example of such an equation of state.

For a simple compressible substance, two thermodynamic coordinates are required to specify the
state completely. E.g. equations [20] and [21] indicate that if the internal energy is known as a
function of entropy and volume, then the state of a simple compressible substance is completely
satisfied .i.e.

is a valid equation of state.

Similarly, other valid equations of state are of the form

NB// Equation [24] is considered to be the fundamental equation from which all other
information about a system may be derived.

Relations for Internal Energy, Enthalpy, Entropy and Specific heats

Specific Heats

Specific heats at constant volume is defined by

From second law of thermodynamics,

Assuming

Therefore,
Substituting [29] into [28] we get

( )

At v = constant equation [30] reduces to

The specific heat at constant pressure is defined as

Also from second law of thermodynamics

Assuming s = s (T, P) and differentiating with respect to T we get

Substituting [34] into [33]

( ]

Or

( ]

At P = constant equation [35] reduces to

Or

From equations [31] and [36] we have

 ( ]

Internal Energy

From equation [31] we know that

Given

Dividing by dv we get

From third Maxwell equation we have

Substituting for in [38] we have

( )

Substituting equation [39] into equation [29] i.e. we have

[ ( ) ]

Along an isometric .i.e. v = constant equation [40] reduces to

And along an isothermal i.e. T = constant

( )
Equation [40] can be used to determine the change of internal energy for a given change of state
for a pure substance if the constant specific heat is known along one isometric and the equation
of state explicit in P.

Enthalpy

Consider equation [35] i.e. ( ]

At t = constant [35] reduces to

( )

Or

( )

From fourth Maxwell Relation

Substituting in equation [41] we get

( )

Or

( )

Consider

Then

Or

[ ( ) ]
Equation [43] is a general equation for the change of enthalpy of a pure substance in terms of
and Cp.

For constant temperature equation [43] becomes

[ ( ) ]

Along an isobar equation [43] becomes

The significance of equation [43] is that it can be integrated to give the change in enthalpy
associated with the change of state i.e.

∫ ∫[ ( ) ]

Entropy

Let

Then

From

This implies that

From fourth Maxwell relation

Or
 ∫ ∫

Along an isobar i.e. P = constant

Along an isotherm i.e. T = constant equation [47] reduces to

Similarly consider

Then

From

This implies that

From third Maxwell relation

Substituting for in equation [50] we get

Or
Or

∫ ∫

In this case this expression for change of entropy involves the change of entropy along an
isometric where the constant volume specific heat is known and along an isotherm where an
equation of state explicit in P is known.

PHYSCICAL COEFFICIENTS

Coefficient of thermal expansion (Volume expansivity)

Consider a simple compressible substance in which this implies that

We define coefficient of thermal expansivity by the equation

Where

is the relative change in volume with temperature at constant pressure.

Coefficient of Isothermal Compressibility

The rate of change of volume with pressure at constant temperature relative to a volume v is
defined as coefficient of isothermal compressibility and is denoted by

is an indication of the change of volume that results from change in pressure while temperature
remains constant. i.e.

It is defined as above since the gradient is always negative .i.e. the volume of a substance
always decreases with increase in pressure when the temperature is constant.

From main solids and liquids can be regarded as constant for many purposes.
The reciprocal of the isothermal compressibility is called isothermal bulk modulus.

Relations between and

When and of a given substance are known the equation may be used
to find partial differentials involving P, v, and T.

Both and are thermodynamic properties of a substance and for a simple substance are
functions of two independent properties.

Considering P, v and T then the cyclic equations becomes

From which

And

Implying that

Alternatively, these relations between and can be derived as follows:

Consider

Or

For constant volume process

And
Implying that

At constant pressure equation [58] reduces to

Differentiating [59] with respect to at constant temperature, we have

At constant temperature and equation [58] reduces to

Differentiating [61] with respect to T and P =constant, we get

Since is a state function and from equations [60] and [62] we have

Implying that

NB/

From equation

( ] ( ]

Given the relation

Or
Rewriting RHS of equation [1] in terms of equation [2] we get

Substituting in [1] we have

From third Maxwell relation

Substituting in [3] we get

( ]

Given

Also

From the cyclic relation

Implying that

Substituting [5*], [6*] and [7*] into [4*] we get

[ ]
Isentropic Compressibility

It is defined as

It indicates the relative change in volume with changes in pressure under quasi-static adiabatic
conditions.

The reciprocal of is isentropic bulk modulus.

Example

1. Show that

2. From the result in [1] evaluate for

a) Perfect gas
b) A Van der Waals gas whose equation is

Solution

Hence

From fourth Maxwell relation

Hence

Since
And

a) For perfect gas

Given

For a perfect gas

Isentropic relation for a perfect gas

b) For Van der Waals gas

Or

Hold P constant

Therefore
 ( )

Joule Thompson Coefficient

When a fluid passes through a throttling device e.g. valve, porous plug, capillary tube or an
orifice, the enthalpy remains constant.

In refrigeration cycle such as device is used to provide a sudden drop in the temperature.

However a drop does not always occur, the temperature may remain constant or it may increase.

Whether these occur depends on the value of the Joule Thompson coefficient defined as

If is positive the temperature decrease follows the pressure decrease across the device.

If is negative a temperature increase results.

The can be expressed in terms of and

The differential is given as

( ]

Holding h constant as demanded by the definition of we get

( ]

In terms of partial derivatives we have

( ]

Since is easy to measure, the relation provides us with a relatively easy method to evaluate Cp.

Clapeyron Equations

It is useful in relation to phase changes as it relates the rate of change of saturation pressure with
temperature to the enthalpy of evaporation, the temperature and specific volume; thus it enables
the evaluation of the enthalpy of evaporation from the measurement of and .
The third Maxwell relation allows the expression of enthalpy of evaporation using data
alone.

Consider the diagram below

Suppose we desire at the point and then from the third Maxwell relation

Since the temperature remains constant during the change of phase we can write

Consequently, the third Maxwell relation gives

Given

Integrating equation [*]

∫ ( ) ∫

But ∫

Hence
Making the subject of the formula we have

Substituting for in equation [68] we have

Making the subject of the formula we have

This is the Clapeyron Equation

The partial derivative can be evaluated from saturated state tables using the central difference
approximations i.e.

( )

Where

and are selected at equal intervals above and below

For relatively low pressure, the Clapeyron equation can be modified when

If then

We may treat the saturated vapour as an ideal gas then from our estimation , then going
further to treat the vapour as ideal gas then

The Clapeyron equation thus becomes

Making the subject we have

Or

The above equation is referred to as Clausius - Clapeyron Equation

It can be used for sublimation process involving a solid change to vapour phase change.

During a phse change, the pressure depends only on the temperature hence we may use the
derivative

Rearranging equation [71] we get

Integrating equation [72] between two states we have

Equation [73] assumes that is constant between states 1 and 2

Equation [73] may be used to approximate the pressure or temperature below the limits of
tabulated values.

NB/

We may also derive Clapeyron equation as follows:

Consider the change of state from saturated liquid to saturated vapour for a simple compressible
substance, then from equation and since and are constant then

Implying that

Using the equation and substituting in equation [**] we have

Therefore

( )
Example 1

Suppose the steam table started at Psat = 2kPa ( Tsat = 17.5 oC an desired Tsat at Psat = 1kPa.
Predict the Tsat and compare with the values from the steam tables.

Solution

Using the Clausius – Clapeyron equation

Example 2

The temperature of liquid helium when the vapour pressure is 0.1013 MPa is 4.2K. To what
value should the pressure be reduced to achieve a temperature of 1K? The latent heat of
vaporization at 4.2K is 83kJ/kmol.

Solution

From Clapeyron equation

( ( )] ( )