UNIVERSITY OF NIGERIA, NSUKKA

DEPARTMENT OF MECHANICAL ENGINEERING

ME 561 – Thermodynamics III

Lecture Notes on
Thermodynamic Relations
for 2017/2018 Session
(Part I)

Lecturer:
Howard O. NJOKU PhD

November 21, 2017

Contents
1 Basic Concepts and Definitions 2

2 Thermodynamic Relations 7
2.1 Review of partial derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2 Maxwell functions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.3 Quantities derivable from P − v − T data . . . . . . . . . . . . . . . . . . 9
2.4 Thermodynamic relations involving enthalpy, internal energy and entropy . 10

1
1 Basic Concepts and Definitions
Thermodynamics:
This is the science dealing with the concepts of energy, the laws governing the conver-
sion of one form of energy into another and the various media employed to effect this
transformation.

Engineering thermodynamics:
This deals primarily with heat and work and the conversion of one into another.

Matter:
Is that which has mass and occupies space. It can be classified as solid, liquid or gaseous.

Energy:
As this is manifested only through its effects, it is very difficult to define energy. It is
sometimes defined as the capacity of matter to do work.

Thermodynamic systems:
In thermodynamics, a system is defined as any collection of matter or any region in space
bounded by a closed surface or wall. The wall may be a real one like that of a tank
enclosing a certain amount of fluid or it may be imaginary, like the boundary of a certain
amount of fluid flowing along a pipe.

Surroundings:
The region of physical space that lies outside the boundaries of the system is called the
surroundings or the environment.

Thermodynamic Properties
The distinguishing characteristics of a system are called the properties of the system. The
essential criterion of a thermodynamic property is that it must have a unique numerical
value when the system is in a particular state. Thus the change in value of a property
will depend only on the initial and final states of the system.

2
 B o u n d a ry

F lu id
w o rk T ra n s fe r

H e a t T ra n s fe r

Figure 1: Closed system

B o u n d a ry

F lu id in

w o rk

F lu id o u t

Figure 2: Open system

Thermodynamic Equilibrium and Equilibrium states

When a collection of matter experiences no more changes in all its properties, it is said
to be in a state of thermodynamic equilibrium. Equilibrium states of a given system are
then characterized by the unique value of all its properties. The concept of equilibrium in
classical thermodynamics is an important and primitive one. It is really an abstraction,
as real systems are never strictly in equilibrium.
When a system has no unbalanced force within it and when the force it exerts on its
boundary is balanced by external force, the system is said to be in mechanical equilibrium.
When the temperature of a system is uniform throughout and equal to the temperature
of the surroundings, the system is said to be in thermal equilibrium.
When the chemical composition of system will remain unchanged, the system is said

3
to be in chemical equilibrium.
In order to have thermodynamic equilibrium, the conditions of mechanical equilibrium,
thermal equilibrium and chemical equilibrium must be satisfied.

Temperature and the Zeroth law of thermodynamics

The concept of temperature, originated in man’s perception of hot and cold. It is a
primitive concept resulting from the accepted scientific fact known as Zeroth law of Ther-
modynamics, which states that: When two systems are each in thermal equilibrium with
a third system, they are also in thermal equilibrium with each other.

First law thermodynamics

The first law of thermodynamics states that during any cycle that a system undergoes,
the cyclic integral of the heat is proportional to the cyclic integral of work.

First law of thermodynamics for a change in state of a system

Many times, we are concerned with a process rather than a cycle and we now consider the
first law for a system that undergoes a change of state. This can be done by introducing
a new property, the energy, which is given the symbol E.

δQ = dE + δW (1)

dE = dU + d(KE) + d(P E) (2)

Thermodynamic work:

Work is energy transferred without transfer of mass, across the boundary of a system.
Z
W = P δV (3)

Summary of work interactions

δW = P δV − τ δL − τ δA − µδ(V, m) − EδZ (4)

where:
P δV - compressible system
τ δL - stretched wire
τ δA - surface film
µδ(V, m) - system involving magnetic work only
EδZ - system with electric work only

4
Heat energy:

Heat is defined as the form of energy that is transferred across the boundary of a system at
a given temperature to another system(or surrounding) at a lower temperature by virtue
of the temperature difference between the two systems.
Sign Convention

Q -v e
W -v e

S y s te m
W +ve
Q +ve

Figure 3: Sign convention.

The concept of Entropy, S

Let us introduce entropy, S, formally as follows: u, the internal energy has the character
of a potential energy. For a reversible change of state of an adiabatically enclosed system.

δq = du + P δv (5)

becomes
0 = du + P δv (6)

δu
P =− (7)
δV
i.e., the pressure is equal to the derivative of the internal energy with respect to volume
or the force is equal to the derivative of u with respect to displacement.

f δL = P δv = −δu (8)

δu
f =− (9)
δL
Can a similar relation be found for the temperature, T ? Let us write u as a function
of two variables such that the partial derivatives are P and T , respectively. Let one of

5
these variables be s. Let us write tentatively

u = u(s, v)

such that  
∂u
−P = (10)
∂v s
 
∂u
T = (11)
∂s v

and hence    
∂u ∂u
du = dv + ds (12)
∂v s ∂s v

= −P dv + T ds (13)

From 1st law

du = −P dv + δq (14)

Hence
T δs = δq (15)

T δs is equal to the element of heat added in a reversible process

δq
δs = (16)
T

Second law of thermodynamics

There is nothing implicit in the first law of thermodynamics to say that some proportion
of the heat supplied must be rejected, and therefore that the cycle efficiency cannot be
unity. All that 1st law states is that net work cannot be produced during a cycle without
some supply of heat i.e that perpetual motion machine of the first kind is possible. The
second law is an expression of the fact that some heat must always be rejected during
the cycle and therefore that the cycle efficiency is always less than unity. There are two
classical statements of the second law, known as the Kelvin-plank statement and the
Clausius statement.

The Kelvin-Plank statement

It is impossible to construct a device that will operate in a cycle, extract heat from a
reservoir and do an equal amount of work on the surrounding.

The Clausius statement

It is impossible to construct a device that operates in a cycle and produce no effect other
than the transfer of heat from a cooler body to a hotter body.

6
2 Thermodynamic Relations
2.1 Review of partial derivatives
First two important relations are reviewed. Consider a variable z which is a continuous
function of x and y
z = f (x, y)
   
∂z ∂z
dz = dx + dy (17)
∂x y ∂y x
Equation (17) may be more conveniently expressed as

dz = M dx + N dy (18)

dz


where M = dx y
i.e., the partial derivative of z with respect to x (the variable y being
 
dz
held constant), while N = dy i.e., the partial derivative of z with respect to y (the
x
variable x being held constant).
The significance of partial derivatives is that they can be used to relate the properties
(P , v, T ) of a pure substance.

∂ 2Z
   
∂M
= (19)
∂y x ∂x∂y

∂ 2Z
   
∂N
= (20)
∂x y ∂y∂x
Since the order of differentiation is immaterial, when point of functions are involved, we
have  2   2 
∂ Z ∂ Z
= (21)
∂x∂y ∂y∂x
and hence show that    
∂M ∂N
= (22)
∂y x ∂x y

This is an important mathematical relation that will be used repeatedly. The second
important mathematical relation is the cyclic relation:
     
∂x ∂y ∂z
= −1 (23)
∂y z ∂z x ∂x y

It is left as an exercise for you to show that this is so.

2.2 Maxwell functions

The Maxwell relations are easily derived by considering four relations involving thermo-
dynamic properties.

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1. Change in internal energy, u (The first T ds equation).

du = T ds − P dv (24)
 
∂u
Comparing Eqn. (24) with Eqns. (17) and (18), we find that T = and
  ∂s v
∂u
P =−
∂v s
2. Change in enthalpy, h (The second T ds equation).

dh = T ds + vdP (25)
 
∂h
Again, comparing Eqn. (25) with Eqns. (17) and (18), we find that T =
  ∂s P
∂h
and v =
∂P s
3. Change in the Helmholtz function, a.

da = −sdT − P dv (26)

Where a is the specific Helmholtz function given by,

a = u − Ts
da = du − T ds − sdT
= T ds − P dv − T ds − sdT
= −sdT − P dv

 
∂a
Comparing Eqn. (26) with Eqns. (17) and (18), we find that s = − and
  ∂T v
∂a
P =−
∂v T
4. Change in the Gibbs function, g.

dg = −sdT + vdP (27)

Where g is the specific Gibbs function given by,

g = h − Ts
dg = dh − T ds − sdT
= T ds + vdP − T ds − sdT
= −sdT + vdP

8
  
∂g
Again, comparing Eqn. (27) with Eqns. (17) and (18), we find that s = −
  ∂T P
∂g
and v =
∂P T
Equations (24), (25), (26) and (27) are in the form of Eqn. (18), viz.,

dz = M dx + N dy (18)
   
∂M ∂N
in which = . It follows from Eqns. (24), (25), (26) and (27) that
∂y x ∂x y

   
∂T ∂P
=− (28)
∂v s ∂s v

   
∂T ∂v
= (29)
∂P s ∂s P
   
∂s ∂P
= (30)
∂v T ∂T v
   
∂s ∂v
− = (31)
∂P T ∂T p
Equations (28), (29), (30) and (31) are known as the Maxwell relations. They are im-
portant in the correlation of properties of simple compressible substances, because they
relate entropy to the directly measureable properties of pressure, specific volume and
temperature.

2.3 Quantities derivable from P − v − T data

Let us examine someof the information that can be deduced directly from P − v − T
∂v
measurements. is a property that can be deduced from the P − v − T data. It
∂T P
is simply the slope of a constant pressure line at a point in the v − T diagram. If we
divide the quantity by v at the point, we arrive at a new property called the coefficient
of expansion, β. By definition,  
1 ∂v
β= (32)
v ∂T P
 
∂v
is another property and represents the slope of a constant temperature line
∂P T
at a point in the v − P diagram. The isothermal compressibility is defined as
 
1 ∂v
κ=− (33)
v ∂P T

 
∂v
The quantity is negative for all known simple compressible substances, conse-
∂P T

9
quently, κ is always positive by definition.
Applying the cyclic relation to the P − v − T equation of state, we have that
     
∂P ∂v ∂T
= −1 (34)
∂v T ∂T P ∂P v

Combining Eqns. (32), (33) and (34), we obtain

 
β ∂P
= (35)
κ ∂T v

From the P − v − T equation of state, we have

   
∂v ∂v
dv = dT + dP (36)
∂T P ∂P T

or
dv = vβdT − vκdP (37)

2.4 Thermodynamic relations involving enthalpy, internal en-

ergy and entropy
 
∂h
cp = (38)
∂T P
 
∂u
cv = (39)
∂T v

Following from Eqn. (25), dh = T ds + vdP , therefore

   
∂h ∂s
cp = =T (40)
∂T P ∂T P

Following from Eqn. (24), du = T ds − P dv, therefore

   
∂u ∂s
cv = =T (41)
∂T v ∂T v

Representing the specific enthalpy as a continuous function of T and P , i.e., h =

f (T, P ), the total derivative of h is expressed as
   
∂h ∂h
dh = dT + dP (42)
∂T P ∂P T

From the relation dh = T ds + vdP , it follows that

   
∂h ∂s
=v+T (43)
∂P T ∂P T

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Substituting the Maxwell relation, Eqn. (31), we have
   
∂h ∂v
=v−T (44)
∂P T ∂T P

Substituting Eqns. (38) and (44) into Eqn. (42), we have

   
∂v
dh = cp dT + v − T dP (45)
∂T P

∂v


Along an isobar, we have dhP = cp dTP , while along an isotherm dhT = v − T ∂T P
dPT .
Therefore the change in specific enthalpy between two states 1 and 2 (Fig. 4) may be ob-
tained by integrating Eqn. (45) first along an isobar (e.g. from 1 to b, noting that Tb = T2 )
and then along an isotherm (e.g. from b to 2, noting that Pb = P1 ), i.e.,
Z 2 Z 2    
∂v
h2 − h1 = cp dT + v−T dP (46)
1 1 ∂T P

The first term on the RHS of Eqn. (46) gives the change in enthalpy along the isobar 1 –
b while the second term gives the change in enthalpy along the isotherm b to 2. The sum
of the two gives the net change in enthalpy between states 1 and 2.

b 2
T

1
x

Figure 4

Alternatively, the integration may be carried out first along the isotherm (e.g. from
1 to x, noting that Px = P2 ), and then along the isobar (e.g. from x to 2, noting that
Tx = T1 ).
Representing the specific internal energy as a continuous function of T and v, i.e.,

11
u = f (T, v), the total derivative of u is expressed as
   
∂u ∂u
du = dT + dv (47)
∂T v ∂v T

From the relation du = T ds − P dv, it follows that

   
∂u ∂s
=T −P (48)
∂v T ∂v T

Substituting the Maxwell relation, Eqn (30), we have

   
∂u ∂P
=T −P (49)
∂v T ∂T v

Substituting Eqns. (39) and (49) into Eqn. (47), we obtain

   
∂P
du = cv dT + T − P dv (50)
∂T v

Along an isochore, duv = cv dTv and along an isotherm, duT = T ∂P



∂T v
− P dvT .
Similarly, representing the specific entropy as a continuous function of T and P , i.e.,
s = f (T, P ), the total derivative of s is expressed as
   
∂s ∂s
ds = dT + dP (51)
∂T P ∂P T

Substituting Eqn. (40) and the Maxwell relation Eqn. (31), we have
 
dT ∂v
ds = cp − dP (52)
T ∂T P

The change in specific entropy between states 1 and 2 is given by

Z 2 Z 2  
dT ∂v
s2 − s1 = cp − dP (53)
1 T 1 ∂T P

2 Z
dT
Along an isobar, we have (s2 − s1 )p = cp while along an isotherm, (s2 − s1 )T =
R 2 ∂v
1 T
− 1 ∂T P
dP .
Alternatively, the specific entropy could be represented as a continuous function of T
and v, i.e., s = f (T, v), in which case the total derivative of s expressed as
   
∂s ∂s
ds = dT + dv (54)
∂T v ∂v T

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Substituting Eqn. (41) and the Maxwell relation (30), Eqn. (54) may be expressed as
 
dT ∂P
ds = cv + dv (55)
T ∂T v

The change in specific entropy between states 1 and 2 is then given alternatively by
Z 2 Z 2  
dT ∂P
s2 − s1 = cv + dv (56)
1 T 1 ∂T v

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