MEC 3401: LAWS OF THERMODYNAMICS

• These are basically statements of thermodynamic behavior.

• They are natural laws based on observable phenomena.

• They are designated as laws because they have never been shown to be contradicted.

There are FOUR basic laws, namely ZEROTH LAW, 1st LAW OF THERMODYNAMICS, 2nd LAW OF
THERMODYNAMICS, and 3rd LAW OF THERMODYNAMICS. The ZEROTH law was stated after the 3rd law became
established.

THE ZEROTH LAW OF THERMODYNAMICS

This law is concerned with THERMAL EQUILIBRIUM.

It states that “if two objects are separately in thermal equilibrium with a third object, then the two objects must be in
thermal equilibrium with each other”.

Thermal equilibrium implies no change of state. It also implies that all the objects are at the same temperature.

THE FIRST LAW OF THERMODYNAMICS

Recall the relation between Heat and Work.

Q=W (1)

Where: Q = Heat Transfer and W = Work Transfer

This is a statement of the first law of thermodynamics.

Consider the figures used to establish the relation between heat and work, i.e. the heating of a given quantity of water using two
different methods e.g. using a burner, paddle wheel or electric coil.

Process 1: This process uses a burner to heat the water (An electric coil could also be used instead of a burner).

Process 2: A disk is rotated at high speed and due to friction between the disk and the water molecules, the water gets heated.

The initial and end states in both cases are the same.

Careful measurements show that the amount of work between the given end states of the system theoretically turn out to be
the same.

Therefore, for various adiabatic processes between two given end states, the work is identical and does not depend on the
details of the process (as long as the process is adiabatic).

The first law is a generalization of this fact and many more experimental facts.

Definition of the 1st law of thermodynamics:

1. The work of a system for any adiabatic process connecting given end states depends on the end states only.

2. When a system undergoes a thermodynamic cycle, then the net heat supplied to the system from its surroundings
plus the net work input to the system from the surroundings must equal zero.

Since for a cycle, there is no net property change,

NET HEAT TRANSFER – NET WORK TRANSFER = 0 (2)

Symbolically,

 Q = W (3)

Where:

 = Summation around a cycle.

NOTE:

The first law implies that there must be heat transfer for there to be work transfer (for a cycle)

For example, an engine which provides work without heat transfer would violate the first law because it would create energy.
This contradicts the principle of energy conservation. An engine provides work from heat and work is converted back into heat in
the end. No violation of the first law has been shown.

NON FLOW ENERGY EQUATION

If a process is carried out on a substance in a closed system such that there is both heat and work transfer, the algebraic sum of
these energy transfers will not necessarily be ZERO. Thus,

Q  W (4)

Now, the principle of energy conservation states that

ENERGY IN = ENERGY OUT (5)

If the heat and work transfers are not equal, then some energy must have been added to, or lost from the system. Therefore, in
order to balance the right hand side with the left hand side of equation (4), a quantity ∆U has to be introduced. Thus,

Q = U + W (6)

Where:
Q = Heat Transfer
∆U = Change in Internal energy = (U2 – U1)
W = Work Transfer

Equation (6) is called the NON FLOW ENERGY EQUATION and is another statement of the first law of thermodynamics.

STEADY FLOW ENERGY EQUATION

This equation relates to an “open system”.

The following assumptions are made in this equation:

(i) The mass flow rate of fluid or substance throughout the system is constant
(ii) The total energy of the fluid mass in the system remains constant

The steady flow energy equation is written as follows:

c1 c
u1 + p1v1 + + gz1 + Q = u 2 + p2 v2 + 1 + gz 2 + W (7)
2 2
Note the relation Q = W
Where:
u = Specific internal energy
p1v1, p2v2 = Specific flow work
c = Velocity
z = Height above given datum level (specific potential energy)
Q = Heat Transfer
W = Work Transfer
g = Gravitational acceleration

Equation (7) is called the STEADY FLOW ENERGY EQUATION and is another statement of the first law of thermodynamics.
(Derive Equation (7) as an exercise! See JOEL page 67).

The law of conservation of energy – “Energy can neither be created or destryed, but can be transformed from one form to
another”

CONTINUITY OF MASS FLOW

For any fluid flowing through a steady flow open system, the mass flow rate through any section in the system must be constant.

AC
m = (8)
v
Also,
A1C1 = A2C2 = A3C3 = ..........= An Cn …for different cross-sections

Where:
m = Mass flow (kg/s)
v = Specific Volume (m3/kg)
A = Cross sectional area (m2)
C = Velocity (m/s)

(Derive Equation 8 as an exercise. See derivation in JOEL page 68)

Go through the corollaries of the 1st law of thermodynamics :

(Chapter 3 Joel, chapter 2 Rodgers and Meyhew)

LIMITATIONS OF THE 1ST LAW

1. The statement “when a closed system undergoes a thermodynamic cycle, the net heat transfer is equal to the net work
transfer” (Equation 2) does not specify the direction of the flow of heat and work i.e. whether the heat flows from a cold
object to a hot object or vice versa). Also no condition under which the transfers take place is given.

2. The law states that “the heat energy and mechanical work are mutually convertibale”
Although mechanical work can be fully converted into heat, only part of the heat energy can be converted back into work
– both are not mutually convertible. Therefore, the limitation is on the conversion from one form into another.
SECOND LAW OF THERMODYNAMICS
This is a directional law stating that heat transfer will occur naturally down a temperature gradient.

Heat transfer can be made to occur up a temperature gradient only with the aid of external energy e.g. refrigeration plants (devices
that transfer heat from low to high temperature), heat pumps etc.

From the first law of thermodynamics, for a cycle (and hence for heat engines, since heat engines work in cycles), in order to
continue in operation,

NET WORK TRANSFER = NET HEAT TRANSFER

W = Q (1)

However, from experience,

NET WORK TRANSFER < NET HEAT TRANSFER

W  Q (2)

Now, since the work transfer is less than the heat transfer,

Q − W  0 ….and has some positive value (3)

This means that some heat transfer must be rejected or lost, and therefore, there will always be some inefficiency.

Equations (1) and (3) also require that there should be heat transfer for there to be work transfer. Hence, there is no work transfer
unless there is heat transfer (i.e. a temperature difference).

The second law therefore suggests that unless there is a temperature difference, there is no heat transfer and therefore no
work transfer.

PRACTICAL IMPLICATION OF THE SECOND LAW

All fuels should be used as efficiently as possible in order to preserve fuel stocks, since once energy has been degraded by heat
transfer down a temperature gradient, further energy is only made available at the expense of further fuel.

Read the various statements of the 2nd law in:

Chapter 3, Joel; Chapter 6, Rodgers and Meyhew

THE THIRD LAW OF THERMODYNAMICS

This law is concerned with the level of availability of energy.

Every object possesses internal energy which results from random motion of the atoms and molecules that make up the
substance. This motion of atoms and molecules is associated with temperature and hence entropy. (Entropy is associated with
temperature and hence the availability of energy). This association with temperature gives rise to the concept of “Absolute
Zero”.

When the motion of atoms and molecules is reduced to Zero, the substance is said to become a “Perfect Crystal” and the
energies associated with the motions is reduced to Zero. This is called the “Ground State” of the substance.

The above considerations led to the development of the 3 rd law of thermodynamics, stated as:

“At Absolute Zero of Temperature, the Entropy of a Perfect Crystal of a substance is Zero”