4.

First Law of Thermodynamics

4.1 Definition
The first law of thermodynamics was developed from the hypothesis by scientists that energy can
neither be created nor destroyed, but can be changed from one form to another.
Definition: When a closed system undergoes a thermodynamic cycle, the network delivered to the
surroundings by the system is equal to the net heat taken from the surroundings into the system.
Mathematically, this law can be expressed as given by Eq. (4.1).

෍ܳ = ෍ܹ

Or
ܳ௡௘௧ = ܹ௡௘௧ (4.1)

4.2 Non-flow Energy Equation and Reversibility

4.2.1 Non-flow energy equation
For a general closed system and applying the principle of conservation of energy, the first law of
thermodynamics may be stated as:
Energy entering the system െ Energy leaving the system = Energy change within the
system
This can be mathematically expressed as shown in Eq. (4.2).
ଵ
ܳ െ ܹ = ο‫ = ܧ‬ο ቀܷ + ݉݃‫ ݖ‬+ ݉‫ ܥ‬ଶ ቁ (4.2)
ଶ

ଵ
Where: οܷ, ο݉݃‫ݖ‬, and ο ݉‫ ܥ‬ଶ are changes in internal energy, potential energy and kinetic energy,
ଶ
respectively. For a closed system change in internal energy is the most significant component. Changes
in kinetic and potential energy are usually assumed to be negligible and are therefore ignored.
Expression of the first law of thermodynamics for a process in a closed system can, therefore, be
reduced to Eq. (4.3):
ܳ െ ܹ = οܷ = ܷଶ െ ܷଵ (4.3)
For a unit mass (1 kg) of fluid within the system, Eq. (4.3) is expressed as:

‫ ݍ‬െ ‫ = ݓ‬ο‫ݑ = ݑ‬ଶ െ ‫ݑ‬ଵ (4.4)

‫ ݑ‬is a property of the system, with the SI unit of kJ/kg. Equation (4.4) is known as the non-flow energy
equation.
Equation (4.4) can be expressed in terms of differential changes of the system as follows:

ߜ‫ ݍ‬െ ߜ‫ݑ݀ = ݓ‬ (4.5)

Delta (ߜ) is used for q and w to indicate the interaction across a system while the normal differential
(d) is used for u to indicate a change of a property within the system. For a cycle, the internal, potential
and kinetic energies are all restored to their initial values by the interactions between heat and work.
Therefore, the right-hand side of Eq. (4.2) becomes zero as expressed in Eq. (4.6).

22
 ܳെܹ =0 (4.6)
Equation (4.6) is the expression of the first law of thermodynamics for a cycle.
Note:
1. From Eq. (4.1), if a net amount of heat is not supplied by the surroundings into the system during a
thermodynamic cycle, no net amount of work will be delivered by the system. This implies that a
perpetual machine of the first kind is impossible.
2. From Eq. (4.4), for an isolated system from the surroundings where both q and w are zero, the
change in internal energy would be zero.

Exercise 4.1:
1. Figure 4.1 shows a steam plant that operates in a closed cycle. The power plant turbine develops
1000 kW. The heat supplied to the steam in the boiler is 2800 kJ/kg, the heat rejected by the system
to the cooling water in the condenser is 2100 kJ/kg and the feed pump work required to pump the
condensate back into the boiler is 5 kW. Calculate the mass flow rate of steam round the cycle in
kg/s. [Solution: 1.421 kg/s]

2. During compression stroke of an internal-combustion engine, the heat rejected to the cooling water
is 45 kJ/kg and the work input is 90 kJ/kg. Calculate the change in specific internal energy of the
working fluid stating whether it is a gain or a loss.
[Solution: ο࢛ = 45 kJ/kg, gain]

4.2.2 Process reversibility

A reversible process is defined as the process where both the system and its surroundings can always
be restored to their original state by performing the process in reverse. A heat engine is not 100%
thermally efficient since some of its heat input is used to overcome frictional forces. Such factors lead
to process irreversibility.

Criteria for reversibility:

x The process must be frictionless. The process fluid must have no internal friction and no
mechanical friction should be experienced as well.
x During the process, pressure difference between the fluid and its surroundings must be
infinitely small. Therefore, the process must take place infinitely slowly due to the infinitely
small force applied to accelerate the boundaries of the system.
x During the process, temperature difference between the fluid and its surroundings must be
infinitely small. Therefore, the heat supplied or rejected to or from the fluid must be transferred
infinitely slowly.

Simulation of a process reversibility can be demonstrated using Fig. 4.2 (a) and (b). In Fig. 4.2 (a), the
piston of a system is pulled very slowly to the right through a very small distance to avoid causing
large-scale motion of the gas. This way, the process can be reversed, i.e., the piston can be pushed
back to its original position and everything returns to the same starting state. In such a case, there is an
ideal work transfer known as the reversible work interaction, in which all properties are restored to
their initial values at the end of the push-pull motion. In this process, friction between the cylinder and
the piston is assumed to be absent (friction causes irreversibility of a process).

23
 Fig. 4.2: Demonstration of (a) reversible and (b) irreversible work transfer
In reality, all processes are irreversible, but the concept of reversibility is central to thermodynamic
analysis. Reversibility implies that everything is infinitesimally close to equilibrium at all times
throughout the process.
Heat interaction reversibility results when heat interacts at virtually constant temperature, with only an
infinitesimal difference to provide heat transfer in the required direction. In Fig. 4.3 (a), if the object is
heated for a very short time and cooled, heat will first flow in one direction and then reverses to the
other direction. Therefore, to achieve reversible heat transfer, temperature difference must be
decreased to an almost zero limit, (infinitesimal difference). Heat transfer across a finite temperature
difference as illustrated in Fig. 4.3 (b) is irreversible.

Fig. 4.3: Demonstration of (a) reversible and (b) irreversible heat transfer
In summary, the concept of reversibility means that the states of the system and its surroundings are
always infinitesimally close to equilibrium.

4.3 Application of Non-flow Energy Equation to Non-flow Processes

4.3.1 Constant volume process
For a constant volume process, the working substance is contained in a rigid vessel. Therefore, other
than the paddle-wheel work (process that involves friction and in which volume of the system does
not change, but work is still done on the system. Friction makes this process irreversible, hence a non-
equilibrium process), no work can be done by or on the system. In general, non-flow energy equation
for a constant volume process may be expressed as follows:
‫ ݍ‬െ ‫ݑ = ݓ‬ଶ െ ‫ݑ‬ଵ (4.7)
During a constant volume process the boundary of the system does not move and hence the work
transfer is zero. Therefore, Eq. (4.7) becomes:
‫ݑ = ݍ‬ଶ െ ‫ݑ‬ଵ (4.8)

Equation (4.8) indicates that the quantity of heat in the system is equal to the change of internal
energy. If the heat is transferred by virtue of infinitesimal temperature difference, then the process is
reversible. The energy equation may then be expressed in differential form as in Eq. (4.9).
݀‫ݑ݀ = ݍ‬ (4.9)
24
4.3.2 Constant pressure process
If heat is applied to a system undergoing a constant pressure process the fluid will expand and the
system will do work to overcome the constant force that maintains the constant pressure. The general
expression in Eq. (4.7) applies. For a reversible process, the energy equation can be written as:
݀‫ ݍ‬െ ‫ݑ݀ = ݒ݀݌‬ (4.10)
Since P is constant, Eq. (4.10) can be integrated to yield Eq. (4.11).

‫ ݍ‬െ ‫ݒ(݌‬ଶ െ ‫ݒ‬ଵ ) = ‫ݑ‬ଶ െ ‫ݑ‬ଵ (4.11)

Thus, if the initial and final states are known i.e., if ‫݌‬ଵ ‫ݒ‬ଵ and ‫ݒ‬ଶ are given, then a definite quantity of
heat q which can be calculated from Eq. (4.11) is transferred during the process. Since ‫ ݌‬is constant,
‫ ݒ݀݌‬is identical to ݀(‫)ݒ݌‬. Thus, Eq. (4.10) can be expressed as:

݀‫ ݍ‬െ ݀(‫ݑ݀ = )ݒ݌‬ (4.12)

Rearranging Eq. (4.12) yields:
݀‫ ݑ(݀ = ݍ‬+ ‫)ݒ݌‬ (4.13)

The term ‫ ݑ‬+ ‫ ݒ݌‬in Eq. (4.12) is defined as the enthalpy, h, which is a system property that combines
properties ‫ݑ‬, ‫ ݌‬and ‫ݒ‬. It is expressed as given in Eq. (4.14). The SI unit for enthalpy is kJ/kg.

‫ ݑ‬+ ‫݄ = ݒ݌‬ (4.14)

The energy equation for a reversible constant pressure process therefore becomes,

݀‫݄݀ = ݍ‬ (4.15)
Or in integrated form,
݀‫݄ = ݍ‬ଶ െ ݄ଵ (4.16)

4.3.3 Polytropic process

The states during expansion or compression in many real processes are approximately described by the
following relation.
ܲ‫ ݒ‬௡ = ܿ (4.17)
Where n is a constant called the index of expansion or compression, and P and v are the average values
of pressure and specific volume for the system. Compression and expansions processes of the form
given in Eq. (4.17) are called Polytropic processes. When ݊ = 0, the relation reduces to ܲ = ܿ‫ݐ݊ܽݐݏ݊݋‬
and when ݊ = λ, it reduces to ‫ ݐ݊ܽݐݏ݊݋ܿ = ݒ‬as shown in Fig. 4.4.

25
 Fig. 4.4: Polytropic process demonstration
For a reversible polytropic process, single values of P and v can truly define the state of a system and
݀‫ݒ݀ܲ = ݓ‬. The work done per unit mass during a change from state 1 to 2 may be determined by
integration as follows: For the initial, the final and any intermediate state,
ܲଵ ‫ݒ‬ଵ௡ = ܲଶ ‫ݒ‬ଶ௡ = ܲ‫ ݒ‬௡ = ܿ (4.18)
Therefore,
ଶ ଶ ௗ௩ ௩ భష೙ ି௩ భష೙ ௉ ௩ ೙ .௩ భష೙ ି௉ ௩ ೙ .௩ భష೙ ௉ ௩ ି௉ ௩
‫׬ = ݓ‬ଵ ܲ݀‫ ݒܲ = ݒ‬௡ ‫׬‬ଵ ೙ = ܲ‫ ݒ‬௡ ቀ మ భ
ቁ= మ మ మ భ భ భ
= మ మ భ భ (4.19)
௩ ଵି௡ ଵି௡ ଵି௡
An integrated form of the energy equation for a reversible polytropic process can therefore be
expressed as shown in Eq. (4.20).
௉మ ௩మ ି௉భ ௩భ
‫ݍ‬െ = ‫ݑ‬ଶ െ ‫ݑ‬ଵ (4.20)
ଵି௡

4.3.4 Adiabatic process

In an adiabatic process, there is no heat exchange across the boundary of a system, i.e., the system is
thermally insulated from its surroundings. For an adiabatic non-flow process, energy equation reduces
to the following expression:
െ‫ݑ = ݓ‬ଶ െ ‫ݑ‬ଵ (4.21)

4.3.5 Isothermal process

This refers to a constant temperature process, i.e., T = constant. For any reversible isothermal process,
energy equation is expressed as:

݀‫ ݍ‬െ ‫ݑ݀ = ݒ݀݌‬ (4.22)

Or,
ଶ
‫ ݍ‬െ ‫׬‬ଵ ܲ݀‫ݑ = ݒ‬ଶ െ ‫ݑ‬ଵ (4.23)

26
4.4 First law of thermodynamics application in open systems
As earlier defined, an open system refers to a system in which the working fluid may flow in or out of
the system across the boundary. Across the boundary, there can be transfer of energy in the form of
heat and work as shown in Fig. 4.5.

Fig. 4.5: Open system – control volume

In addition, there is fluid input at 1 which leaves at 2. The fluid flow can be measured in terms of mass
flow rate, ݉ሶ; mass of the fluid entering or leaving per unit time, and given in units of kg/s. If the mass
flow rate through the system remains constant and does not change with time the flow is referred to as
steady. Mass is always conserved in steady flow open systems, i.e.

݉ଵ = ݉ଶ = ݉ (4.24)
Or,
஼భ ஺భ ஼మ ஺మ ஼஺
= = (4.25)
௩భ ௩మ ௩

Where: C is the working fluid velocity, A is the flow area, and v is the specific volume of the working
fluid. Equation (4.25) is known as the continuity equation.
To derive the energy equation that is applicable to open systems, it is important to consider what
happens when the working fluid is introduced into the control volume and when it leaves. Consider the
open system in Fig. 4.5, the fluid entering the system at section 1 is pushed in by the fluid behind it.
Therefore, work is being done on the fluid inside the system. Similarly, the fluid leaving the system at
section 2 has to push the fluid in front of it, to represents the work out of the system. The work done in
moving the fluid is called flow work.
Consider a fluid flowing through a pipe as shown in Fig. 4.6. The shaded part, length L, represents the
length of a fluid column having a unit mass. The pressure, p, on the fluid at section a causes the fluid to
flow to the right towards section b.

Fig. 4.6: Open system – work demonstration

27
Work done in moving the fluid through length L is given by force multiplied by distance, and
expressed as:
‫)ܮܣ(݌ = ܮ)ܣ݌( = ݓ‬ (4.26)

Since the volume defined by (‫ )ܮܣ‬contains 1 kg of fluid, it represents specific volume v. Therefore,
flow work can be expressed as ‫ݒ݌‬.

4.4.1 Steady flow energy equation

From the defined flow work, it is possible to evaluate energy of the fluid that enters and leaves an
open system. Consider the fluid entering an open system at section 1 as shown in Fig. 4.7.

Fig. 4.7: Open system for evaluating fluid energy into and out of the system

In Fig. 4.7, a unit mass of the fluid enters the system with a particular value of internal energy, ‫ݑ‬ଵ ,
ଵ
kinetic energy, ܿଵଶ , potential energy, ‫ݖ‬ଵ ݃, and having flow work, ‫݌‬ଵ ‫ݒ‬ଵ , done on it. Combining these
ଶ
energy terms yields total energy for the fluid entering at section 1 as:
ଵ
‫ ݐܽ ݕ݃ݎ݁݊݁ ݈ܽݐ݋ݐ‬1 = ‫ݑ‬ଵ + ‫݌‬ଵ ‫ݒ‬ଵ + ܿଵଶ + ‫ݖ‬ଵ ݃ (4.27)
ଶ

Similarly, the total specific energy of fluid leaving at section 2 is given by:
ଵ
‫ ݐܽ ݕ݃ݎ݁݊݁ ݈ܽݐ݋ݐ‬2 = ‫ݑ‬ଶ + ‫݌‬ଶ ‫ݒ‬ଶ + ܿଶଶ + ‫ݖ‬ଶ ݃ (4.28)
ଶ

For a steady flow process, energy entering the system must be equal to the energy leaving the system
as long as there are steady flows of heat and work. This can be expressed by combining Eq. (4.27) and
(4.28) as follows:
ଵ ଵ
‫ݑ‬ଵ + ‫݌‬ଵ ‫ݒ‬ଵ + ܿଵଶ + ‫ݖ‬ଵ ݃ + ‫ݑ = ݍ‬ଶ + ‫݌‬ଶ ‫ݒ‬ଶ + ܿଶଶ + ‫ݖ‬ଶ ݃ + ‫ݓ‬ (4.29)
ଶ ଶ

Rearranging Eq. (4.29) yields,

ଵ
‫ ݍ‬െ ‫݌( = ݓ‬ଶ ‫ݒ‬ଶ + ‫ݑ‬ଶ ) െ (‫݌‬ଵ ‫ݒ‬ଵ + ‫ݑ‬ଵ ) + (‫ݖ‬ଶ െ ‫ݖ‬ଵ )݃ + (ܿଶଶ െ ܿଵଶ ) (4.30)
ଶ

Equation (4.30) is known as the steady flow energy equation (S.F.E.E). As explained earlier, the sum
of internal energy and flow work, ‫ ݑ‬+ ‫ݒ݌‬, represents enthalpy, h, of the system and expressed as ݄ =
‫ ݑ‬+ ‫ݒ݌‬. Also, changes in potential and kinetic energies are represented by (‫ݖ‬ଶ െ ‫ݖ‬ଵ )݃ = οܲ. ‫ܧ‬. and
ଵ
(ܿଶଶ െ ܿଵଶ ) = ο‫ܭ‬. ‫ܧ‬., respectively. Using these terms in Eq. (4.30) yields:
ଶ

‫ ݍ‬െ ‫ = ݓ‬ο݄ + οܲ. ‫ܧ‬. +ο‫ܭ‬. ‫ܧ‬. (4.31)

28
Equation (4.31) is valid based on the following assumptions:
1. Mass flow with respect to time is constant at inlet, and is equal to the mass flow rate at outlet.
2. Properties at any point within the open system do not vary with time.
3. Heat and work cross the boundary at uniform rates.
For consistency, similar units must be used for all the terms in the steady flow energy equation. In Eq.
(4.31), the SI unit for ‫ݍ‬, ‫ݓ‬, and ο݄ is kJ/kg. Therefore, the units for the οܲ. ‫ܧ‬. and ο‫ܭ‬. ‫ܧ‬. terms must
௠మ
be converted to kJ/kg. For instance, the SI unit for ο‫ܭ‬. ‫ܧ‬. is మ . This can be converted to kJ/kg by
௦
multiplying its numerator and denominator by mass (kg) as follows:
݉ଶ ݇݃ ݇݃݉. ݉ ݇݃. ݉ ݉ ܰ݉
ଶ
× = ଶ =൬ ଶ ൰ =
‫ݏ‬ ݇݃ ‫݃݇ ݏ‬ ‫ݏ‬ ݇݃ ݇݃

Exercise 4.2:
An insulated steady flow device operates with steam entering at a pressure of 600 kPa, a temperature of
25௢ C, and a velocity of 200 m/s. If the steam leaves the device as a saturated vapour at a pressure of
100 kPa and with a velocity of 50 m/s, determine the specific work done by the device.

4.4.2 Application of steady flow energy equation in open systems

1. Boiler:
Steady flow energy equation can be applied to the heating processes in a steam generating boiler.
Figure 4.8 shows a simplified water-tube boiler system while Fig. 4.9 illustrates a simplified boiler
system including the system boundary.

Fig. 4.8: A simplified water-tube boiler system

Fig. 4.9: A simplified boiler system illustration

29
Consider the general expression for the SFEE in Eq. (3.31).
‫ ݍ‬െ ‫ = ݓ‬ο݄ + οܲ. ‫ܧ‬. +ο‫ܭ‬. ‫ܧ‬.
For a boiler, this equation can be simplified by making the following assumptions:

a. There is no work done i.e., ‫ = ݓ‬0

b. Velocity change across the device is very small, therefore, ܿଵଶ = ܿଶଶ
c. Height difference between the inlet and outlet, measured from a reference point, is very small.
Thus, change in potential energy is negligible.
With these assumptions, the SFEE for the boiler reduces to the following:
‫ = ݍ‬ο݄ = ݄ଶ െ ݄ଵ (4.32)

2. Condenser:
A condenser is a device that is used for condensing vapour back to liquid state. Figure 4.10 shows a
simple shell-and-tube condenser while Fig. 4.11 illustrates a simplified condenser system with
boundary clearly indicated.

Fig. 4.10: Simple shell-and-tube condenser system

Fig. 4.11: A simplified condenser system illustration

Similar to the boiler case, both kinetic and potential energy terms are negligible compared to the other
terms in the S.F.E.E. Therefore, the steady flow equation for a condenser also reduces to:
‫ = ݍ‬ο݄ = ݄ଶ െ ݄ଵ (4.33)

30
However, in this case ݄ଵ is greater than ݄ଶ and, therefore, q is negative.

3. Turbines, Compressors, Pumps, and Fans:

In power plants like steam, gas, or hydroelectric, a turbine is used for driving electric generator. A
turbine refers to a device that is used for extracting work from a fluid flow expanding from a high-
pressure region to low-pressure region as simplified in Fig. 4.12.

Fig. 4.12: Simplified turbine system

Working principle of a turbine: As the working fluid passes through the turbine, work is done against
the turbine blades attached to a shaft. Consequently, the turbine shaft rotates thereby producing useful
work. The first approximation for applying S.F.E.E. to a turbine assumes that flow velocities at inlet
and outlet are equal. Therefore, the kinetic energy term is zero. Potential energy term is also negligible
and can be dropped from the S.F.E.E. Since the average flow velocity through the turbine is very high,
the process can be assumed to be adiabatic, i.e., ‫ = ݍ‬0. The S.F.E.E for the turbine therefore becomes:

െ‫݄ = ݓ‬ଶ െ ݄ଵ (4.34)

If the mass flow of the fluid is ݉ሶ kg/s, then work done per second is expressed as follows:

ܹሶ = ݉ሶ(݄ଵ െ ݄ଶ ) (4.35)
Compressors, pumps and fans are devices that are used to increase the pressure of a fluid. These
devices therefore consume work in the process. Similar to turbines, heat transfer from these devices is
usually negligible, i.e., ‫ = ݍ‬0. The potential energy changes associated with these devices are also
negligible.

4. Throttle valve:
A throttle valve is a device used for reducing the pressure of a fluid flowing from state 1 to 2 as
demonstrated in Fig. 4.13. This is particularly applied in a refrigerator where a simple and low-cost
throttle valve is used to effect flow pressure drop from high -pressure side to low-pressure side of the
cycle.

Fig. 4.13: Throttle valve

31
The drop in pressure can be achieved by simply putting a restriction, either in the form of an orifice or
a capillary tube, in the flow path as shown in Fig. 4.14. Figure 4.15 shows a simple illustration of a
throttling process.

Fig. 4.14: Flow restriction devices

Fig. 4.15: Throttling process illustration

To analyze a throttle valve, the steady flow energy equation, ‫ ݍ‬െ ‫ = ݓ‬ο݄ + οܲ. ‫ܧ‬. +ο‫ܭ‬. ‫ܧ‬. is used.
The S.F.E.E. can be simplified by making the following assumptions:

i. There is no work done, hence ‫ = ݓ‬0

ii. The valve has negligible heat loss, or gain, so flow through the valve is adiabatic i.e., ‫ = ݍ‬0
iii. The mass flow rate through the valve is constant, therefore there is no change in velocity, i.e.,
ܿଵ = ܿଶ .

5. Nozzles and Diffusers:

These are commonly utilized in jet engines, rockets, spacecrafts etc. A nozzle is used to increase the
velocity of a fluid at the expense of pressure, while a diffuser is used for increasing the pressure of a
fluid by slowing down its velocity. Figure 4.16 shows simple forms of open system (nozzle and
diffuser). Nozzles and diffusers perform opposite tasks. The rate of heat transfer between the fluid
flowing through a nozzle or diffuser and the surroundings is usually very small. Similarly, nozzles and
diffusers typically involve no work. Therefore, for both cases, ‫ = ݍ‬0 and ‫ = ݓ‬0.

Fig. 4.16: Simple forms of open system

32
6. Heat Exchangers:
These are devices where two streams of moving fluids exchange heat normally without mixing. An
example of a heat exchanger is the shell and tube as shown in Fig. 4.13. Heat exchangers typically
involve no work interactions (i.e., ‫ = ݓ‬0) and negligible kinetic and potential energy changes. Note
also that if the entire heat exchanger is selected as the control volume (system), the heat exchange with
the surroundings can be neglected (i.e., ‫ = ݍ‬0).

Fig. 4.13: Shell and tube heat exchanger

Tutorial 4.1:
1. In a gas turbine unit, gases flow through the turbine at 17 kg/s and the power developed by the
turbine is 14000 kW. The enthalpies of the gases at the inlet and outlet are 1200 kJ/kg and 360
kJ/kg, respectively, and velocities of the gases at inlet and outlet are 60 m/s and 150 m/s,
respectively. Calculate the rate at which heat is rejected from the turbine. Find also the area of the
inlet pipe given that the specific volume of the gases at inlet is 0.5 m3/kg.
[ࡿ࢕࢒࢛࢚࢏࢕࢔: ࡽሶ = െ૚૚ૢ. ૜ ࢑ࢃ; ࡭૚ = ૙. ૚૝૛ ࢓૛ ]

Assignment 1:
Air flows steadily at the rate of 0.4 kg/s through an air compressor, entering at 6 m/s with a pressure of
1 bar and specific volume of 0.85 m3/kg, and leaving at 4.5 m/s with a pressure of 6.9 bar and specific
volume of 0.16 m3/kg. The specific internal energy of the air leaving is 88 kJ/kg greater than that of the
air entering. Cooling water in a jacket surrounding the cylinder absorbs heat from the air at the rate of
59 kJ/s. Calculate:
i. The power required to drive the compressor.
ii. The inlet and outlet pipe cross-sectional areas.

33