First law of thermodynamics for a control

mass undergoing a cycle

Dr. Mst. Nasima Bagum

Professor, Dept. of I.P.E, SUST
FIRST LAW OF THERMODYNAMICS

 The first law of thermodynamics is the thermodynamic expression of

the conservation of energy.

 Simply stated that ―energy can not be created or destroyed‖ or that

―the energy of the universe is constant‖.

 This law can be stated for a system (control mass) undergoing a

cycle or for a change of state of a system.
 Stated for a system undergoing a cycle, the cyclic integral of the
work is proportional to the cyclic integral of the heat.
 Mathematically stated, for a control mass undergoing a cyclic
process such as in Joule’s experiment and for consistent set of units
∫dQfrom system= ∫dWon system
or ∫dQfrom system- ∫dWon system = 0

 The important thing to remember is that the first law states that the
energy is conserved always.
Sign convention
The work done by a system on the surroundings is treated as a
positive quantity.

Similarly, energy transfer as heat to the system from the

surroundings is assigned a positive sign. With the sign
convention one can write,

∫dQ = ∫dW
 Consequences of the first law:
Suppose a system is taken from state 1 to state 2 by the path 1-a-2 and
is restored to the initial state by the path 2-b-1, then the system has
undergone a cyclic process 1-a-2-b-1. If the system is restored to the
initial state by path 2-c-1, then the system has undergone the cyclic
change 1-a-2-c-1.
Let us apply the first law of thermodynamics to the cyclic processes 1-
a-2-b-1 and 1-a-2-c-1 to obtain
∫1-a-2dQ+ ∫2-b-1dQ - ∫1-a-2dW - ∫2-b-1dW =0

∫1-a-2dQ+ ∫2-c-1dQ - ∫1-a-2dW - ∫2-c-1dW=0

Subtracting, we get

∫2b1dQ- ∫2c1dQ –( ∫2b1dW - ∫2c1dW) =0

We know that the work is a path function and hence the term in
the bracket is non-zero. Hence we find

∫2b1dQ = ∫2c1dQ

That is heat is also a path function.

Path function
A Path function is a function whose value depends on the
path followed by the thermodynamic process irrespective of the
initial and final states of the process. An example of path
function is work done in a thermodynamic process. Work done
in a thermodynamic process is dependent on the path followed
by the process
Energy is a property of the system ?:
By rearranging we can have

∫2b1 (dQ - dW) = ∫2c1 (dQ - dW)

It shows that the integral is the same for the paths 2-b-1 and 2-c-1,
connecting the states 2 and 1. That is, the quantity ∫ (dQ - dW) does not
depend on the path followed by a system, but depends only on the
initial and the final states of the system. That is ∫ (dQ - dW) is an exact
differential of a property. This property is called energy (E). It is given
by
dE = dQ-dW
E = KE + PE +U
where U is the internal energy. Therefore,
dE = d(KE) + d(PE) + dU = dQ-dW

Quit often in many situations the KE or PE changes are negligible.

dU = dQ – dW

An isolated system does not exchange energy with the surroundings in

the form of work as well as heat. Hence dQ = 0 and dW = 0. Then the
first law of thermodynamics reduces to dE = 0 or E2 = E1 that is

energy of an isolated system remains constant.

Perpetual Motion Machine of the first kind:

An imaginary device which delivers work continuously

without absorbing energy from the surroundings is called
a Perpetual Motion machine of the first kind.

Since the device has to deliver work continuously, it has to operate on

a cycle. If such a device does not absorb energy from its surroundings
∫dQ =0. From the first law, it can be observed that ∫dW =0, if ∫ dQ = 0.
Therefore such a device is impossible from first law of
thermodynamics.
First law analysis of non-flow processes:
The first law of thermodynamics can be applied to a system to evaluate
the changes in its energy when it undergoes a change of state while
interacting with its surroundings. The processes that are usually
encountered in thermodynamic analysis of systems can be identified as
any one or a combination of the following elementary processes:
Constant volume (isochoric) process
Constant pressure (isobaric) process
Constant temperature (isothermal) process.
Adiabatic process.
Constant volume process:
Suppose a gas enclosed in a rigid vessel is interacting with the
surroundings and absorbs energy Q as heat. Since the vessel is
rigid, the work done W due to expansion or compression is zero.

Applying the first law, we get

dU = dQ or Q = U2 –U1
That is, heat interaction is equal to the change in internal
energy of the gas. If the system contains a mass m equal of an
ideal gas, then
Q = ΔU = mCv (T2 –T1)

The path followed by the gas is shown on a P-V diagram. Now

consider the fluid contained in a rigid vessel as shown. The
vessel is rigid and insulated. Shaft work is done on the system
by a paddle wheel as shown in Fig. a. In Fig. b electric work is
done on the system. Since the vessel is rigid, the PdV work is
zero. Moreover, the vessel is insulated and hence dQ = 0.
Application of the first law of thermodynamics gives
dU = dQ – dW = dQ – (dWpdv + dWs)
or dU = -dWs or – Ws = ΔU = U2 –U1
Where dWpdv is the compression /expansion work and dWs is the
shaft work. That is increase in internal energy of a system at a
constant volume, which is enclosed by an adiabatic wall, is
equal to the shaft work done on the system.
Constant pressure process: Several industrial processes are carried out at
constant pressure. A few examples of constant pressure processes are: (a)
reversible heating/cooling of a gas (b) phase change (c) paddle wheel work
(d) electrical work. For a constant pressure process, the work done W is
given by
W = ∫PdV = P (V2-V1)
Application of the first law of thermodynamics gives
dU = dQ – dW = dQ – PdV = dQ – d(PV)
or dQ = dU + d(PV) = d(U + PV) = dH
 Energy Balance for Closed Systems

 The phrase net amount used in the word statement of the energy balance must
be carefully interpreted,
 The two terms on the right side account for the net results of all the energy
transfers by heat and work, respectively, taking place during the time interval
under consideration
The energy balance can be expressed in symbols as
OTHER FORMS OF THE ENERGY BALANCE

where dE is the differential of energy, a property. Since Q and W are not properties,
their differentials are written as Q and W, respectively.

The instantaneous time rate form of the energy balance is

Alternative forms of the energy balance is convenient starting

points when applying the principle of conservation of energy to
closed systems
When applying the energy balance in any of its forms,
• be careful about signs and units and to distinguish carefully
between rates and amounts.
• location of the system boundary can be relevant in determining
whether a particular energy transfer is regarded as heat or work.
 Three alternative systems are shown that include a quantity of a gas (or liquid)
in a rigid, well-insulated container.
1. Fig a. the gas itself is the system. As current flows through the copper plate, there is an energy
transfer from the copper plate to the gas. Since this energy transfer occurs as a result of the
temperature difference between the plate and the gas, it is classified as a heat transfer
2. Fig b. the boundary is drawn to include the copper plate. It follows from the thermodynamic
definition of work that the energy transfer that occurs as current crosses the boundary of this
system must be regarded as work
3. Fig c. the the boundary is located so that no energy is transferred across it by heat or work
 Energy Analysis of Cycles

Thermodynamic cycle: When a system at a given initial state goes

through a sequence of processes and finally returns to that state, the
system has executed a thermodynamic cycle
Cycle Energy Balance
∆Ecycle = Qcycle + Wcycle
Where, Qcycle and Wcycle represent net amounts of energy transfer by heat and work,
respectively, for the cycle.

Since the system is returned to its initial state after the cycle, there is no net
change in its energy.
Therefore, Qcycle=Wcycle

 This is an expression of the conservation of energy principle that must be satisfied by

every thermodynamic cycle, regardless of the sequence of processes followed by the
system undergoing the cycle or the nature of the substances making up the system.
 Two general classes of cycles

Power Cycles: Systems undergoing

cycles of the type shown in Fig. deliver
a net work transfer of energy to their
surroundings during each cycle. Any
such cycle is called a power cycle.

 the net work output equals the net

heat transfer to the cycle, or
Wcycle = Qin - Qout (power cycle)

Where Qin represents the heat transfer of energy

into the system from the hot body, and
Qoutrepresents heat transfer out of the system to
the cold body.
(a) Power cycles. (b) Refrigeration and heat pump
cycles.
 For a power cycle Qin must be
greater than Qout.

 Thermal efficiency:
 The performance of a system
undergoing a power cycle

 Thermal efficiency of every power

cycle must be less than unity: 1.
 Refrigeration and Heat Pump Cycles
Objectives.
 The objective of a refrigeration cycle is to cool a refrigerated
 space or to maintain the temperature within a dwelling or
other building below that of the surroundings.

 The objective of a heat pump is to maintain the temperature

within a dwelling or other building above that of the
surroundings or to provide heating for certain industrial
processes that occur at elevated temperatures.

(b) Refrigeration and heat pump cycles.

Refrigeration and Heat Pump Cycles

Wcycle = Qout – Qin (refrigeration and heat

pump cycles)
 Coefficients of performance:
The ratio of the amount of energy
received by the system undergoing the
cycle from the cold body, Qin, to the
net work into the system to
accomplish this effect,Wcycle.

 the coefficient of performance of

refrigerator

(a) Power cycles. (b) Refrigeration and heat pump

cycles.

For a household refrigerator, Qout is discharged to the space in which the refrigerator is
located. Wcycle is usually provided in the form of electricity to run the motor that drives the
refrigerator.
• The coefficient of performance of heat pump:
the ratio of the amount of energy discharged from the system
undergoing the cycle to the hot body, Qout, to the net work into the
system to accomplish this effect, Wcycle

• From this equation it can be seen that the value of 𝛾is never less
than unity.
• The coefficients of performance𝛽and𝛾 are defined as ratios of the
desired heat transfer effect to the cost in terms of work to
accomplish that effect. Based on the definitions, it is desirable
thermodynamically that these coefficients have values that are as
large as possible.
Description:
• Consider as a control mass the gas in the container as shown:

• Let this system go through a cycle that is made up of two processes.

• In the first process work is done on the system by the paddle that
turns as the weight is lowered.
• Let the system then return to its initial state by transferring heat
from the system until the cycle has been completed.
• Measurements of work and heat were made during a cycle for a wide
variety of systems and for various amounts of work and heat. When
the amounts of work and heat were compared, it was found that they
were always proportional. Such observations led to the formulation
of the first law of thermodynamics, which in equation form is written
J∮δQ = ∮δW
The first law of thermodynamics
Defination: The first law of thermodynamics states that during
any cycle a system (control mass) undergoes, the cyclic
integral of the heat is proportional to the cyclic integral of
the work.

• ∮δQ = ∮δW basic statement of the first law of

thermodynamics

Where
∮δQ = the cyclic integral of the heat transfer, represents
the net heat transfer during the cycle
∮δW=the cyclic integral of the work, represents the net
work during the cycle
J=proportionality factor that depends on the units used
for work and heat
 units work heat

Originally, mechanical units of heat was measured in thermal units, such as

force times distance, the British thermal unit (Btu) or the calorie
such as foot pounds
force or joules
SI joule joule

English the foot pound force British thermal unit (Btu)

The International British thermal unit (Btu) is defined in terms of the

basic SI metric units:

1 Btu = 778.17 ft lbf

Because these units are equivalent, it is not necessary to include the

factor J explicitly in Eq1, but simply to recognize that for any system of
units, each equation must have consistent units throughout. Therefore,
Eq1 may be written as:
 INTERNAL ENERGY—A THERMODYNAMIC PROPERTY
• In the absence of motion, gravity, surface effects, electricity, or other
effects, the state of a pure substance is specified by two independent
properties
• the internal energy may be one of the independent properties of a pure
substance.
• if we specify the pressure and internal energy (with reference to an
arbitrary base) of superheated steam, the temperature is also specified
• In the liquid–vapor saturation region,
U=Uliq +Uvap
or
mu = mliquf+mvapug
Dividing by m and introducing the quality x gives
u=(1-x)uf+xug
U=uf+xufg
As an example, the specific internal energy of saturated steam having a
pressure of 0.6 MPa and a quality of 95% can be calculated as?
THE THERMODYNAMIC PROPERTY ENTHALPY
let us consider a control mass undergoing a quasi-equilibrium constant-
pressure process Fig. 5.7.
 Assume that there are no changes in kinetic or potential energy and that
the only work done during the process is that associated with the boundary
movement.
 Taking the gas as our control mass and applying the first law, Eq. 5.11, we
have, in terms of Q, the heat transfer during the process is given in terms
of the change in the quantity U + PV between the initial and final states

 Because all these quantities are thermodynamic properties, that is,

functions only of the state of the system, their combination must also have
these same characteristics. Therefore, we find it convenient to define a
new extensive property, the enthalpy,
 THE CONSTANT-VOLUME AND CONSTANT-PRESSURE SPECIFIC HEATS

Neglecting changes in kinetic and potential energies, and assuming a simple compressible
substance and a quasi-equilibrium process,
• contains only thermodynamic properties,
– from which we conclude that the constant-volume and constant-pressure
specific heats must themselves be thermodynamic properties.
– This the result ultimately expresses a relation among a set of
thermodynamic properties and therefore constitutes a definition that is
independent of the particular process leading to it.

– As an example, consider the two identical fluid masses shown in

Fig. 5.9. In the first system 100 kJ of heat is transferred to it, and
in the second system 100 kJ of work is done on it. Thus, the
change of internal energy is the same for each, and therefore the
final state and the final temperature are the same in each. In
accordance with Eq. 5.14, therefore, exactly the same value for
the average constant-volume specific heat would be found for
this substance for the two processes, even though the two
processes are very different as far as heat transfer is concerned.
THE FIRST LAW AS A RATE EQUATION