First Law of

Thermodynamics
Dr. Rohit Singh Lather

The First Law of Thermodynamics

The internal energy E of a system tends to increase, if energy is added as heat Q and tends to
decrease if energy is lost as work W done by system
dE = dQ dW ( first law)
(Q is the heat absorbed and W is the work done by the system)

The quantity (Q W) is the same for all processes

It depends only on the initial and final states of the system
Does not depend at all on how the system gets from one to the other
This is simply conservation of energy

Internal Energy
Internal energy (u): that portion of total energy E which is not kinetic or potential
energy. It includes thermal, chemical, electric, magnetic, and other forms of energy
Change in the specific internal energy
du = CdT
In case of gases internal energy is given by u = CvdT
Specific heat changes with temperature is given by
C = Co (a+bT), a and b are constants and Co is specific heat at 0oC
The total energy in the mass m is the sum of internal energy as well as PE and KE in the mass
!

E = U + PE + KE = m .u + mg. Z + " m V2
For unit mass E = em = u +

$
%

!
"

+ V2 (p = gZ)

Enthalpy
1Q2

=U2 U1 + P2V2 P1V1

= (U2 + P2V2) (U1 + P1V1)

Enthalpy h = u + pvs
u = h - pv
The enthalpy is especially valuable for analyzing isobaric processes

The heat transfer in a constant-pressure quasi-equilibrium process is equal to the change in

enthalpy, which includes both the change in internal energy and the work for this particular
process
This is by no means a general result
It is valid for this special case only because the work done during the process is equal to the
difference in the PV product for the final and initial states
This would not be true if the pressure had not remained constant during the process

Sir Benjamin Thompson

Count Rumford

Thompsons theory of heat was demonstrated by a test tube full

of water within wooden paddles
Water boiled due to friction
The heat of friction is unlimited

Source: http://www4.ncsu.edu/~kimler/hi322/Rumford-expt.gif

The Joules Experiment

=

proportionality constant - mechanical equivalent of heat

Rise in
temperature

As the weight falls at

constant speed, they
turn a paddle wheel,
which does work on
water

One calorie corresponds to the amount

of heat that is needed to get one gram
of water from 14.5 C to 15.5 C
W

1 Cal = 4.1840 J
Insulating walls
prevent heat transfer from the
enclosed water to the surroundings

H
A paddle wheel turns
in liquid water

If friction in mechanism is negligible, the work done by the paddle wheel on the water equals the
change of potential energy of the weights

Work can be transformed into heat

Heat and work are of the same nature and constitute different forms of energy

Joule showed that the same temperature rise could be obtained using an electrical resistor heated
by an electric current

First Law of Thermodynamics

If a system executes a cycle transferring work and heat through its boundaries,
then net work transfer is equal to net heat transfer
During any cycle, the cyclic integral of heat added to a system is proportional to the cyclic
integral of work done by the system
=
E2 E1 = Q - W
dE = Q - W
dE = E2 E1 =

"
! (

For a closed system

"

dU = U2 U1 = !
dU = U2 U1 = Q - W

Adiabatic processes
Process that occurs so rapidly or occurs in a system that is so well insulated that no transfer of
thermal energy occurs between the system and its environment
Constant-volume processes
If the volume of a system (such as a gas) is held constant, so that system can do no work
Cyclical Processes
Processes in which, after certain interchanges of heat and work, the system is restored to its initial
state. No intrinsic property of the systemincluding its internal energycan possibly change
Free expansion
Adiabatic processes in which no heat transfer occurs between the system and its environment and no
work is done on or by the system

First Law Corollaries

Corollary 1
There exists a property of a closed system such that the change in its value is equal to the
difference between heat supplied and work done during the change of state

Corollary 2
The internal energy of a closed system remains unchanged if the system is isolated from its
surroundings

Corollary 3

The perpetual motion machine (PMM) of first Kind is impossible

Corollary 1

There exists a property of a closed system such that the change in its value is equal to the
difference between heat supplied and work done during the change of state

"
"
"
"
! A + ! B = ! A + ! B
"
"
"
"
! C + ! B = ! C + ! B

Pressure

=
A, B, & C are arbitrary processes
between state 1 and state 2

"
"
"
"
! A - ! C = ! A - ! C

Subtracting and rearranging

"
! (

- )

"
= ! (

- )

1
Volume


Therefore depends only on the initial and final states and not the path followed
between the two states
dE =
E2 E1 = 1Q2 1W2
The physical significance of the property E is that it represents all the energy of the system in the given
state
In thermodynamics, it is convenient to consider the bulk kinetic and potential energy separately and then to
consider all the other energy of the control mass in a single property that we call the internal energy and to
which we give the symbol U

E = Internal energy + kinetic energy + potential energy

E = U + KE + PE

The perpetual motion machine (PMM)

HYPOTHETICAL SYSTEM

produce useful work

indefinitely

produce more work or

energy than they
consume

There is undisputed scientific consensus that Perpetual motion would violate the Laws of Thermodynamics

What is Perpetual Motion?

Describes a theoretical machine that, without any losses due to friction or other forms of
dissipation of energy, would continue to operate indefinitely at the same rate without any external
energy being applied to it
Machines which comply with both the 1st & 2nd Laws of Thermodynamics but access energy from
obscure sources are sometimes referred to as Perpetual Motion machines

Perpetual Machine of First Kind (PMFK)

A perpetual motion machine of the first kind produces work without the input of energy

It thus violates the 1st Law of Thermodynamics: the Law of conservation of energy

First law states that the total amount of energy in an isolated system remains constant over

A consequence of this law is that energy can neither be created nor destroyed: it can only be
transformed from one state to another

So, It is clearly impossible for a machine to do the work infinitely without consuming energy

Examples of the 1st Kind of Perpetual Motion Machine

The Overbalanced Wheel

The Float Belt

The Capillary Bowl

Laws of Conservation
Law of Conservation of Mass: Mass can neither be created nor be destroyed, but may be converted
from one form to another form

A1V11 = A2V22 (One dimensional

continuity equation)

Law of Conservation of Momentum: If no external force acts on a system, linear momentum is

conserved in both direction and magnitude
m1V1 + m2V2 = (m1+m2)V
Law of Conservation of Energy: Energy can neither be created nor be destroyed

Energy and System

Change in Total Energy
of the System

= Total Energy Entering

the System

Total Energy Leaving

the System

E = Ein - Eout
Esystem = Efinal

state

Einitial

state

Mechanism of Energy Transfer

Heat Transfer

Mass Transfer

Work Transfer
0 for steady state

Energy balance in rate form, Ein Eout

For a closed system undergoing a cycle , Esystem = E2 E1 = 0 -> Ein = Eout

Conservation of Energy for Control Volumes

The conservation of mass and the conservation of energy principles for open systems or control
volumes apply to systems having mass crossing the system boundary or control surface
Thermodynamic processes involving control volumes can be considered in two groups: steady-flow
processes and unsteady-flow processes
Defining a Steady Flow Process: A process during which the fluid flows steadily through the
control volume (CV)
- Flow process fluid flows through CV
- Steady not changing with time
- During a steady flow process:
- Conditions (fluid properties, flow velocity, elevation) at any fixed point within the CV are unchanging with time

- Properties, flow velocity or elevation may change from point to point within CV
- Size, shape, mass and energy content of the CV do not change with time
- Rate at which heat and work interactions take place with surroundings do not change with time

- Devices/systems which undergo steady flow process:

compressors, pumps, turbines, water supply pipes, nozzles, heat exchangers, power plants, aircraft engines etc.

 During a steady-flow process, the fluid flows through

experiencing no change with time at a fixed position

Z height
Q Heat
W Work
m Mass
V Velocity

Wnet

miVi

i - inlet

the control volume steadily,

Vcm

Zi

Zcm

Qnet

Control Surface
meVe
Ze

e exit

The mass and energy content of the open system may change when mass enters or leaves the control volume

For Steady-State, Steady-Flow Processes

Most energy conversion devices operate steadily over long periods of time

The rates of heat transfer and work crossing the control surface are constant with time

The states of the mass streams crossing the control surface or boundary are constant with time

Under these conditions the mass and energy content of the control volume are constant with time
MNOP
= cv = 0
MQ

MROP
= = 0
MQ

Steady-state, Steady-Flow Conservation of Mass:

m! = m!
in

out

( kg / s)

Steady-state, steady-flow conservation of energy: The energy of the control volume is constant
with time during the steady-state, steady-flow process

E! in E! out
"$#$%

Rate of net energy transfer

by heat, work, and mass

E! system
"#
$ $
%

Rate change in internal, kinetic,

potential, etc., energies

( kW )

Conservation of Energy for General Control Volume

The conservation of energy principle for the control volume or open system has the same word
definition as the first law for the closed system

Expressing the energy transfers on a rate basis, the control volume first law is

E! in E! out
"$#$%

Rate of net energy transfer

by heat, work, and mass

E! system
"#
$ $
%

( kW )

Rate change in internal, kinetic,

potential, etc., energies

Considering that energy flows into and from the control volume with the mass, energy enters
because net heat is transferred to the control volume, and energy leaves because the control volume
does net work on its surroundings, the open system, or control volume, applying the first law of
thermodynamics
Energy balance in differential form
Time rate form of energy balance

dE = Q - W
MR
MQ

. .

= QW

MR
Time rate change of energy is given by
MQ
Time rate change of energy is given by Q

MSR
MQ

W=

MSR
MQ

MTR
MQ

MTR
MQ

MU
MQ

MU
MQ

Where the time rate change of the energy of the control volume has been written as E! CV
Considering that energy flows into and from the control volume with the mass, energy enters
because heat is transferred to the control volume, and energy leaves because the control volume
does work on its surroundings, the steady-state, steady-flow first law becomes

Total energy crossing

boundary per unit time

Total energy of mass

leaving CV per unit time

Total energy of mass

entering CV per unit time

Q! net = Q! in Q! out

W!net = W!out W!in

Steady Flow process Involving one fluid stream at the inlet and exit of the control volume

Mass flow rate (kg/s)

VW
= P! !
!

V"W"
P"

Where, V = Velocity (m/s)

v = specific volume (m3/kg)

Steady-State, Steady-Flow for One Entrance and One Exit

A number of thermodynamic devices such as pumps, fans, compressors, turbines, nozzles,

diffusers, and heaters operate with one entrance and one exit

The steady-state, steady-flow conservation of mass and first law of thermodynamics for these
systems reduce to
2
2
V
V
Q! W! = m! (he + e + gz e ) m! (hi + i + gzi )
2
2

2
2
V

V
1
Q! W! = m! [h2 h1 + 2
+ g ( z2 z1 )]
2

V22 V12
q w = h2 h1 +
+ g ( z2 z1 )
2
or

V 2
q = h +
+ gz + w
2

since

m! = m! = m!
e

Using subscript 1 and subscript 2 for denoting

inlet and exit states
Dividing the equation by

V 2

q = u + pv +
+ gz + w
2

!
m

yields

Solving Steady Flow Energy Equation

( +

+ ) + = +

+ +

[h, W, Q should be in J/kg and V in m/s and g in m/s2]

+ ) +

+ +

[h, W, Q should be in kJ/kg and V in m/s and g in m/s2]

Work

Work

-ive (negative)

+ive (positive)

Heat

Heat
+ive (positive)

-ive (negative)

Our aim is to give heat to the system and gain work output from it.
So heat input +ive (positive) Work output +ive (positive)

Applications of SFEE
Nozzles and diffusers (e.g. jet propulsion)
Turbines (e.g. power plant, turbofan/turbojet aircraft engine), compressors and pumps (power
plant)
Heat exchangers (e.g. boilers and condensers in power plants, evaporator and condenser in
refrigeration, food and chemical processing)
Mixing chambers (power plants)
Throttling devices (e.g. refrigeration, steam quality measurement in power plants)
All elements of a simple power plant/ refrigeration cycle and more! In principle, you can take the
elements together to calculate power generated/required, heat removed/supplied.

Gas Turbines
Source: www.google.com

Heat Exchangers

Throttling Devices

Water Turbine

+ +

+ + =

+ +

+ +

+
+ + + = +
+ +

= =

Water Turbine

Datum

+ (p2 p1)

Steam / Gas Turbine

Steam/Gas In

+ +

+ + =

+ +

+ +

+ +

+ +

Steam/Gas Out
Steam/Gas
Turbine

Steam Nozzle

Steam In

+
+

+ + =

+ +

+ +

Steam Out

+ +

+=

+ +

+ ( )

( )

Boiler
Control Surface

Boiler

+ +

+ +

+ + =

+ +

+ +

+ + =

+ +

+ +

h1 + q = h
q = h - h

Heat Exchanger

Control Surface
1 kg steam

Tw1

+ +

+ +

+ + =

+ =

h - q = h

+ +

+ +

Tw2

+ +

+ +

q - heat lost by 1 kg steam to water passing through condenser

q = (hw2 hw1) mw = mw Cw (Tw2 Tw1)

q - heat gained by water by passing through condenser

h - (hw2 hw1) mw = h

mw flow of water per kg steam

h - h = (hw2 hw1) mw =mw Cw (Tw2 Tw1)

Reciprocating Compressor

+ +

+ +

+ + =
+ =

+ +

+ +

+ +

Control Surface

+ =
If Velocity changes are neglected and flow process is
treated as adiabatic

Due to large area in contact and low flow rates appreciable heat transfer can take place between the system
and the surroundings. Therefore water cooling is required

Rotary Compressor

Control Surface

+ +

+ + =

+ +

+ +

+ =

+ +

+ +

Centrifugal Pump

+ +

+ + =

+ +

+ + + = +
+ =

Control Surface

+ +

+ + +

+ ( )

Water Sump

Steam/Gas Out

A blower handles 1 kg/s of air at 20C. Find the exit air temperature, assuming adiabatic
conditions. Take cp of air is 1.005 kJ/kg-K.

100 m/s

150 m/s

m1 = m2 = kg /s
W = 15 kW

+ +

+ +

+ + =
+=

+ +

+ +

+ +

Throttling process

A flow is throttled when, for example, it flows through a partially open valve
When it does so, we notice that there can be a significant pressure loss from one side of the
partially open valve to the other

A throttling process is modeled as steady device with one entrance and exit, with no control volume work or
heat transfer
Changes in area as well as potential energy are neglected

In throttling devices there may be a change in velocity due to compressibility effects, but it is
observed to be small when the flow velocity is much less than the speed of sound.
We shall assume here the velocity is small relative to the speed of sound so as to recover v1 v2
Thus, h1 = h2
So, we can say that such a throttling device is one in which pressure drops and enthalpy remains constant

This shows that enthalpy remains constant during adiabatic throttling process.
The throttling process is commonly used for the following purposes :
1. For determining the condition of steam (dryness fraction)
2. For controlling the speed of the turbine
3. Used in refrigeration plants
4. Liquefaction of gases

The Joule-Thomson Experiment

In this experiment gas is forced through a porous plug and is called a throttling process
piston

Pi vi Ti

adiabatic walls

porous plug

Pf vf Tf

In an actual experiment, there are no pistons and there is a continuous flow of gas
A pump is used to maintain the pressure difference between the two sides of the porous plug

In this experiment, as pressures are kept constant work is done

0

vf

w = Pi dv + Pf dv = Pf v f Pi v i
vi

= +

0 = (uf ui ) + (Pf vf Pi vi ) or uf + Pf vf = ui + Pi vi
From the definition of enthalpy

h f = hi

Hence, in a throttling process, enthalpy is conserved

 In the region where the atoms or molecules are very close together, then repulsive forces
dominate and as the volume expands, the energy goes down. Thus, for these conditions, pT is
negative
In the region where the atoms or molecules are close enough that attractive forces dominate,
then as the volume expands, the energy goes up. Thus, for these conditions, pT is positive
For most gases at not too large pressures, the molecules don't interact very much and so there is
little dependence of energy on volume so pT is very small.
In the extreme of zero
interaction, pT is zero. This is the defining condition for an ideal (perfect) gas.

39

Throttling Process

(Joule-Thomson or Joule-Kelvin expansion widely used in refrigerators)

Pump

The pump maintains the pressures Pi and Pf

In the experiment Pi, Ti and Pf are set and Tf is
measured
Pi Ti

Pf

Tf

Porous plug

Consider a series of experiments in which Pi and Ti are

constant (hi constant) and the pumping speed is changed to
change Pf and hence Tf
Since the final enthalpy does not change, we get points
of constant enthalpy

Pi > Pf
The enthalpy is the same on the
two sides of the porous plug i.e.,
hf = hi.

We plot Tf as a function of Pf
40

Temperaturef

Isenthalpic Curve

Pf , Tf

Pi, , Ti

Pressuref
- A smooth curve is placed through the points yielding an isenthalpic curve
- Note that this is not a graph of the throttling process as it passes through irreversible states

41

Temperaturef

We now change Pi and Ti and obtain another isenthalpic curve

Maximum Inversion T
Inversion Curve
Cooling
d

Heating

We are interested in the temperature change

due to the pressure change, therefore it is
useful to define the Joule-Thomson coefficient

= (TP )h

This is the slope of an isenthalpic curve and

hence varies from point to point on the graph
Ideal Gas

Inversion Curve

Pressuref
A point at which = 0 is called an inversion point
Connecting all of these points produces the inversion curve
42

Temperaturef

Maximum inversion T, the value of which depends on the gas.

For cooling to occur, the initial T must be less than the maximum inversion T, for such a T the
optimum initial P is on the inversion curve
Maximum Inversion T
Inversion Curve
Cooling
d

If we start at point c
( > 0) and go to point
d, then the T of the
gas will drop, i.e. we
have cooling

b a

Heating
Ideal Gas

Inversion Curve

If point a on the diagram

( < 0) is a starting point
and point b is the final
point, then the T of the
gas will rise, i.e. we have
heating

Pressuref
These curves are horizontal
lines for an ideal gas

As higher initial starting temperatures are used, the isenthalpic curves become flatter and more
43
closely horizontal

 This also tells us that we cannot just use any gas at any set of pressures to make a refrigerator,
for example
- At a given pressure, some gases may be cooling (m > 0) but others may be heating (m < 0)
The proper choice of refrigerant will depend on both the physical properties, esp. the JouleThompson coefficient as well as the mechanical capacity of the equipment being used.
Thus, we cannot just exchange our ozone-depleting freon in our car's air conditioner with any
other coolant unless the two gases behave similarly in the pressure - temperature ranges of the
mechanical device, i.e., they must have the same sign of m at the pressures the equipment is
capable of producing.
Generally, to use a more environmentally friendly coolant, we need to replace the old equipment
with new equipment that will operate in the temperature range needed to make m positive.

 The sign of the JouleThomson coefficient, , depends on the conditions

The temperature corresponding to the boundary at a given pressure is the inversion temperature
of the gas at that pressure

The maximum inversion temperatures of

some gases are given below :
(i) He=24K
(ii) H2=195K

Positive

Negative

(iii) Air=603K
(iv) N2 =261K
(v) A=732K
(vi) CO2 =1500K

http://faculty.chem.queensu.ca/people/faculty/mombourquette/Chem221/3_FirstLaw/ChangeFunctions.asp

For a given pressure, the temperature must be below a certain value if cooling is required
but, if it becomes too low, the boundary is crossed again and heating occurs
Reduction of pressure under adiabatic conditions moves the system along one of the isenthalps, or
curves of constant enthalpy
To make the discussion clear, we have exaggerated the slopes in the above T-P diagram. In fact, for
most gases at reasonable Ts and Ps the isenthalpic curves are approximately flat and so 0

It can be shown that

= cP = cP
P T
P h

=0

then

h
= 0
P T

and so

h = h(T )

u
h
(Pran
oblem
.1)
ideal 5gas
We now have
=
= 0 for
v T P T
Constant temp. coefficient and can be
determined by Joules Thompson experiment

46

Liquefaction of Gases
Some gases can be liquefied in a simple process
- For example, carbon dioxide can be liquefied at room temperature by a simple isothermal
compression to about 60 bar
To liquefy nitrogen or air is not so simple.
- At room temperature, regardless of any increase in pressure, these gases will not undergo a
phase transformation to the liquid state
A method for these gases, using the throttling process, was invented in 1895 and is called the
Hampson-Linde Process
- The basis idea is to use the gas cooled in the throttling process to precool the gas going towards
the throttle
until the T is below the maximum inversion T
- Starting from room temperature, this cycle can be used to liquefy all gases except hydrogen and
helium
- To liquefy H by this process, it must first be cooled below 200K and to accomplish this liquid N
at 77K is used
- To liquefy He by this process, it must first be cooled below 43K and to accomplish this liquid H
can be used. (A device called the Collins helium liquifier is used to liquefy He.
47

Hampson-Linde Process

If a throttling process is used to liquefy a gas, the cooled gas is recycled through a heat exchanger to
precool the gas moving towards the throttle. The gas continues to cool and when a steady state is
reached a certain fraction, y, is liquefied and a fraction (1 - y) is returned by the pump.
Using the notation:
- hi = molar enthalpy of entering gas
- hf = molar enthalpy of emerging gas
- hL = molar enthalpy of emerging liquid
Since the enthalpy is constant we have
hi = y h L + (1-y)hf
Of course, as some of the gas liquefies, additional gas must be added to the system.

It should be mentioned that Joule-Thomson liquefaction of gases has these advantages:

No moving parts that would be difficult to lubricate at low T.
The lower the T , the greater the T drop for a given pressure drop.

49

Controlling the speed of the steam turbine by Throttling