CLB 20703

Chemical Engineering
Thermodynamics
Chapter 3:
The First Law of Thermodynamics

Objective of Chapter 3
To discuss ideas about energy for
engineering analysis and develop
equations for applying the principle of
the First Law of Thermodynamics on
conservation of energy in open and
closed systems

Outline

Introduction to First Law of

Thermodynamics.

Energy balance for closed system

Mass and Energy balance for open system

(Steady Flow)

3.1 INTRODUCTION
First

Law of Thermodynamics (also known as conservation of

energy principle) states that energy can be neither created
nor destroyed during a process but can only change forms.
Conservation of Energy Principle the net change (increase
or decrease) in the total energy of the system during a
process is equal to the difference between the total energy
entering and the total energy leaving the system during that
process:
Total energy Total energy Net change in the total

entering the system leaving the system energy of the system
Ein Eout Esystem
This

relation is applicable to any kind of system undergoing

any kind of process.

Energy Balance for any system

Ein Eout

Energy tra nsfer of a system

Energy
transfer
are
recognized at the system
boundary as they cross it
represent the energy gained
or lost by a system during a
process.
Energy can be transferred to
or from a system in three
forms: heat, work and mass
flow.
Only two forms of energy
transfer associated with a
closed system are heat
transfer and work.

Esystem

Energy change of a system

Energy change of a system during a

process = difference of the energy of the
system at the beginning and at the end of
the process:
Esystem=Efinal-Einitial =E2-E1
Energy is a property the value of a
property does not change unless the state
of the system changes the energy change
of a system is zero if the state of the system
does not change during the process.
The change in the total energy of a system
during a process is the sum of the changes
in its internal, kinetic, and potential
energies:
E system= U + KE + PE

3.2 ENERGY BALANCE FOR CLOSED SYSTEMS

Ein Eout

Net energy tra nsfer by

work, heat & mass

For closed systems, only Q and

W involved.
By using the sign convention of
heat and work, heat to be
transferred into the system (heat
input) in the amount of Q and
work to be done by the system
(work output) in the amount of W:

Esystem

Change in kinetic, potetial,

internal, etc. energies

The change in the total energy =

sum of the changes in its
internal, kinetic and potential
energies:

E U KE PE
with, U mu2 u1

KE 12 m v22 v12

PE mg z 2 z1

Q-W=E

Q W U KE PE
with, W Wb Wother

Overall 1st Law of

thermodynamics for closed
systems

Energy Balance for closed systems

(closed tank, rigid tank, piston-cylinder device)
with, W Wb Wother
Q W U KE PE
STATIONARY SYSTEMS (KE=PE=0)

Q W U

with,

W Wb Wother

CONSTANT VOLUME PROCESS / ISOCHORIC

PROCESS (V=0)

CONSTANT PRESSURE PROCESS / ISOBARIC

PROCESS (P=0)

RIGID TANK / PISTON-CYLINDER

DEVICE

PISTON-CYLINDER DEVICE (W=Wb)

Q Wb U
V=0 Wb=0
Q=U

Q U Wb
Q
U

P
Entalphy definition

Q H

Energy change for a cycle

For a closed system undergoing a cycle, the initial and final states
are identical:
Esystem = E2 - E1 = 0.
Then the energy balance for a cycle simplifies to Ein - Eout = 0 or
Ein = Eout.
A closed system does not involve any mass flow across its
boundaries, so the energy balance for a cycle can be expressed in
terms of heat and work interactions the net work output during a
cycle is equal to net heat input:

Qnet Wnet

Example 4.1
A rigid tank contains a hot fluid that is cooled while being stirred by a
paddle wheel. Initially, the internal energy of the fluid is 800kJ. During
the cooling process, the fluid loses 500J of heat, and the paddle wheel
does 100kJ of work on the fluid. Determine the final internal energy of
the fluid. Neglect the energy stored in the paddle wheel.
Example 4.2
A 0.5 m3 rigid tank contains refrigerant-134a initially at 160 kPa and
40% quality. Heat is now transfer to the refrigerant until the final
pressure reaches 700kPa. Determine
a)
The mass of the refrigerant in tank
b)
The amount of heat transferred
c)
Show on the process on PV diagram with respect to saturation line

Example 4.3
A piston cylinder device initially contains steam at 200 kPa, 200 OC and
0.5 m3. at this state, a linear spring (F x) is touching the piston but
exerts no force on it. Heat is now slowly transferred to the steam,
causing the pressure and the volume to rise to 500 kPa and 0.6 m3,
respectively. Show the process on a PV diagram with respect to
saturation line and determine
a)
The final temperature
b)
The work done by the steam
c)
The total heat transferred

3.3 MASS AND ENERGY BALANCE FOR

OPEN SYSTEM

Open systems are characterized by flowing

streams, there are 4 common measures of flow:
Velocity, u
Volumetric flowrate, q = uA
Molar flowrate, n uA
Mn uA
Mass flowrate, m
where M = molar mass/molecular weight
A = cross-sectional area
= specific or molar density

Energy Analysis Of Open System

An open system or a control volume (CV) = a selected region in space

and usually encloses a device that involves mass flow in and out of the
system such as a compressor, turbine or nozzle.
Besides heat transfer and work across the boundary, the mass and
energy content of a control volume can change when the mass flows in
and out of the system.

To simplify the energy analysis of CV:

The system should be assumed undergoing steady-flow process, and
Conservation of Mass Principle for CV should be firstly defined
before the 1st Law of Thermodynamics can be applied to CV.

Steady-flow Process

A large number of engineering devices such as turbines, compressors,

and nozzles operate for long periods of time under the same conditions
steady-flow devices.
Steady-flow process = a process during which a fluid flows through a
control volume steadily the fluid properties within the control volume
may change with position but not with time.

Therefore, the volume V, mass m, and total energy content E of the CV

remain constant during a steady flow process:
dmCV
CV 0
m
dt
dE CV
E CV 0
dt

Conservation of Mass Principle

Conservation of Mass Principle for CV: The net mass transfer to or

from a control volume during a time interval t is equal to the net
change (increase or decrease) in the total mass within the CV
during t:

Total mass entering Total mass leaving Net change in mass

CV
during

t
CV
during

t
within
CV
during

min mout mCV

m in m out m CV dmCV dt

m m
in

Also known as mass

balance and applicable
to any CV undergoing
any kind of process

For control volumes

undergoing steady-flow
process

out

For CV, mass and volume normally expressed in the rate forms
mass flow rate and volume flow rate. The mass and volume flow
rates are related by:

m V
v

or

Vav A

m Vav A
v

kg s

Conservation of Energy Principle

conservation of energy principle (1st Law of Thermodynamics)
for control volumes has the similar definition with that of closed
systems:
For steady-flow

The

E in E out

E system

Rate of net energy tra nsfer across

CV by heat, work and mass

(kW)

process,=0

Rate of change in internal, kinetic,

potential etc energies of CV

E in

Rate of net energy tra nsfer in

by heat, work and mass

E out

Rate of net energy tra nsfer out

by heat, work and mass

Qout Wout m

Qin Win m
in

out

V2
V2


Qin Win m
Pv

u
gz Qout Wout m
Pv

u
gz
2
2
in
out
h

V2
V2
h
h
Qin Win m
gz Qout Wout m
gz
2
2
in
out

for each inlet

for each outlet

= energy per
unit mass
flowing in and
out of CV

Energy Balance for control volumes

2
2

V
V

Qin Win m h
gz Qout Wout m h
gz
2
2
in
out

for each inlet

for each outlet

2
2

Vi
Ve

hi
he
Qin Win m
gzi Qout Wout m
gze

2
2

Q net Q in Q out

Q net W net

for each inlet

for each outlet

2
2

V
V
he e gze m
hi i gzi
m

2
2

for each inlet

W net Wout Win

for each outlet

Q W H K E P E

Overall 1st Law of

thermodynamics for
CV undergoing
steady-flow process

Steady-flow Engineering Devices

Nozzles and Diffusers

Nozzle and diffuser are commonly utilized in jet engines, rockets, spacecraft and
even garden hoses.
Nozzle = device that increases
Diffuser = device that
increases the pressure of
a fluid by slowing it down

the velocity of a fluid at the

expense of pressure

The rate of heat transfer between the fluid flowing through a nozzle or a diffuser and
the surroundings is usually very small (Q0), involve no work (W=0), any change in
potential energy is negligible (pe0) but involve very high velocities the kinetic
energy changes must be taken into account (ke0).

in m
out m
1 m
2 m

Mass balance : m
Energy balance : E in E out
2
2

V
V
h1 1 m
h2 2
m

2
2

2
V2 2h1 h2 V1

Turbines
Control
Surface

W
2

In steam, gas, or hydroelectric power plants, the device that drives

the electric generator TURBINE. As the fluid passes through the
turbine, work is done against the blades, which are attached to the
shaft shaft rotates, and the turbine produces work produce
power output.
By ignoring the change in KE and PE energies (ke=pe=0) through
an adiabatic turbine (Q=0) with a single stream (one inlet-one outlet)
that undergoes a steady flow process:

Mass balance : m in m out m 1 m 2 m

Energy balance : E E
in

out

m h1 m h2 W
W m h h
1

Compressors and Fans

Compressors,

as well as pumps and fans, are devices used to increase the

pressure of a fluid. Work is supplied to these devices from an external source
through a rotating shaft involve work inputs require power input.
The differences between the three devices:
A fan increases the pressure of a gas slightly and is mainly used to
mobilize a gas at low pressure.
A compressor is capable of compressing the gas to very high pressures.
Pumps work very much like compressors except that they handle liquids
instead of gases.
Heat transfer, kinetic and potential energies are also negligible for
compressors (Q=0, pe=0, ke=0):
Control
Surface

Mass balance : m in m out m 1 m 2 m

Energy balance : E E
in

out

m h1 W m h2
W m h h
2

Throttling Valves
Throttling valves are any kind of flow-restricting devices that
cause a significant pressure drop in fluid.
Unlike turbines, they produce a pressure drop without involving
any work but often accompanied by a large drop in temperature
devices are commonly used in refrigeration and airconditioning applications.
Throttling valves are usually small devices, and the flow through
them may be assumed to be adiabatic (q=0), no work done (w=0),
the change in potential energy is very small (pe=0), the increase
in kinetic energy is insignificant (ke=0):

i m
e
m
i hi m
e he
Energy balance : m
Mass balance :

hi he

Enthalpy values at the inlet and exit of a throttling

valve are the same throttling process =
isenthalpic process

Throttling process of an ideal gas

he hi
he hi 0

Te

Ti

C P (T )dT 0
Te Ti

The temperature of an ideal gas remains constant

during a throttling process since h=h(T)

Mixing Chambers
In engineering applications, mixing two streams of fluids is
not a rare occurrence. The section where the mixing process
takes place mixing chamber.
The mixing chamber does not have to be a distinct
chamber. An ordinary T-elbow or a Y-elbow in a shower =
mixing chamber for the cold and hot water streams.
The conservation of mass principle for a mixing chamber
requires that the sum of the incoming mass flow rates equal
the mass flow rate of the outgoing mixture.
Mixing chambers are usually well insulated (q=0), usually do
not involve any kind of work (w=0), the kinetic and potential
energies of the fluid streams are usually negligible (ke=0,
pe=0):

1
2

MIXER

2
????

m out m 1 m 2 m 3
Energy balance : E in E out
m 1h1 m 2 h2 m 3h3
Mass balance :

in

Heat Exchangers
Heat

exchangers are devices where two moving fluid streams exchange

heat without mixing.
widely used in various industries, and they come in various designs.
The simplest form of a heat exchanger is a double-tube (also called
tube and-shell) heat exchanger.

Q=0

Heat

is transferred from the hot fluid to the cold one through the wall
separating them and the outer shell is usually well insulated to prevent
any heat loss to the surrounding medium.
Heat exchangers typically involve no work interactions (w=0) and
negligible kinetic and potential energy changes (ke=0, pe=0) for each
fluid stream.

Heat transfer rate associated with heat exchangers depends on how the control

When the entire heat exchanger

is selected as the control volume,
Q becomes zero, since the
boundary for this case lies just
beneath the insulation no heat
crosses the boundary.
3

If only one of the fluids is selected as

the control volume, then heat will
cross this boundary as it flows from
one fluid to the other and will not be
zero the rate of heat transfer
between the two fluids.
3

m in m out m 1 m 3 m 2 m 4
EB : E in E out
m 1h1 m 3h3 m 2 h2 m 4 h4
MB :

MB :

in

m out m 1 m 2 and m 3 m 4

EB : E in E out
Q m 1h1 m 2 h2 or m 3h3 Q m 4 h4
Q m 2 h2 h1 or Q m 3 h3 h4

Pipes and Duct Flows

The

transport of liquids or gases in pipes and ducts is of great

importance in many engineering applications.
Flow through a pipe or a duct usually satisfies the steady-flow
conditions.
Sometimes heat transfer is desirable and is the sole purpose of
the flow. Water flow through the pipes in the furnace of a power
plant, the flow of refrigerant in a freezer, and the flow in heat
exchangers are some examples of this case.
At other times, heat transfer is undesirable, and the pipes or
ducts are insulated to prevent any heat loss or gain, particularly
when the temperature difference between the flowing fluid and
the surroundings is large. Heat transfer in this case is
negligible.

Liquid Pumps
Work is required to pump a compressed liquid in an adiabatic (q=0)
and steady flow process.
For compressed liquid, the density and specific volumes are
constant (v2=v1=v) and the process of pumping compressed liquid
is isothermal (u=cvdT=0). By neglecting KE and PE:

MB : min mout m
2
2
Fluid exit, 2

V1
V2

h1
h2
EB : W m
gz1 m
gz2

2
2

2 2

Pump
V2 V1

h2 h1
W m
g z 2 z1

2
u2 u1 Pv 2 Pv 1

W
pe 0

ke 0

u 2 u1 Pv 2 Pv 1
W m

u 0
Pv 2 Pv 1
W m
vP P
W m
2

Fluid inlet, 1
Liquid flow through a pump

Example 4.4
Steam enter a nozzle at 400 OC and 800 kPa with a velocity
of 10m/s, and leaves at 300 OC and 200 kPa while losing
heat at a rate of 25 kW. For an inlet area of 800 m2,
determine the velocity and the volume flow rate of the steam
at the nozzle exit.

Example 4.5
Steam enters the condenser
of a
steam power plant at 20 kPa and a
quality of 95% with a mass flow rate of
20000 kg/hr. it is to be cooled by water
from a nearby river by circulating the
water through the tubes within the
condenser.
To
prevent
thermal
pollution, the river water is not allowed
to experienced a temperature rise
above 10 OC. If the steam is to leave
the condenser as saturated liquid at 20
kPa, determine the mass flow rate of
the cooling water required.