CHAPTER IV

1 SL AW OF
T

THERMODYNAMICS
K K K R 1 2 4 3 C H E M I C A L E N G I N E E R I N G T H E R M O DY N A M I C S I
( P R O F. I R . D R . S I T I R O Z A I M A H S H E I K H A B D U L L A H &
P R O F . M A D Y A D R . I R . M A S T U R A H M A R K O M @ J K K P, F K A B , U K M )
LEARNING OUTCOMES OF CHAPTER IV
• Identify the first law of thermodynamics as a statement of the conservation of energy
1 principle for closed (control mass) and control volume (open) systems.

• Develop the general energy balance applied to closed systems and solve energy balance
2 problems that involve heat and work interactions.

• Develop and apply the conservation of mass principle for steady-flow control volumes.
3

• Apply the first law of thermodynamics as the statement of the conservation of energy
4 principle to control volumes.

• Solve energy balance problems for common steady-flow devices such as nozzles,
5 compressors, turbines, throttling valves, mixers, heaters, and heat exchangers.
INTRODUCTION
1ST LAW OF
THERMODYNAMICS
• Energy can be neither created nor destroyed during a process but
= Conservation of
can only change forms
Energy Principle =
Energy Balance
• Net change (increase or decrease) in the total energy of the
Conservation of system during a process is equal to the difference between the
Energy Principle 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

Applicable to any kind of system

undergoing any kind of process
 ENERGY BALANCE FOR ANY SYSTEM
𝐸𝑖𝑛 −𝐸𝑜𝑢𝑡 = ∆𝐸𝑠𝑦𝑠𝑡𝑒𝑚
Energy transfer of a system Energy change of a system

Energy change of a system during a

Energy transfer are recognized at process = difference of the energy of the
the system boundary as they system at the beginning and at the end
cross it  represent the energy of the process:
gained or lost by a system during
a process. Esystem=Efinal-Einitial =E2-E1

Energy is a property  energy change

of a system is zero if the state of the
Control volumes: Q, W and m system does not change during the
process.

The change in the total energy = the

Closed system: Q and W sum of changes in U, KE and PE:
E system= U + KE + PE
 ENERGY BALANCE FOR CLOSED SYSTEMS
𝐸𝑖𝑛 −𝐸𝑜𝑢𝑡 = ∆𝐸𝑠𝑦𝑠𝑡𝑒𝑚
Net energy transfer by 𝑊, 𝑄 and 𝑚 Change in 𝐾𝐸, 𝑃𝐸, 𝑈 etc. energies

For closed systems, only Q and Change in the total energy = sum
W are involved of the changes in its internal,
kinetic and potential energies

Sign convention (+ve): Heat to ∆𝐸 = ∆𝑈 + ∆𝐾𝐸 + ∆𝑃𝐸

be transferred into the system
with, ∆𝑈 = 𝑚 𝑢2 − 𝑢1 ,
(heat input) in the amount of Q
1
and work to be done by the ∆𝐾𝐸 = 2 𝑚 𝑣22 − 𝑣12 ,
system (work output) in the
amount of W ∆𝑃𝐸 = 𝑚𝑔 𝑧2 − 𝑧1

𝑄 − 𝑊 = ∆𝑈 + ∆𝐾𝐸 + ∆𝑃𝐸
(Overall 1st Law of Thermodynamics for Closed Systems)
 ENERGY BAL ANCE FOR CLOSED SYSTEMS
(CLOSED TANK , RIGID TANK , PISTON -CYLINDER DEVICE)
Q  W  U  KE  PE with, W  Wb  Wother 

STATIONARY SYSTEMS (KE=PE=0)

Q  W  U with, W  Wb  Wother 

CONSTANT VOLUME PROCESS / CONSTANT PRESSURE PROCESS /

ISOCHORIC PROCESS (V=0) ISOBARIC PROCESS (P=0)

RIGID TANK / PISTON-CYLINDER PISTON-CYLINDER DEVICE (W=Wb)

DEVICE
Q  Wb  U
V=0  Wb=0
Q  U  Wb
Q=U
Q
U 
PV
Entalphydefinition

 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
𝑬𝒊𝒏 −𝑬𝒐𝒖𝒕 = ∆𝑬𝒔𝒚𝒔𝒕𝒆𝒎
𝐍𝐞𝐭 𝐞𝐧𝐞𝐫𝐠𝐲 𝐭𝐫𝐚𝐧𝐬𝐟𝐞𝐫 𝐛𝐲 𝑾, 𝑸 𝒂𝒏𝒅 𝒎 𝐂𝐡𝐚𝐧𝐠𝐞 𝐢𝐧 𝑲𝑬, 𝑷𝑬, 𝑼 𝐞𝐭𝐜. 𝒆𝒏𝒆𝒓𝒈𝒊𝒆𝒔

𝑬𝒊𝒏 − 𝑬𝒐𝒖𝒕 = 𝟎
∴ 𝑬𝒊𝒏 = 𝑬𝒐𝒖𝒕

The energy balance for a cycle of a closed system can

also be expressed in terms of heat and work
interactions:
𝑸 − 𝑾 = ∆𝑼 + ∆𝑲𝑬 + ∆𝑷𝑬
=𝟎

𝑸𝒏𝒆𝒕 = 𝑾𝒏𝒆𝒕
1ST LAW OF THERMODYNAMICS FOR CLOSED SYSTEMS
(Ein-Eout=Esystem)

GENERAL (W=Wb+Wother)
Q-W=U+KE+PE

STATIONARY SYSTEMS (KE=PE=0)

Q-W=U

RIGID TANK (W=0) PISTON-CYLINDER DEVICE & CYCLIC PROCESS (U=0)

ISOBARIC PROCESS (P=0)
Q=U Q-Wother=H Q=W

ONLY INVOLVE Wb (Wother=0)

Q=H
 ENERGY ANALYSIS OF CONTROL VOLUMES
OPEN SYSTEM ENERGY ANALYSIS

Also known as control volume (CV) 2 steps to be taken before 1st Law of
Thermodynamics can be applied to CV
= selected region in space and usually
encloses a device that involves mass Step 1: The system should be assumed
flow in and out of the system such as undergoing steady-flow process, and
a compressor, turbine or nozzle.
Step 2: Conservation of Mass Principle
Besides Q and W across the boundary, for CV should be firstly defined.
the mass and energy content of a
control volume can change when the
mass flows in and out of the system.
 STEP 1: STEADY-FLOW PROCESS (???)
• Engineering devices (turbines, compressors, and
Steady-flow nozzles) operate for long periods of time under the
devices same conditions.

• 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.

Steady flow
process

V, m, and E of dmCV
CV remain  m CV  0
dt
constant
dECV
during a steady  E CV  0
flow process dt
 STEP 2: CONSERVATION OF MASS PRINCIPLE

Conservation • The net mass transfer to or from a control volume during a time
of Mass interval t is equal to the net change (increase or decrease) in the
Principle = total mass within the CV during t.
• Applicable to any CV undergoing any kind of process.
Mass Balance

 Total mass entering   Total mass leaving   Net change in mass 

       
 CV during t   CV during t   within CV during t 
Mathematical m in  m out  m CV  dmCV dt
formula  
 0 Steady flow process 

  m   m
in out

• For CV, mass and volume normally

Mass flow expressed in the rate forms.
rate / volume 
 
flow rate V V A
m  V   Vav A  av kg s 
v v
 STEP 3: CONSERVATION OF ENERGY PRINCIPLE
1st Law of E in  E out  E system (kW)
  
Thermodynamics Rate of net energy transfer across
CV by heat, work and mass
Rate of changein internal, kinetic,
potentialetc energies of CV
for CV For steady-flow
 process,Ė=0
E  E out
in 
Similar definition Rate of net energy transfer in Rate of net energy transfer out
by heat, work and mass by heat, work and mass
with that of
closed systems 
Qin  Win   m  Qout  Wout   m 
in out

In terms of rate 
2 2
 V   V 
Qin  Win   m  
Pvu  gz  Qout  Wout   m  
Pvu  gz 
in  h 2  out  h 2 
  = energy per unit
2 2 mass flowing in
 V   V  and out of CV
Qin  Win   m  h   gz  Qout  Wout   m  h   gz 
 
in 2 out 2
for each inlet for each outlet
 Energy Balance for control volumes
2 2
 V   V 
Qin  Win   m h 
   gz  Qout  Wout   m h 
    gz 
 
in 2 out 2
for each inlet for each outlet


2 2
 Vi   Ve 
Qin  Win   m
  
 hi 
  gzi   Qout  Wout   m
   
 he 
  gze 
 2   2
   
Q net   Q in   Q out
for each inlet for each outlet


2 2
 V   V 
Q net  W net  m
  he  e  gze    m
 
  hi  i  gzi 
 
 2  2
   

for each inlet for each outlet

Wnet  Wout  Win 

Q  W  H  K E  P E
Overall 1st Law of
thermodynamics for CV
undergoing steady-flow
process
 1st LAW OF THERMODYNAMICS FOR CONTROL VOLUMES
(Ėin-Ėout=ĖCV)

STEADY-FLOW PROCESS UNSTEADY-FLOW PROCESS

(ĖCV=0) (ĖCV0)

STATIONARY SYSTEM (KE=PE=0)

Q  W  H

NO WORK (W=0) ADIABATIC PROCESS (Q=0)

Q  H H  W
APPROACH TO APPLY 1ST LAW ON CONTROL VOLUMES

STEP 1
Steady flow assumption

STEP 2
Perform mass Balance

STEP 3
Apply Energy Balance (1st Law)

Application of the basic 1st

Law for CV Concentrate on
directions
(Q-W=ΔH+ΔKE+ΔPE)

Focus on direction (Ignore the sign convention)

Stick to Sign
WHAT GOES IN = WHAT GOES OUT
Convention
(Δm=0; ΔE=0)
STEADY-FLOW ENGINEERING DEVICES
NOZZLES AND DIFFUSERS
• Nozzles and diffusers are commonly utilized in jet engines, rockets, spacecraft, and even garden hoses.

NOZZLES
Rate of heat transfer between the fluid
flowing through a nozzle or a diffuser and
Device that increases
the surroundings is usually very small (Q0)
the velocity of a fluid
at the expense of
pressure Involve no work (W=0)

Change in potential energy is negligible

DIFFUSERS (pe0)
Device that increases
the pressure of a fluid
by slowing it down Involve very high velocities  the kinetic
energy changes must be taken into account
(ke0)

M ass balance : m  in m  out m  1 m 2 m


Energy balance : E in  E out
2 2
 V1   V2 
m  h1  m   h2  
   
 2   2 
 2
V2  2h1  h2   V1
TURBINES
Control
Surface
1
W

Change in KE and PE energies are

TURBINE- device negligible (ke=pe=0).
that drives the
electric generator
in steam, gas, or Adiabatic turbines (Q=0).
hydroelectric
power plants Involve a single stream (one inlet-
As the fluid one outlet) and undergo a steady
passes through flow process.
the turbine,
work is done
Turbine
M ass balance : m in m out m 1 m 2  m
against the
blades, which
produces work Energy balance : E  Ein out
 Power
later rotate shaft
output m h1  m h2  W
W  m h  h 1 2 
COMPRESSORS AND FANS
• Used to increase the pressure of a fluid.
Compressors, pumps
• Work supplied to these devices from an external source through a
and fans rotating shaft  involve work inputs  require power input.

Fans

Pumps
Compressors

• Capable of • Increases the • Pumps work very

compressing the pressure of a gas much like
gas to very high slightly and is compressors
pressures. mainly used to except that they
mobilize a gas at handle liquids
low pressure. instead of gases.

• Kinetic and potential energies are also negligible for compressors

Assumptions (pe=0, ke=0)
• Adiabatic compressors (Q=0)

M ass balance : m in m out m 1 m 2  m Control

Surface
Energy balance : E  E
in out
1 W
m h1  W  m h2
2
W  m h  h 2 1
THROTTLING VALVES
Throttling valves ???
Any kind of flow-restricting
Throttling valves ≠ Turbines
devices that cause a Assumptions
significant pressure drop in They produce a pressure
fluid. drop without involving any
Throttling valves are usually
Commonly used in work but often accompanied
small devices, and the flow
refrigeration and air- by a large drop in
temperature through them may be
conditioning applications.
assumed to be adiabatic
(q=0),
No work done (w=0),
Change in potential and
kinetic energy is very small
(pe=0, ke=0):

M ass balance : m i  m
e
 i hi  m
Energy balance : m  e he
Enthalpy values at the inlet and exit of
 hi  he
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 Usually well
insulated (q=0),
Do not involve
any kind of work
(w=0),
The mixing chamber
does not have to be  Kinetic and
a distinct potential energies
“chamber.” An of the fluid streams
ordinary T-elbow or are negligible (ke=0,
In engineering pe=0)
a Y-elbow in a
applications, mixing
shower = mixing
two streams of
chamber for the
fluids is common.
cold and hot water
The section where
streams.
the mixing process 1
takes place  MIXER 3
Mixing chamber. 2

Mass balance :  m   m out m 1  m 2  m 3

in
2
Energy balance : E in  E out 1 ????
3
 m 1h1  m 2 h2  m 3h3
HEAT EXCHANGERS (HE)

The simplest form of a

Devices where two Widely used in various
heat exchanger is a
moving fluid streams industries, and they
double-tube heat
exchange heat come in various
exchanger  Tube
without mixing designs
and-shell HE

Heat is transferred from Heat exchangers

the hot fluid to the cold typically involve no
one through the wall work interactions
separating them and the (w=0) and negligible
outer shell is usually well kinetic and potential
insulated to prevent any energy changes
heat loss to the (ke=0, pe=0) for
surrounding medium. each fluid stream.
Q=0
 H E AT T R A N SFER R ATE A S SO CI AT ED W I T H H E AT E X C H ANGER S
D E P EN DS O N H O W T H E C V S E L ECTE D A S A S Y S TEM

Whole system Individual system

The entire heat exchanger is selected as the control
The individual fluid is selected as the control volume
volume

Heat crosses the boundary as it flows from one fluid to

Q=0, due to insulation  no heat crosses the boundary
another  the heat transfer between two fluids, Q≠0

3 3

2 1 2 1

4 4
To determine mass flow rate (m) To determine heat transfer (Q)

MB:  m in   m out m 1  m 3  m 2  m 4 M B:  m in  m

 out m
 1 m 3  m
 2 and m 4
EB : E in  E out
EB : E in  E out
Q  m  1h1  m 2 h2 or m 3h3  Q  m  4 h4
m 1h1  m 3h3  m 2 h2  m 4 h4
 Q  m  2 h2  h1  or Q  m  3 h3  h4 
 PIPES AND DUCT FLOWS
Desirable Heat loss /
Usage
heat transfer gain
Transport of liquids or
gases in pipes and ducts
Be the sole purpose of the
is of great importance in
flow To prevent any heat loss
many engineering
applications or gain, pipes or ducts
are insulated  Heat
Eg. Water flow through the transfer in this is
Flow through a pipe or a pipes in the furnace of a negligible
duct usually satisfies the power plant, the flow of
steady-flow conditions refrigerant in a freezer, and
the flow in heat exchangers
LIQUID PUMPS
Pumps Compressed liquids Assumptions

• Work is required • Density and • Neglecting KE and

to pump. specific volumes PE.
compressed liquid are constant
in an adiabatic (v2=v1=v) .
(q=0) and steady • Process of pumping
flow process. compressed liquid
is isothermal
(u=cvdT=0).

Fluid exit, 2 MB : min  mout  m

2 2
 V   V 
EB : W  m
  h1  1  gz1   m
 
  h2  2  gz 2 
 
 2   2 
Pump
  2 2 
W h   V2  V1  
   h2  h1 
W  m     g  z 2  z1 
      
u2 u1   Pv 2  Pv 1   2
   pe  0
 ke  0 
Fluid inlet, 1  

W m u 2  u1   Pv 2  Pv 1 
Liquid flow through a pump  
u  0
 
W  m  Pv 2  Pv 1   m
 vP2  P1 
 NOZZLES (2>> 1; P2<P1)
DIFFUSERS (2<< 1; P2>P1)
[W=0, PE=0]

MIXING CHAMBER (Inlets>Outlets)

SEPARATOR (Outlets>Inlets)
[∆P=0,W=0, KE=PE=0]

STEADY-FLOW TURBINES (P2<P1; Work produced)

ENGINEERING COMPRESSORS (P2>P1; Work required)
DEVICES [KE=PE=0]
BOILERS / EVAPORATORS
(CONTROL (Liquid to Vapour)
VOLUMES)
HEAT EXCHANGERS
[∆P=0,W=0, KE=PE=0]
CONDENSERS
(Vapour to Liquid)

THROTTLING VALVE / FLASH

THROTTLING VALVES / FLASH
CHAMBERS WITH IDEAL GAS
CHAMBERS (h2=h1;T2<T1; P2<P1)
(h2=h1; T2=T1; P2<P1) [∆H=0, ∆T=0,
[∆H=0,W=0, KE=PE=0]
W=0, KE=PE=0]