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Chemical Engineering
Thermodynamics (BNQ20104)
BY:
Dr. Nadirul Hasraf Bin Mat Nayan
Department of Chemical Engineering
Faculty of Engineering Technology
Universiti Tun Hussein Onn Malaysia
+
HEA
T
POWE
R
1st
Law
Energy is
conserved, its
formed can be
converted
0th
Law
2nd
Law
Law of
Thermodynamics
Thermal
equilibrium is
transitive
Energies can
flow
independent
of
the
Energy cannot be
destroyed, it can
only change form
PE =
7
KE =
3
Conservation of energy
principle for the human
body
1 lbm = 0.45359 kg
1 ft = 0.3048 m
The
definition
of the
force units
-Thermodynamics system,
surroundings, and boundary-
- The boundary of a
system can be fixed or
movable.
- Boundary is the contact
surface shared by both
the system and the
surroundings.
- Mathematically, the
boundary has zero
thickness, thus it
neither contain any
mass nor occupy any
volume in space.
Thermodynamics
Isolated System
- Examples of closed
system:
i. Pressure cooker
ii. A rubber balloon filled with
air and tightly closed
iii. The gas confined between
a piston and cylinder
(energy)
YES
m=
constant
Mass
(energy)
YES
NO
GAS
2 kg
1 m3
Fixed
boundary
-A Closed System With A Moving
boundary-
Open System
Mass In
Energy Out
Energy In
Mass Out
Mass
Energy
Air Out
An open system (a
control volume)
with one inlet and
one exit
Energy
Yes
Mass
Transfer
No
Examples
Open
Yes
Yes
Turbines,
pumps,
valves
Isolated
No
No
Thermos
flask
Gas in sealed
container
P,
State 1
State 2
A system at two
different states
- Illustration of thermal
equilibrium -
B
100
B
50
No net heat
transfer
- 2nd Law of
Thermodynamics -
- The
- Static
- Dynamic
The upward
force
- The upward
and downward
forces cancel out
each other, so
the net force is
0.
The downward
force
- No net force
means no
acceleration!
- Static
Equilibrium -
have
no
further
2 NO2(g)
N2O4(g)
N2O4(g)
Reaction vessel
At this
point,
reactant is
being
produced
and used
up at equal
rates and
so is the
product.
Reaction begins
No products yet
formed
High rate of
collisions
between
reactant and
product
Products formed
Collisions
between
reactants
decrease
Rate of forward
reaction
decreases
Rate of forward
reaction equal to
rate of reverse
reaction
Dynamic
equilibrium
established
Concentrations
Intensive = the value of the property is not dependent on that amount of material
A process
between states 1
and 2 and the
process path
State
Process
path
i. Characteristic 1:
. No property at any given location within the system boundary
changes with time.
. That also means, during an entire steady flow process, the total
volume Vs of the system remains a constant, the total mass ms of
the system remains a constant, and that the total energy content Es
iii.Characteristic 3:
. Rates at which heat and work are transferred across the boundary of
the system remain unchanged.
e = E / m (kJ / kg)
atmospheric
CO2levels are increasing, and the major reason for this
increase is the combustion of fossil fuels.
temperature
scale
is
called
thermodynamic
Fahrenheit scale:
32 and 212F
Kelvin scale:
273.15K and
373.15K
HOT
COLD
Environme
nt
HOT
COLD
= =
Environme
nt
HOT
COLD
= =
Environme
nt
HOT
COLD
C
A
force
exerted
That is:
1 Pa = 1 N / m
Pabs=Patm+Pgauge
ii. Gauge Pressure
Pressure greater than atmospheric pressure that are measured
relative to atmospheric pressure.
Gauge pressure is the difference between the absolute pressure
and atmospheric pressure:
= P
- P
P = Patm + gh or Pgauge
C
R
E
EX E
IS
-The basic
manometer-
-The basic
manometer-
-Schematic for
in-class
In stacked-up fluid
layers, the pressure
change across a fluid
layer of density and
height h is gh.
Th
eith e work
er a
in
gas g fluid
o
c
den r a liqu an be
sity
i
is d whos
1
Di
h.
ight,
e
h
d
ui
tial fl
fferen
-The basic
barometer-
-The basic
barometer-
The standard atmospheric pressure Patm changes from 101.325 kPa at sea
level to 89.88, 79.50, 54.05, 26.5, and 5.53 kPa at altitudes of 1000, 2000,
5000, 10,000, and 20,000 meters, respectively.
For example, cooking takes longer at high altitudes since water boils at a
lower temperature at lower atmospheric pressures.
pressure
with
elevation
has
far-reaching
H and Spontaneity:
Many chemical events occur spontaneously, meaning on their own,
without the input of additional energy.
Example:
Water spontaneously freezes at -5oC ad 1 atm. It spontaneously melts at 80oC and 1 atm.
Some spontaneous changes need a little input of energy initially, but once they get rolling, it
continues without the need for this extra energy.
H and Spontaneity:
It was believed, that if a reaction was exothermic or endothermic, that
the sign of H would predict whether or not a reaction was
spontaneous.
It was also believed that exothermic reactions were spontaneous while
endothermic reactions were nonspontaneous.
While many exothermic reactions are spontaneous, there are several
real world simple examples of spontaneous endothermic reactions.
o Ice placed in your hand removes the heat from your hand and uses that heat energy to
Example:
change from a solid to a liquid.
o Water vaporizing is also an endothermic reaction.
H and Spontaneity:
Think about the order and disorder associated with solids, liquids,
gases and ions in solution.
As we proceed from the solid state to the liquid state to the gas state
disorder increases (or order decreases).
It appears that order, or lack thereof might be important for
determining if a reactions is spontaneous or not.
Therefore, there must be other factors that we must consider when
determining if a reaction is spontaneous or not.
=/
Where =
T is temperature in Kelvin
S =