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ChE 122

Chemical Engineering Thermodynamics I

Thermodynamics- thermos hot, therme-heat, dynamis-strength/power


-it is a science which deals with the transformations of energy of all kinds from one form to another.

Limitation of Thermodynamics:
It does not establish the rates of chemical or physical processes
It is concerned with the macroscopic quantities; not the microscopic variables that characterize
individual molecules.
Dimension- a measure of a physical variable but it does not have numerical value.
7 primary dimensions:
1. Length
2. Mass
3. Time
4. Temperature
5. Electric current
6. Amount of matter
7. Amount of light
Secondary dimensions:
1. Force
2. Acceleration
3. Power
4. Energy

Unit- is a way to assign a number or measurement to that dimension. (SI/metric units, English units,
British units)
Definition of SI Base Units:
1. Meter (m)- length of the path travelled by the light in the vacuum during a time interval
1/299,792,458 of a second
2. Kilogram (kg)- mass of international prototype kilogram (cylinder of platinum and platinum-
indium alloy)
3. Second (s)- duration of 9,192,631,770 cycles of periods of the radiation corresponding to the
transition between the two-hyperfine levels of the ground state of the Cesium 133 atom.

Measures of amount or size


Mass, m
Number of moles, n
Total Volume, Vt

Number of Moles n=m/M where M=molar mass


Specific Volume V=Vt/m
Molar Volume V=Vt/n

Exercise:
Mark and his friends are having a bonding session. His friend dared him to calculate the no. of
moles of ethyl alcohol in a 500-ml, 6.9% ABV liquor. (density of ethyl alcohol=0.79 g/ml)
Ans. (n=0.59 moles of C2H5OH)
Force
SI unit - Newton (N)
English - Pound Force (lbf)
F=ma ,where m=kg , a=acceleration (m/s2)
F=ma(1/gc) ,where m=lbm , a=acceleration (ft/s2) , gc=32.1740 (lbm ft)/(lbf s2)

Exercise:
So as to post something #YOLO-worthy picture on Facebook, Jay tried skydiving. Just before
opening his parachute, Jay with a mass of 50 kg reaches its terminal velocity. Calculate the force of air
resistance.
Ans. (F=490.50 N)

Temperature
Celsius: Fahrenheit: Kelvin: Rankine
t(oC) = t(K) - 273.15 t(R) = 1.8 t(K)
t(oF)= t(R) 495.67 t(oF)= 1.8 t(oC) +32

Pressure
Pascal (Pa) = N/m2 P=Force/Area

Exercise:
At what certain temperature of the oC and oF where they have the same numerical values?
Ans. (-40 oC = -40 oF)

Work
Joules=Newton-m (N-m); foot-pound force (ft-lbf)
dW=Fdl
P=F/A ; F=PA ; L=Vt/A
t
dW=PA d(V /A)
dW=PdVt at constant Pressure
Energy
Kinetic Energy
dW=Fdl ; F=ma
dW=ma dl ; a=du/dt
dW=m(du/dt) dl ; u=dl/dt ; dl=u dt
dW=mu du ; u-velocity
=

= 2 (2 2 1 2 )

= (2 2 1 2 )
2
Potential Energy
W=Fdl
= m=mass; z=height; g=gravitational constant

Heat
Calories; Btu
Calories- amount of energy needed to raise 1 gram of H2O to 1oCelsius
= where Cp- specific heat capacity (J/gram oC)
Seatwork:
1. Pressures up to 2,000 bar are measured with a dead-weight gauge. The piston diameter is 3.5
mm. What is the approximate mass in kg of the weights required?
2. An automobile having a mass of 1,250 kg is travelling at 40 m/s. what is its kinetic energy in KJ?
How much work must be done to bring it to a stop?

Assignment:
What is the 1st law of thermodynamics?
Give one example of the application of this law.

Zeroth Law of Thermodynamics


If two systems A & B, are in thermal equilibrium with a third system, C, then A and B are in
thermal equilibrium with each other.

Joules Experiment
Q=AL

System- the region in which the process occur around which a boundary can be drawn.
Surroundings- everything in with which the system interacts

Internal Energy
-Energy of the molecules internal to the substance
-It is the total energy of a closed system
-Express as change in internal energy

1st Law of Thermodynamics


Although energy assumes many form, the total quantity of energy is constant, and when energy
disappears in one form, it appears simultaneously in other forms.
( ) + ( ) = 0

Closed Systems- the boundary of a system does not permit the transfer of matter between the system
and its surroundings, thus mass is constant.

Open Systems- the boundary of a system permits the transfer of matter between the system and its
surroundings, thus mass is transferred.

Extensive Properties- Depend on the quantity of material in a system. (e.g. Total Volume & Total
Internal Energy). Molar volume vs Specific Volume.

Intensive Properties-Independent of the quantity of material in a system. (e.g. Temperature & Pressure)

Energy Balance for Closed Systems


( ) =
( ) =
( ) = +
= +
() = = +
() = = +
+ =
=
+ =
=

Exercise:
A gas in a system has constant pressure. The surroundings around the system lose 62 J of heat
and does 474 J of work onto the system. What is the internal energy of the system?
= + = (+62 ) + (+474 ) = 536

State Functions
Property whose value does not depend on the path taken to reach that specific value (Path
Independent)

Thermodynamic State
This is defined by specifying values of a set of measurable properties to determine all other
properties.

For a closed system undergoing the same change in state by several processes, experiment
shoes that the amount of heat and work required differ from different processes, but that the sum Q+W
is the same for all processes.

Exercise:
One mole of gas in a closed system undergoes a four-step thermodynamic cycle. Use the data
given in the table to determine numerical values for the missing quantities.
Step
1-2 -200 -6,000
2-3 -3,800
3-4 -800 300
4-1 4,700
1-2-3-4 0 -1400
Answer:
Step
1-2 -200 5,800 -6,000
2-3 -4000 -3,800 -200
3-4 -500 -800 300
4-1 4,700 200 4,500
1-2-3-4 0 1400 -1400

A closed system consisting of an elastic membrane enclosing a colloidal suspension is squeezed.


The compressive Pressure is 10 Pa and the volume of the system changes from 100 L to 80 L. During this
process, 1 J of heat is released. Calculate the change in internal energy of the system.
Solution:
=
Work done to the system (+)
Work done by the system (-)
Compression W=(+)
= +
=
= (2 1 )
= 10 (80 100 )
13 3
= 10 (80 3 100 3 )( 3 )
10 3
3
= 0.2

= 0.2 2 3

= 0.2
= 0.2

= +
= 1 + 0.2
Final Answer: = .

Seatwork:

1. An egg, initially at rest, is dropped onto a concrete surface and breaks. With the egg treated as the
system.
a) What is the sign of ?
b) What is the sign of ?
c) What is the sign of ?
d) What is the sign of ?
e) What is the sign of ?

2. Heat in the amount of 10 kJ is added to a closed system while its internal energy decreases by 15 kJ.
How much is transferred as work? For a process causing the same change of state but for which the
work is zero, How much heat is transferred?

Assignment:

In thermodynamic sense, describe the following:

1. Equilibrium
2. Phase Rule
3. Reversible Process
Equilibrium
It is the absence of any tendency toward change on a macroscopic scale.
Systems at equilibrium = no change in state can occur
All forces are in exact balance
Equilibrium Conditions:
1. Mechanical Equilibrium- No unbalanced forces within the system and between the system
and its surrounding. Pressure throughout the system and between the system and surrounding
is same.
2. Chemical Equilibrium- No chemical reactions going on within the system or there is no
transfer of matter from one part of the system to the other due to diffusion.
3. Thermal Equilibrium- Temperature of the system is uniform and not changing throughout the
system and in the surroundings.
Phase Rule
=+
=
=
=
Process- the system undergoes a change from its initial state to its final state
Reversible process- the direction of the process can be reversed at any point by an infinitesimal change
in external conditions.
Frictionless
Never more than differentially removed from equilibrium
Transverses a succession of equilibrium states
Flow (mass or heat) occurs when the net driving force is differential in size
=
2
=
1
() = ()
Exercise:
1. A horizontal piston-cylinder arrangement is place in a constant-temperature bath. The piston
sides in the cylinder with negligible friction, and an external force holds it in place against an initial gas
pressure of 14 bar. The initial gas volume is 0.03 m3. The external force on the piston is reduced
gradually, and the gas expands isothermally as its volume doubles. If the volume of the gas is related to
its pressure so that the product PVt is constant, what is the work done by the gas in moving the external
force?
How much work would be done if the external force were suddenly reduced to its initial value
instead of being gradually reduced?
NOTE! Wreversible > Wirreversible
Constant Volume Process
Work is zero
Isochoric Process
=
Constant Pressure Process
Isobaric Process
=
= + ()
= +
Enthalpy
Thermodynamic property of a system
Sum of the Internal Energy added to the product of pressure and volume of the system.
Capacity to don non-mechanical work and release heat.
Allows to determine whether a reaction is endothermic or exothermic
Used to calculate the heat of reaction of a chemical process
Measure heat floe in calorimetry
Evaluate throttling processes in Joule-Thomson expansion

Exercise:
1. A container of gas is compressed from state 1 to state 2 via the two paths shown in the figure
below. Path A goes through state A and path B goes through state B. Calculate and compare the work
done in compressing the gas by the two paths.
Check phone for graph and solution.

2. Calculate and for 1 kg of water when it is vaporized at the constant temperature of


100oC and the constant pressure of 101.33 kPa. The specific volumes of liquid and vapor water at these
conditions are 0.00104 m3/kg and 1.673 m3/kg. For this change, heat in the amount of 2,256.9 kJ is
added to the water.

Heat Capacity
It is the amount of heat required to change its temperature by one degree.
The smaller the temperature change in a body caused by the transfer, the greater is its capacity.

=

Heat Capacity at Constant Volume

= ( )

=
2
=
1
2
= =
1
Heat Capacity at Constant Pressure

= ( )

=
2
=
1
2
= =
1

NOTE!
= Constant Volume
= Constant Pressure
Exercise:
1. One Kg of liquid water at 180oC and 1,002.7 kPa has an internal energy (on an arbitrary scale) of
762.0 kJ/kg and its specific volume of 1.123 cm3/g.
a) What is the enthalpy?
b) The water is brought to the vapor state at 300oC and 1,500 kPa where its internal energy is
2,784.4 kJ/kg and its specific volume is 169.7 cm3/g. Calculate and for the process.

2. One kilogram of air is heated reversibly at constant pressure from an initial state of 300 K and 1
bar until its volume triples. Calculate W, Q, , and for the process. Assume for air that PV/T= 83.14
bar cm3 mol-1 K-1 and CP = 29 J mol-1 K-1

Mass and Energy Balance for an Open System

Measures of Flow
Mass Flowrate = where M= molar mass

=

Thus, =
Molar Flowrate
Volumetric Flowrate
Velocity

Control Volume- It is the region of space for analysis for open systems.
Control Surface- It separates control volume to its surroundings.

Mass Balance:
Accumulation in the System= In-Out + Generation- Consumption

Closed System: no mass balance no mass transfer taking place

Open System (Constant Volume): Accumulation in the system= Mass in Mass out
()
+ = 0

At Steady State:
= 0
=
1 = 2
=

Exercise:
Consider the flow of liquid water at 25oC in a horizontal pipe. For one of the sets of conditions
given below. Determine mass flowrate (kg/s) and the molar flowrate (kmol/s). Note: Density=996 kg/m 3
a) D=2 cm, u=1 m/s
b) D=5 cm, u=1 m/s
c) D=2 cm, u=5 m/s
d) D=5 cm, u=5 m/s
General Energy Equation:
( ) = + + = +

Energy Balance for a Closed System:


= +

Energy Balance for an Open System:


Energy in: ( + + ) + +
Energy out: ( + + )
()
= ( + + ) + +

= +
= ()
() = ( )
(+) in= work done to the System
(-) out=work done by the System
Thus:
()
= ( + + ) + + ()

If no shaft work:
= ()
()
= ( + + + ) + +

= +
()
= ( + + + ) + +

Open Steady State System:
= +
= +
= +
Closed Steady State System:
= +
= + +
Exercise:
1. A stream of warm water is produced in a steady-flow mixing process by combining 1.0 kg/s of
cool water at 250C with 0.8 kg/s of hot water at 750C. During mixing, heat is lost to the
surroundings at the rate of 30 kJ/s. What is the temperature of the warm-water stream?
Assume the specific heat of water is constant at 4.18 kJ/kg K.
2. Water flows through a horizontal coil heated from the outside by high temperature flue gas. As
it passes through the coil, the water changes state from liquid at 200 kPa and 80oC to vapor at
100 kPa and 125OC. Its entering velocity is 3 m/s, and its exit velocity is 200 m/s. Determine the
heat transferred through the coil per unit mass of water. Enthalpies of the inlet and outlet
streams are: Inlet=334.9 kJ/kg ; Outlet: 2,726.5 kJ/kg
Calorimetry
It is used to measure amounts of heat transferred to or from the substance
Heat is exchanged with a calibrated object (calorimeter)
Change in temperature is converted to amount of heat
Ex. Coffee Cup Calorimeter & Bomb calorimeter
=
=
= +
=
=
Exercise:
1. 1.150 g of sucrose goes through a combustion in a bomb calorimeter. If the temperature rose
from 23.43oC to 27.64oC and the heat capacity of the calorimeter is 4.90 kJ/oC, then determine
the heat of combustion of sucrose, C12H22011, in kJ/mole of C12H22011.
=

=


=

2. Comment on the feasibility of cooling your kitchen in the summer by opening the door to the
electrically powered refrigerator.