CHEMICAL ENGINEERING THERMODYNAMICS

 “THERMODYNAMICS” means heat power or power derived from heat

 In its broader sense, THERMODYNAMICS is the science that deals with the transformations of all kinds of
energy from one form to another.
 Like all sciences, THERMODYNAMICS is based on experimental observations. And these findings have been
formalized into four laws, which were also given mathematical expressions, leading to a network of equations
from which practical results and conclusions may be derived.
► First Law of Thermodynamics ► Third Law of Thermodynamics
► Second Law of Thermodynamics ► Zeroth Law of Thermodynamics
 The study of thermodynamics involves adopting a macroscopic point of view. Concerns are only focused on
the effects of the action of many molecules as perceived by our senses.

Thermodynamic Systems

1. A system is defined as a region in space or a quantity of matter upon which attention is focused for study.
2. Everything that is external to the system is known as the surroundings.
3. The system is separated from the surroundings by system boundaries or control surfaces. These boundaries
may either be movable or fixed.
4. Types of Systems
a. Open System (Control Volume) - a system that allows matter to go in and out through the system
boundaries
b. Closed System (Closed Control Mass) - a system where matter does not enter or exit through the
system boundaries. Transient energy, however, can
be present. Heat and Work are transient energies.
c. Isolated System - a closed system that does not interact in any way with its surroundings.
d. Insulated System - a system that does not allow heat to enter and exit through the boundaries.
Note:
Fw
1. The system boundary, denoted by the
dotted lines, is movable.
2. Although the boundary is movable, the
Gas expands gas comprising the system does not
against the go through the boundaries.
GAS weights, doing 3. Transient energies like heat and work
work. go through the system boundary.

Q (heat applied)

Figure 1.0 A Closed System

Note:
1. The system boundary, denoted by
the dotted lines, is fixed.
Air Compressor 2. Matter (air) passes through the
boundaries.
W (work by the motor)
3. Transient energies also go through
the system boundaries.
4. Work is provided from the motor
through the driving shaft of the
compressor.
5. Heat is transferred across the
Low Pressure Air High Pressure Air boundaries from the cylinder walls.

Figure 2.0 An Open System

Fundamental Quantities

 These are quantities representing fundamental concepts which are known only from experience.

1. TIME(t) - the fundamental unit of time is the second, defined as 1 / 86,400 part of a mean solar day.
2. DISTANCE(L) - the fundamental unit of distance or length is the meter, as defined by the distance between
two marks on a platinum-iridium bar at 0oC, kept inside a vault in Sevres, France.
3. MASS(m) - the fundamental unit of mass is the kilogram, defined by a standard lump of platinum-iridium, also
kept at Sevres.
4. TEMPERATURE(T) - There are two common scales for measuring the “degree of hotness or coldness of a
substance. These are the Fahrenheit (oF) and the Centigrade or Celcius (oC) scales.
 Useful Conversions:
o
1 day = 24 hours 1 meter = 100 centimeters 1 kilogram = 1000 grams F = 1.8 x oC + 32
1 hour = 60 minutes 1 kilometer = 1000 meters 1 ton (short) = 2000 lb K = oC + 273
1 minute = 60 seconds 1 inch = 2.54 cm 1 metric ton = 1000 kg R = oF + 460
1 foot = 12 inches 1 kilogram = 2.2 pound mass
1 yard = 3 feet (lbm)

Secondary Quantities

 These are defined in terms of the basic fundamental quantities of time, distance, mass, and temperature.

1. VOLUME(V) - a common unit of volume is the liter. This is defined as the amount of space enclosed by a
cube whose edges measure 10 cm. Volume may also be looked at as the product of three
distances or lengths (i.e., cm3, ft3, in3)
2. DENSITY(ρ) - a common unit of density is kg/L (kilogram per liter). Density is the amount of mass occupying
a certain amount of space. Other common units include g/ml , lbm/ft 3 , and g/gallon.
3. SPECIFIC VOLUME(ν) - This is the amount of volume occupied by a certain amount of mass. A common
unit of specific volume is L/kg. Specific volume is the exact reciprocal of density.
4. VELOCITY(v) - This is a vector quantity denoting speed. Common units include m/s (meters per second)
and fps (feet per second). Transport vehicles normally use km/hr or mph (miles per
hour).
5. ACCELERATION(a) - Another vector quantity, this time representing the rate of change of a body’s velocity.
A common unit is m/s2 (meters per second squared).
6. FORCE(F) - defined by Newton’s Second Law as the product of a body’s mass and its acceleration. 1
Newton is equivalent to 1 kg-m/s2.
7. PRESSURE(p) - defined as the force applied per unit area. Common units include lbf/in 2 (pound force per
square inch) and N/m2 (Newton per square meter) or Pascal.
8. HEAT (Q ) - thermal energy associated with changes in temperature and / or changes in phase. A common
unit is calories.
9. WORK (W) - another form of energy defined as the product of the force applied on a body and the
subsequent distance it travels as a result of this force. Common units are ft-lbf (foot
pound force) and N-m (Newton-meter) or Joule.

FORCE

According to Newton’s Second Law of Motion, the force on a body of fixed mass is proportional to the product of the
mass and its acceleration.

F  ma F = force Force Mass Acceleration gc

F  k  ma m = mass 1 lbf 1 slug 1 ft/s2 1 slug-ft / lbf-s2
a = acceleration 1 lbf 1 lbm 32.174 ft/s2 32.174 lbm-ft / lbf-s2
ma 1 poundal 1 lbm 1 ft/s2 1 lbm-ft / poundal-s2
F  k =proportionality constant
gc 1 dyne 1 gram 1 cm/s2 1 g-cm / dyne-s2
1N 1 kg 1 m/s2 1 kg-m / N-s2
Examples:

1. Calculate the weight or force of gravity in lbf units of an object having a mass of 15.24 lbm, located at an area where the acceleration
due to gravity is 31.97 ft/s2.
mg
 15.24 lbm   31.97 ft/s 2 
 
Fw    15.14 lbf
gc 2
32.174 lbm  ft / lbf  s

2. A mass of 2 kgs is accelerated with a force of 10 lbf. What is its acceleration in ft/s 2 and cm/s2?
 2.2 lbm 
m  2 kg    4.4 lbm

 1 kg 

F gc
 10 lbf   32.174 lbm  ft / lbf  s 2 
a      73.12 ft/s 2
m 4.4 lbm
2  12 in  2.54 cm  2
a  73.12ft / s     2228.78 cm/s
 1 ft  1 in 

PRESSURE

Pressure is defined as the normal force exerted by a fluid on a unit area of surface. Pressure is associated with liquids
and gases, rarely with solids. The pressure in a liquid at rest at a given point is the same in all directions. If force is
measured in terms of lbf while area is in in2, then the unit for pressure is lbf /in2 or psi.

F P = pressure
P
A F = force
A = area
 Fw mg Vg hAg g
P     h
h A Ag c Ag c Ag c gc
g
H PA   H
gc
B C g
A PB   h  PC
gc
Hh
PA  PB PA  PC

Figure 3.0 Fluid Pressure vs. Elevation

In most thermodynamic investigations, we are often concerned with absolute pressure. Pressure and vacuum gages,
however, reflect the difference between absolute pressure and the atmospheric pressure existing at the gage. This is
referred to as the gage pressure.
Pressure above
atmospheric pressure

Absolute pressure greater than Pressure gage reading of pressure

atmospheric pressure above atmospheric (psig)

Atmospheric pressure

Vacuum gage reading of pressure

below atmospheric (psig)
Atmospheric pressure = 14.7 psi
Pressure less than
atmospheric pressure

Absolute pressure less than

atmospheric pressure

Zero pressure

Standard Atmospheric Pressure:

This is the pressure produced by a column of mercury 760mm in length. The density of mercury is 13.6 g/ml.

3
g  2.2 lbm  2.54 cm 
 Hg  13.6 3 
 
   0.4903 lbm3
cm  1000 g  1in  in
 1in 
h Hg  76 cm    29.92 in
 2.54 cm 
 32.174 ft 
g    2 
Patm   Hg h Hg   0.4903 lbm3   s
  29.92 in   14.67 psi  14.7 psi  1 atm
gc  in   32.174 lbm  ft 
2
 lbf  s 

Manometers for Pressure Readings: Figure 4.0 Manometer

at level A, Patm
PF  Patm  Pcolumn
g
PF  14.7 psi   L L
gc Fluid
For instance, if the manometer liquid is mercury PF
and L= 1 ft …… L
A
  32.174 ft 
  2  manometer
PF  14.7 psi   0.4903 lbm3   s   12 in   20.58 psia liquid
 in   32.174 lbm  ft 
2
 lbf  s 
More Useful Conversions:

1 ml = 1 cm3 1 N = 1 kg-m/s2 1 atm = 29.92 inches Hg

1000 L = 1 m3 1 N/m2 = 1 Pascal 1 atm = 101.325 kPa
1 ft3 = 7.481 gallons 1 atm = 14.7 psi 1 atm = 1.01325 bar
1 ft3 = 28.32 L 1 atm = 760 mm Hg

Examples:

1. A cylindrical piston with a diameter of 12 cm exerts a pressure of 10 lbf/in 2 above atmospheric on the gas enclosed in the cylinder.
Determine the mass of the piston, assuming standard gravitational acceleration.
2 2 2
A   d  144  cm  113.1 cm
4 4

 in 

F  PA   10 lbf2  113.1 cm  1 in

2
 2.54 cm
  2  175.31 lbf  mg
gc
 
 175.31 lbf   32.174 lbm  ft2 
F gc  lbf  s 
m   175.31 lbm
g 32.174 ft2
s
2. A mercury manometer used to measure a vacuum reads 29.3 inches while a barometer reads 29.7 inches Hg. Determine the absolute
pressure in terms of lbf/in2.
Pabs  Patm  Pvacuum
Pabs  29.7 in  29.3 in  0.4 in
3  32.174 ft2 

 g  2.2 lbm  2.54 cm 
Pabs   13.6  
   s
 0.4 in Hg   0.196 lbf2
3
 1000 g lbm  ft
 cm  1 in   32.174 
2 
in
 lbf  s 
 14.7 psia 
Pabs   0.4 in Hg     0.196 psia

 29.92 in Hg 
3. Due to the unavailability of mercury, a barometer was constructed using water in the closed column, with a certain amount of oil on top
to prevent the boiling of water. For standard atmospheric pressure of 101.325 kPa, what height of oil, in cm, will be required if the
minimum pressure at the water-oil interface is kept at 14.2 kPa? What must be the height of the water, also in cm, inside the column to
achieve the required minimum pressure at the interface? Assume the specific gravity of the oil used to be 0.92.
g
Pint   oil H
gc
 m
3  9.8 2 
 g  1 kg  100 cm  
14,200 N2   0.92  1 3  
 1m  s H oil   9016 H oil
 cm  1000 g   kg m
m   1 2 
 N s 
 m 
3  9.8 2 
N   1 g  1 kg  100 cm 
 101,325  14,200 2 3  
   s

 H
m  water
  9800 H water
m  cm  1000 g  1m   1 kg
 2 
 N s 
H oil  1.575 m H water  8.89 m

WORK

When a force acts on a body, causing it to move a certain displacement, then the action is said to have produced work.
The quantity of work done is defined as the product of the force and the distance through which it moves.
W  Fs
W = work
dW  F ds F  f s
F = force
s2
s = displacement
W 
s 1
F ds
In thermodynamics, one of the most important types of work is that which accompanies a change in the volume of a
gas. Consider the expansion or compression of a gas inside a cylinder by the movement of a piston.
Note:
dW  F ds 1. The displacement of the piston may be computed
V  P = pressure by dividing the change in the volume of the gas by
dW    PA  d   A = cross-sectional area
 A  the constant cross-sectional area.
dW   P dV V = volume 2. From the definition of pressure, force is equivalent
P  f V  to pressure multiplied by the area.
V2
3. Work can also be represented by the area under


W   P dV
the curve in the Pressure-Volume Diagram.
V1

Work and Energy:

Energy is one of the most important concepts in all of physical science, yet it is one of the most ambiguous. To
oversimplify, energy may be considered as the capacity to do work. Thus, there exists a close relationship between
work and energy. There are a number of different forms of energy and the two most common are kinetic energy and
potential energy.

1. Kinetic Energy (KE) - energy associated with motion, specifically an object’s velocity. When a force is applied
on an object, causing it to move a certain displacement, work is done. This same force also imparts an
acceleration as stated by Newton’s Second Law. Therefore, a change the object’s velocity can be expected.

dW  F ds
ma  m  dv   m  ds  m v dv
dW  ds     
 dt ds   g  dt dv  g
gc g
 c   c  c
v
m v2 m v
2  2  1 mv 2   1 mv 2 
  
  2 1   KE
W  v dv  final  KE initial
gc v1 gc  2   2 g   2 g 
  v1  c   c 

2. Potential Energy (PE) - energy associated with elevation. When a body is raised from an initial elevation to
one that is higher, a force at least equal to the body’s weight must be applied in an upward direction.

dW  F dZ
z2 mg    m g Z1 
W 
z Fw dZ  Fw  Z 2  Z1   Z2  Z1   m g Z2 
  g
  PEfinal  PEinitial

1 gc  gc   c 

Total Mechanical Energy:

P Wtotal  W p  Wgravity  KE

 m g Z1 m g Z2   1 m v 2 2   1 m v 12 
W p    
  2 g 
  
 gc gc   c   2 gc 
 1 mv 2   1 mv 2   m g Z 
Wp   2  1  2  m g Z1 
 2 gc   2 gc   gc gc 
a      
W p  KE  PE  E

Fgravity Note:
1. E = total mechanical energy
2. For free fall conditions, E = 0

Examples:

1. Gas inside a cylinder is held down by a piston, on which a number of small weights were placed. The pressure exerted by the weights
was determined to be 10 psia while the initial volume of the gas is 0.5 ft 3. If heat is applied, causing the gas to expand to a volume of 2
ft3, how much work is associated with the expansion?

W 
V2
V1 
 
P dV  P  V 2  V1    10 lbf2  12 in
 in 
 1 ft
2 3 3
 2 ft  0.5 ft   2,160 ft  lbf
 
2. A 0.84 ton automobile is traveling at 80 kph. How much work is required to bring it to a complete stop?
 W  KE
 0.84 2000
 1 mv 2
W 
 2 g
1
  1 mv 2

  2 g
2

 m
 2 gc
v 1  2 
 kg  m 
kg
20 kmhr  2  1000
1 km
m  2  1hr  2
3600s
 c   c  2 1 2 
 Ns 
W  51,851.85 N  m  51.85 KJ
3. A 4000-lbm elevator car rests 20 ft from the base of the shaft. It was raised to a height of 100 ft from the base when the cable snaps,
causing the car to plunge in freefall. A strong spring located at the bottom of the shaft eventually brought it to a stop.
a. What is the potential energy of the elevator car at its initial position with respect to the bottom of the shaft?
b. How much work is required in raising the car to the 100 ft mark at constant velocity?
c. Determine the velocity and kinetic energy of the car just before it strikes the spring.

 4000lbm   32.174 ft 
2
mg  s 
a). PE  Z2  Z1    20 ft  0 ft   80,000 ft  lbf
gc 32.174 lbm  ft2
lbf  s

 4000lbm   32.174 ft 
2
mg  s 
b). W  PE  Z2  Z1    100 f t  20 ft   320,000 ft  lbf
gc 32.174 lbm  ft2
lbf  s
c).
KE  PE  0
 1 mv 2   1 mv 2   mgZ 
 2  1  2  m g Z1 0
 2 g   2 g   
 c   c   gc gc 
 1 mv 2   mgZ 
 2  1 0
 2 gc   gc 
   
1 v 2 gZ
2 2 1

 
v2  2 g Z1  2 32.174 ft2  100 ft   80.22 ft
 s  s

1 mv
2  4000lbm  80.22 ft
s
2
KE    400,027.87 ft  lbf
2 gc  
2  32.174 lbm  ft2 
 lbf  s 

4. The turbines in a hydroelectric plant are fed by water falling from a height of 120 ft. Assuming 90% efficiency for converting the
potential to electrical energy, and 5% loss of resulting power in transmission, how many metric tons of water per hour are needed to
keep an 80-watt light bulb burning?

Basis : 1hour
W   PE   80 W  3600 s   288,000 J
Wactual  288,000  0.190  0.195   336,842.11 J
 m kg   9.8 m 
  2.541incm  1001mcm   336,842.11N  m
2
mg  s 
 h1  h 2  
kg  m
 120 f t  0 f t  12 in
1 ft
gc 1 2
Ns
358.445  m   336,842.11 N  m

m  939.732 kg  1 ton   0.94 tons

 1000kg 
HEAT

When a hot object is brought in contact with a cold object, the hot object becomes cooler while the cold object
becomes hotter. Clearly, something was transferred from the hot object to the cold object, and that something is called
heat. The transfer of heat almost always affects a change in temperature. The degree of this relationship is
dependent on the object’s capacity to absorb heat. Heat is normally expressed either in terms of calories or BTU
(British Thermal Unit). Like work, heat is also considered as transient energy.
m = mass
Q  mCT C = heat capacity (cal/g-Co and BTU/lb-Fo are numerically equal)
Q  mC  T2  T1  T = temperature

Heat transfer does not cause a change in the temperature of a body whenever a phase change is involved (i.e.,
melting of ice). Phase changes for pure substances occur at constant temperature.
 Q  m v m = mass
 v = latent heat of vaporization (cal/g or BTU/g)
Q  mf
 f = latent heat of fusion

Still More Useful Conversions:

1 calorie = 4.184 J 1 BTU = 252 calories = 778 ft-lbf 1kW=1.341 hp

Examples:

1. How much heat is needed in melting 10 lbs of ice at –10 oC by placing it at room temperature? ( Room T = 30 oC, Cice = 0.5 cal / g-C o,
Cwater = 1 cal / g-Co, fusion = 6.01kJ/mol )

QT  Q   1 0C  0C   Q melting  Q  0C  3 0C 

QT   10 lb   0.5 c al
gC
o

 0  10 C o 
 
1000g 
 2.2 lb    10 lb  6010 mol

J  4.
1 ca l
18 4 J
 
 1 mo l   100 0g 
 18.0 2 g   2.2 lb 
  
 
 ca l  o  10 00g 
  10 lb  
 1 g  Co  30  0  C 
   22,727.27 cal  362,330.86 cal  136,363.64 cal  521.42 kc
   2.2 lb 

2. The inside compartment of a calorimeter contains 300g of acetone at 20 oC while the outside compartment contains 200 g of ethylene
glycol at 110 oC. At what temperature will the two liquids equilibrate? (C acetone = 0.53 cal/g-Co and Cethylene glycol = 0.68 cal/g-Co)
Q gain  Q loss
   
 300 g   0.53  Tf  20   200 g   0.68 cal

cal
o  o
 110  Tf
 
 gC  gC 
159Tf  3180  14,960  136 Tf
o
295 Tf  18,140 Tf  61.49 C

THE FIRST LAW OF THERMODYNAMICS

Joule’s Experiments: It was discovered that a definite amount of work was required per unit mass of water for every
degree of temperature rise caused by stirring. To lower the temperature back to its initial
state, a certain amount of heat had to be removed. Energy was added to the water in the form
of work, and was retrieved in the form of heat.

Internal Energy (U) - energy stored inside a substance, manifested as the ceaseless motion of the molecules,
possessing kinetic energy, not only of translation but also vibration and rotation.

The First Law of Thermodynamics states that although energy takes many forms, the total quantity of energy is
constant, and when energy disappears in one form, it appears simultaneously in another form.

Energy system  Energy surroundin gs  0 +Q -Q

System

KE  PE  U   E surroundin gs 0 -W +W
KE  PE  U  Q  W U
U  Q  W
Note:
Q added to the system= + Heat (Q) and Work (W) are transient energies and are path dependent.
Q extracted from the system= -
W done by system = - Internal Energy (U) is a state function, just like pressure, volume, and temperature.
W done on system = + For pure substances, fixing one or two of these parameters automatically fixes the others.

Enthalpy (H) -
sum of the internal energy and the product of pressure and volume. Enthalpy, also a state function, is
particularly significant in the analysis of open systems.
H = change in enthalpy Note:
H  U  PV U = change in internal energy 1. Flow energy only occurs when fluids enter or leave an open system.
H  U  PV PV = flow energy 2. The product PV represents energy only when flow through the boundaries
of the system is involved.

Flow Energy:

Flow energy is not associated directly with the matter crossing the boundary, but is associated with the fact that
somewhere, a pumping process occurs which forces the fluid across the system boundary.
 U  KE  PE  Q  W
P1V1
U  KE  PE  Q  W s  P2V 2  P1V1 
U 2  U 1   P2V 2  P1V1   KE  PE  Q  W s
U 2  P2V 2    U 1  P1V1   KE  PE  Q  W s
Heat Exchanger

H 2  H 1  KE  PE  Q  W s
H  KE  PE  Q  W s
Turbine
P 2V 2 = work (flow energy) done on surroundings
P2V2 P 1V 1= work (flow energy) done by surroundings
W s = shaft work

Ws

Figure 5.0 Flow Energy in Open Systems

Examples:

1. Determine the changes in both internal energy and enthalpy in terms of BTU for 1 lbm of water as it is vaporized at its normal boiling
point temperature and pressure. The specific volumes of water in the liquid and vapor phases are 0.017 and 26.8 ft 3/lbm respectively.
960 BTU of heat was added to complete this vaporization.

1lbm of water at 1 atm,

Wexpansion  PV   1 atm  26.8  0.017 ft 

3 14.7 psia  144 in 2   56,694.25 ft  lbf
 1 atm  1 ft 2 
Wexpansion  56,694.25 ft  lbf  7781BTU
ft  lbf
  72.87 BTU
E  Q  W
E  960BTU  72.87 BTU  887.13 BTU
3 14.7 psia  144 in 2 
H  E  PV  887.13 BTU   1atm   26.8  0.017 ft    1BTU
 1 atm  1 ft 2  778 ft  lbf
 
H  887.13 BTU  72.87 BTU  960BTU

2. The mass flow rate into a steam turbine is 10,000 lbm/hr, and the heat loss is 30,000 BTU/hr. The following information are known for
the inlet and outlet streams.

Inlet conditions Outlet conditions

velocity 200 fps 600 fps
elevation from ground 16 ft 10 ft
enthalpy 1368 BTU/lbm 1152 BTU/lbm

What is the power output of the turbine (in horsepower), assuming g = 32.174 ft/s 2?

H  KE  PE  Q  W s

10,000 lbm   6002  2002  ft

2
10,000 lbm  
 32.174 ft


  hr
hr 2 2
 s 
 1152  1368 BTU 10,000 lbm
lbm hr
s

   
2  32.174 lbm  ft2   32.174 lbm  ft2 
 lbf  s   lbf  s 

  30,000 BTU  Wturbine
hr

hr

- 2,160,000 BTU  49,729,595.33 ft  lbf
hr
1BTU
778 ft  lbf
   60,000 ft hrlbf   7781BTU
ft  lbf
  30,000 BTU
hr
 2,096,157.33 BTU  30,000 BTU  Wturbine
hr hr

Wturbine  2,066,157.33 BTU

hr
 252
1BTU
cal  4.184 J  1hr   1.341hp   811.49 hp
1 cal 3600s  1000 W 

3. Air at 1 bar and 250C enters a compressor at very low velocity, discharges at 3 bar, and enters a nozzle in which it expands to a final
velocity of 600 m/s at the same pressure and temperature conditions as when it first entered the compressor. If the work of
compression is 200 kJ/kg of air, how much heat must be removed during compression?
 H  KE  PE  Q  W s
 1kg  600 m 2 

s
kg  m 

 Q    200 kJ  1000N  m
1kJ

2 1 2 
 N s 
Q   180,000  200,000 J   70 kJ Q removed  70 kJ
kg air kg air

4. In a non-flow process, the pressure increases from 50 psia to 200 psia, following the relationship PV=k. The internal energy increases
by 20 BTU and the initial volume is 3 ft3. How much heat was removed?

E  Q  W

V2 
P1V1

 
 50 psi a  3 ft 3  0.75 ft 3
P2 200 psia

W 
V2
V PdV 
V
V2
kdV
V

0.75

3

  50 psia 144 in
 ft
2
2 
 3 ft  dV

3
 V
 21,600 ln 0.75  29,943.96 ft  lbf
3
1 BTU
778 ft  lbf
 
1 1
Q  E  W  20 BTU    38.49 BTU  18.49 BTU

PROPERTIES OF PURE SUBSTANCES

A pure substance is one that has a homogeneous and invariable chemical composition even if there exists more than
one phase. Properties of pure substances can be divided into two general classes, namely intensive and extensive
properties.

If a quantity of matter in a given state is divided into two equal parts, each part will have the same value of intensive
properties as the original, and half the value of the extensive properties. Intensive properties include pressure,
temperature, and density. Mass and total volume are examples of extensive properties. Specific volume, like density,
however, is intensive.

Gibb’s Phase Rule:

The Phase Rule states that the number of known properties of a pure substance needed in order to also determine its
other properties may be computed if the number of phases and the number of components present in the said
substance is known.

P = number of phases (homogeneous region of matter)

PF C2 C = number of components (minimum number of chemical species required to prepare the system)
F = degrees of freedom (number of properties that can be independently varied)

For instance, if the degrees of freedom for a given system is equal to two, then, it means that knowing only two
properties of the system will exactly determine the state of the system, hence, all its other properties will also be
known.

Examples:

Determine the degrees of freedom for the following systems:

No. P C F=C+2-P
1 2 1 1+ 2–2=1
1. liquid water in equilibrium with its vapor
2. liquid water in equilibrium with a mixture of water vapor and nitrogen 2 2 2 2+ 2–2=2
3. liquid solution of alcohol in water in equilibrium with its vapor 3 2 2 2+ 2–2=2
4. decomposition of calcium carbonate 4 1 2 2+ 2–1=3
5. mixture of ice, liquid water, and gaseous water 5 3 1 1+ 2–3=0
6 1 2 2+2–1=3
6. CO 2  CO  1 2 O 2

The Ideal Gas Law:

The simplest P-V-T relationship for pure substances in the gaseous phase is the Ideal Gas Law. For pure gases, the
Phase Rule dictates that 2 properties can be varied independently to determine the other properties.
P V T n R
atm ft3 R lbmole 0.73 atm-ft3/lbmole-R
PV  nRT
psia ft3 R lbmole 10.73 psia-ft3/lbmole-R
lbf/ft2 ft3 R lbmole 1545 ft-lbf/lbmole-R
P = pressure n = moles atm ft3 K lbmole 1.314 atm-ft3/lbmole-K
T = temperature R = Gas constant (units depend atm cm3 K gmole 82.06 atm-cm3/gmole-K
V = volume on P, T, V, and n) BTU R lbmole 1.987 BTU/lbmole-R
calories K gmole 1.987 cal/gmole-K
 Examples:

1. Air is pumped into a 0.5 m3 tank until the pressure is 120 psig. When the pumped is stopped, the temperature is 210 oF. What mass is
in the tank and what is its density? What is the pressure if the air is then cooled to 80 oF?

V  0.5 m
3
 1 010mc m  3  2.514inc m  3  112ftin  3  1 7.66 ft 3
T   21 0  460 R  6 70R P   1 20  1 4.7  p sia  1 34.7 ps ia

n  PV 

 1 3 4.7 p s ia 1 7.6 6 ft 3

0.33 1lb mo l 
m   0.3 31lbmol 29 lb m   9.6 0lb m   9.6 lb m  0
RT  3  lb mo l 1 7.6 6 ft
3
 1 0.7 3 psi a ft   6 7 0R 
 l bm ol  R 
 
T2   80  46 0 R  5 40R
 3 
 0.3 3 1lb m o l  1 0.7 3 psi a ft
l bm ol R
  5 4 0R 

n RT2  
P2    1 08.5 6 p sia
V 1 7.6 6 ft
3

2. The height of a cylindrical tank, containing 10 lbm of gas at 60 psia and 320K, measures three times its diameter. If the gas constant is
50 ft-lbf/lbm-R, what are the dimensions of the tank in feet?

 2
P   60 psia  12 in  8640 lbf2
1 ft
 ft

T   320 K  1.8 R  576 R
K

 10 lbm   50 fft lbf  576 R  3 2 2 3
V  mRT  lbm R
 33.33 ft  D h  D  3D   3D
P 8640 lbf2 4 4 4
ft

D3

33.33 ft  4 
3
  2.419 ft
3
h  3D  7.256 ft

Other Equations of State for Gases:

1. Van der Waal’s Equation:

a and b = constants, characteristic of the gas
 
 P  a2  V  b   RT T c = critical temperature
 V  P c = critical pressure
2
27R Tc 2 RTc Note: Actual pressure is less than ideal, while actual volume is
a b 
64Pc 8Pc greater than ideal.

2. Compressibility Factor

Vactual Vactual PV V c = critical volume Note:

Z  nRT  actual T c = critical temperature The compressibility factor, Z, can normally be taken
Vpredicted P
nRT
P c = critical pressure from the Generalized Compressibility Factor Diagram,
PVactual  nZRT Z = compressibility factor which introduces two additional parameters, P r and Tr,
T r = reduced temperature the reduced temperature and reduced pressure.
Pr  P Tr  T P r = reduced pressure
Pc Tc

Examples:

1. It is required to store 1 lbmole of methane at a temperature of 122 oF and a pressure of 600 atm. What is the volume of the vessel that
must be provided based on: a). the Ideal Gas Law, b). the Van der Waal’s Equation, and c). the Compressibility Factor method?
(Tc = 190K, Pc = 46 atm, Z = 1.34)

 1lbmol   0.73 
3
atm  fft
  122 460 R
a).  lbmol  R
 3
V  nRT   0.708 ft
P 600 atm

b).
 2

27R Tc
2 2

27  0.73 atm  fft
lbmol R
3
  190 K 
2
1.8 R
K
2 6
a      783.07 atm  ft2
64Pc 64 46 atm
 lbmol

RTc

 0.73 atm  fft
lbmol R
3
  190K  1.8  R
K
 3
b      0.678 ft
8Pc 8  46 atm  lbmol
 
 P  a2  V  b   RT
 V 
  3
 600  783.207  V  0.678   0.73 582 V  0.984 ft
 V 

 1lbmol  1.34  0.73 

3
atm  fft
  122  460 R
c).  lbmol  R
 3
V  nZRT   0.95 ft
P 600 atm

2. 3 lbmol of ammonia, initially at 20 atm and 400 oF, occupies 100 ft3. It was then compressed to 50 ft 3 and a final temperature of 500oF.
What is the %difference in the computed final pressure between the Ideal Gas Law and the compressibility factor method?

 3 
3 lbmol   0.73 atm  fft
lbmol R
  960 R 
P  nRT     42.05 atm
V 50 ft
3

ZR  PV
P1V1 PV PV T
P2   1 1  2  
 
 20 atm  100 ft 3  960 R   44.65 atm
nT T1
 2 2
T2  T1  V2   860 R  50 ft 3  
%D  44.65  42.05 x 100  6.19%
42.05

3. What will be the temperature of propane when it has a specific volume of 0.102 ft 3/lbm and a pressure of 1000 psia using the
Generalized Compressibility Chart? For propane, Tc = 665 R, Pc = 618 psia, R = 35 ft-lbf/lbm-R.


 1000 lbf
2
 121 fftin  2 0.102 lbm

 fft
3 

T  PV   in     419.657
mZR Z  35 lbm fft  lbf 
R
Z
1000psia
Pr  P   1.618 Tr  T  T
Pc 618 psia Tc 665
assume T  765 R , Tr  765  1.15
665
From the Generalized Compressibility Chart, Z  0.55
T  419.657  763.01R
0.55

Thermodynamic Properties of Steam (Steam Table / Mollier’s Diagram):

1. Saturation Temperature - temperature at which vaporization or condensation takes place at a given pressure.
2. Saturation Pressure - pressure where vaporization or condensation occurs
3. Saturated Liquid - liquid existing at the point of saturated temperature and saturated pressure.
4. Saturated Vapor - vapor existing at the point of saturated temperature and saturated pressure.
5. Subcooled Liquid - liquid at which the temperature is lower than the saturation pressure at a given pressure
(compressed liquid).
6. Superheated Vapor - vapor at which the temp. is higher than that at saturation conditions for a given pressure
7. Quality - the ratio of the mass of vapor to the total mass when substances exist as a mixture of liquid and vapor.
8. Triple Point - the point at which solid, liquid, vapor exist in equilibrium.

Saturated Steam Table:

Temperatur Absolute Pressure Specific Volume Enthalpy Entropy ( )f = saturated liquid
e ( )g = saturated vapor
o
F psia inches Hg vf vg hf hg sf sg
32.0 0.0886 0.181 0.01602 3305.7 0.0 1075.1 0.0 2.1865 v = ft3/lbm
86.0 0.6153 1.253 0.01609 527.6 54.01 1098.4 0.1042 2.0181 h = BTU/lbm
122.0 1.7880 3.640 0.01621 193.18 89.91 1114.0 0.1679 1.9285 s = BTU/lbm-R
212.0 14.696 29.92 0.01672 26.83 180.07 1150.4 0.3120 1.7566 x = steam quality
390.0 220.29 - 0.01850 2.083 364.17 1199.9 0.5540 1.5375
570.0 1226.7 - 0.02240 0.3528 575.4 1181.9 0.7737 1.3627
h mix   1  x  h f   x  h g s mix   1  x  s f   x  s g v mix   1  x  v f   x  v g

Examples:

1. During the vaporization of water at 1 atm, a sample was found to have a quality of 0.68. How much enthalpy will this sample possess?
 h mix   1  x  h f   x  h g
h mix   1  0.68 180.07   0.68 1150.4   839.89 BTU
lbm

2. At room temperature of 30oC, the specific volume of a water and steam mixture is 60 ft 3/lbm. Determine the enthalpy of the mixture.

v mix   1  x  v f   x  v g   1  x  0.01609   x  527.6   60

527.584x  59.984 x  0.114
h mix   1  0.114 54.01   0.114 1098.4   173.07 BTU
lbm

Superheated Steam Table:

Absolute Saturated Saturated Temperature ( oF)

Pressure Liquid Vapor 200 300 400 500 600 700 800
(Saturation T)
1.0 psia v 0.0161 333.79 392.50 452.10 511.70 571.30 630.90 690.60 750.20
(101.76oF) h 69.720 1105.2 1149.2 1194.4 1240.2 1286.7 1333.9 1382.1 1431.0
s 0.1326 1.9769 2.0491 2.1128 2.1694 2.2206 2.2673 2.3107 2.3512
14.7 psia v 0.0167 26.828 - 30.520 34.650 38.750 42.830 46.910 50.970
(212.0oF) h 180.07 1150.4 - 1192.0 1238.9 1285.4 1333.0 1381.4 1430.5
s 0.3120 1.7566 - 1.8148 1.8727 1.9238 1.9709 2.0145 2.0551
30.0 psia v 0.0170 13.763 - 14.820 16.890 18.920 20.940 22.940 24.940
(250.34oF) h 218.83 1164.0 - 1189.2 1237.4 1284.2 1332.1 1380.8 1429.9
s 0.3680 1.6992 - 1.7335 1.7930 1.8444 1.8918 1.9357 1.9763

Examples:

1. Determine the enthalpy of superheated steam at 420 oF and 30 psia.

h  1237.4
1284.2  1237.4
 420 400
500 400
 100 
h  1237.4   46.8  20 h  1246.76 BTU
lbm

2. Superheated steam at atmospheric pressure and 560 oF is cooled at constant pressure until it is partially liquefied. How much enthalpy
change was involved if its final quality is 0.45?

h1  1285.4
1333 1285.4
 560 500
600 500
h 1  1285.4   47.6   400
40  h 1  1304.44 BTU
lbm
h 2   1  x  hf   x  h g
h 2   1  0.45 180.07   0.45 1150.4   616.72 BTU h 2  h 1  687.72 BTU
lbm lbm

THERMODYNAMIC PROCESSES

1. Isometric (Constant Volume) 4. Adiabatic (Q=0)

U  Q  W U  Q  W U  W
T2
U  Q  C v  T 
T1
Cv dT
Cv dT  PdV  RT dV
V
2. Isobaric (Constant Pressure) dT   R dV
T Cv V
H  Q  W s
Cp C R
T2    v  1 R
H  Q  C p  T 
T 1
C p dT Cv Cv Cv
dT     1 dV
dH  dU  d  PV  T V
C p dT  Cv dT  RdT T V
C p  Cv  R ln 2     1 ln 2
T1 V1
3. Isothermal (Constant Temperature)  1
  1 
T2 V
U  Q  W  0 T1 V
 2 
V2 V2  1
Q W 
V1
PdV 
V 1
nRT dV
V
T2
T1
  2 
P
 P1 


V2 P
W  nRT ln  nRT ln 1 W   U  Cv T   R T
V1 P2
 1
RT1  RT2 PV P V
W   11 2 2
 1  1
The Throttling Process:
This is a steady flow process across a restriction, which causes a drop in pressure. A typical example is the flow
through a partially-opened valve. In most cases, this happens so rapidly and in such a small place, that there is
neither sufficient time nor large enough area for much heat transfer. Therefore, this process may be assumed to be
adiabatic.

H  KE  PE  Q  W s
H   KE  0

There is no work, no change in potential energy, and no heat transfer. However, the specific volume always increases
after undergoing a throttling process, and therefore if the cross-sectional area of the conduit is constant, there will be
an increase in the velocity of the fluid as well. In reality, this change in velocity is often negligible because the diameter
of the conduit is rarely kept constant (i.e., diameter of the exit pipe is larger than the inlet). Hence, change in enthalpy
may be considered zero.

Examples:

1. Air is to be compressed reversibly from an initial condition of 1 atm and 60 oF to a final state of 5 atm and 60 oF by the following
processes: a). heating at constant volume then cooling at constant pressure, b). isothermal compression, and c). adiabatic
compression followed by cooling at constant volume. At these conditions, air may be considered an ideal gas having constant heat
capacities of Cv = 5 BTU/lbmol-Fo, Cp = 7 BTU/lbmol-Fo. Calculate the work required, the heat transferred, and the changes in internal
energy and enthalpy of air for each of the processes.

a). Basis: 1 lbmole

 3 
 0.73 atm f f t
l bm ol R
  60  460 R
  3
V  nRT   379.6 ft
P 1 atm

T2 
P2V

5 
atm  379.6 ft
3
  2600 R  2140 F
o
nR at m f f t
3
0.73 l bm ol R

 
U  Q  W U  Q  Cv T   5 BTU
o 
 2140  60 o F  10,400 BTU
 lbmol  F 
 
 H  2  Q  Ws  H  2  Q  C p T   7 BTU
o 
 60  2140 o F  14,560 BTU
 lbmol  F 
 
 U  2  Q W  U  2
 Cv  T   5 BTU
o 
 60  2140 o F  10,400 BTU
 lbmol  F 
W 2   H  2   U  2  14,560    10,400  4160 BTU

b). Basis: 1 lbmole

Q  W  RT ln
P1
P2

 1.987 BTU
lbmol R
 520R  ln 1 atm  1662.94 BTU
5 atm

c). Basis: 1 lbmole

 3
 0.73 a tm fft
lbm ol R
  60  460 R
3
V 2  nRT     75.92 ft
P 5 atm
Cp
   7  1.4
Cv 5
 1

 
 1 
 V1    2 
P   V1    P2  379.6 1.4   P2  P2  9.52 atm
 V   V   P   1 atm 
 2   P1   2   1  75.92  

U  W  
RT1 

1   2 
P
 1 

BT U 
   1.987 lbm olR  520 R  1  9.52  1 .4  1 
 
 1  
1 .4
  2334.33 BTU
 P1  1.4- 1 

1

 

ΔH  ΔU  ΔPV  2334.33   9.52 atm   75.92 ft    1 atm  379.6 ft   

 
3
 
3 14.7 psia  12 in 2
   1 atm  1 f t
 1 BTU 
778 ft  lbf
 
H  3268BTU