Chapter 1

Introduction and Fundamental

Concepts
Thermodynamics means:
 Heat power or power developed from heat

 Transformations of energy from one kind to another

 Chemical Engineer: the most important problems to solve are

the determination of heat and work requirements, and the
determination of equilibrium conditions.

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 Definitions and Fundamental Concepts
 System
Any part of the universe we choose to
study or analyze. A system may be
enclosed in real boundaries, or the
boundaries may be imaginary. The
boundaries may also either be
movable or rigid. A system should
always be DEFINED.
 Surroundings
The remainder of the universe after
the system has been chosen. Only
the part that is affected by the
processes occurring within the system
is taken into consideration.

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Types of Systems:
 Open system
Exchange of mass and energy with
surroundings is possible

 Closed system
No exchange of mass between a system and
the surroundings. Heat and work may be
exchanged, therefore changes in Internal
energy and volume may occur.

 Isolated system
Can exchange neither energy nor matter with
its surroundings. This is a system, which is
totally unaffected by the changes in its
surroundings.

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Processes
The changes taking place within the system is referred to as
a process. (e.g. hydrocarbon fuel and oxygen in a
combustion chamber)

 Isothermal Process
Any process occurring in a system taking place at a
constant temperature. To maintain the constant
temperature, the system has to exchange heat with the
surroundings.

 Adiabatic Process
A process occurring in either an open or closed system
without the exchange of heat with the surroundings.
(Perfect insulation against the flow of heat). NB: This does
not mean that heat cannot be generated within the system.

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 Isobaric Process
A system in which the pressure of the working fluid remains
constant from the initial to its final state

 Isochoric Process
A system in which the volume of the working fluid remains
constant from the initial to its final state

 Isentropic Process
A system in which no heat crosses the system boundary
NB: this process is thermodynamically reversible

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Properties and Variables

 State Variable
A variable whose value depends on the
state in which the system exists.
e.g. Temperature, Pressure, Volume

 Path variable
Changes depend on the path traveled by
the system. These variables have meaning
only when applied to a process in which a
path exists between two states and that
path is specified.
e.g. Work, Heat

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 Extensive Property
A property which depends on the size of the system
e.g. Volume NB: When the system
is homogenous, an
extensive property can
be converted into an
intensive property by
dividing by the total
quantity of the system
 Intensive Property
Properties which do not depend on the size of the system
e.g. Temperature, Pressure, Specific Volume

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Equilibrium

Denotes a static condition, or the absence of change.

Thermodynamically speaking – the absence of any tendency

toward change on a macroscopic scale.

No change in state can occur.

Changes in state are caused by a driving force – therefore there
can be no driving force at equilibrium. All forces are in exact
balance at equilibrium.

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Force
The SI unit of force is Newton and the symbol is N

F=ma
Force = mass x acceleration
N = kg x m/s2

The Newton is defined as the force which when applied to a

mass of 1kg produces an acceleration of 1m/s2.
Therefore 1N = 1kg.m.s-2.

1
In terms of Pound Force (lbf): F ma
gc
a = 32.174 ft/s2, gc (dimensional constant) = 32.174 (lbm)(ft)(lbf)-
1(s)-2

Conversion(s): 1 lbf = 4.4482216 N

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Example 1(pp4)
An astronaut weighs 730 N in Houston, Texas, where the local
acceleration of gravity is g = 9.792 m/s2. What are the
astronaut’s mass and weight on the moon,where g = 1.67
m/s2?
Solution
F  ma
F  mg
F 730
m   74.55kg
g 9.792
weight of astronaut on moon is:
F (moon)  mg  74.55x1.67  124.5N
Example 2
A block of iron weighs 1.120 lbf at a location on earth where the
acceleration due to gravity is 32.05 ft/s2. What would this
block weigh on the planet Krypton, where g = 260 ft/s2?
Solution
To find the mass of the block on earth
Fxg c 1.120 x32.17
m   1.124lb
g 32.05
The force of the block on Krypton is
mg 1.124 x 260
F   9.084lb f Chemical Engineering Thermodynamics -
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Temperature
There are various definitions of temperature.

Temperature is a numerical measure of the degree of hotness

Temperature is a measure of the kinetic energy of a

homogenous set of molecules

S.I. Units: Kelvin and degree Celsius

British Units: Rankine and Fahrenheit

Conversions:
t 0C = T K – 273.15
T (R) = 1.8 T K
t (0F) = T (R) – 459.67
t (0F) 1.8 t0C + 32

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VOLUME

Volume is a property associated with cubic measure.

S.I. Units: cubic meter (m3)

If the volume of a substance increases, the substance has

expanded
If the volume of a substance decreases, the substance has
been compressed

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Pressure

Pressure is defined as force per unit area. If a force, F, is

applied to an area, A, and if this force is uniformly distributed
over the area, then the pressure, P, exerted is given by the
equation: F
P
A
If F is the force in Newton and A is the area in Meter Square,
The unit of pressure is Newton/meter2 (N/m2) – Basic S.I Unit

Other units: Pa = 1N/m2

1 Bar = 105 N/m2

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Absolute pressures must be used in thermodynamic
calculations

Absolute pressure = atmospheric pressure + gauge pressure

OR
Absolute pressure = atmospheric pressure – vacuum
pressure

Pressure is also expressed as the equivalent height of the fluid

column (i.e. manometers)

P  hg

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Example 3 (pp8)
A dead weight gauge with a 1cm diameter piston is used to
measure pressure very accurately. A mass of 6.14kg (including
piston and pan) brings it into balance. If the local acceleration of
gravity is 9.82 m/s2. What is the gauge pressure being
measured? If the barometric pressure is 748 (torr), what is the
absolute pressure?

Solution
F  mg  6.14 x9.82  60.295N
F 60.295
Gauge Pr essure    76.77 N .cm 2
A (1 / 4)( )(1) 2

The absolute pressure is therefore:

P  76.77  (748)(0.013332)  86.47 N .cm 2

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Example 4 (pp8)
At 270C the reading on a manometer filled with mercury is
60.5cm. The local acceleration of gravity is 9.784m/s2. To what
pressure does this height of mercury correspond?

Example 5
A special manometer fluid has a specific gravity of 2.95 g/cm3
and is used to measure a pressure of 1.15 bar at a location
where the barometric pressure is 760 mmHg. What height will
the manometer fluid indicate? The gravitational acceleration is
9.81 m/s2.

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