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ChE 122 Lecture notes 02 (2.1 2.6 of syllabus)

STATEMENT OF FIRST LAW, FORMS OF ENERGY,
THERMODYNAMIC SYSTEMS, THERMODYNAMIC
STATES, STATE PROPERTIES, PHASE RULE,
REVERSIBLE AND IRREVERSIBLE PROCESSES
STATEMENT OF THE FIRST LAW OF
THERMODYNAMICS
Although energy assumes many forms, the total
quantity of energy is constant and when energy
disappears in one form it appears simultaneously
in other forms.
-law of conservation of energy
- energy of universe is constant (Clausius)
Important terms:
System part in which the process occurs;
portion of the unvierse under study; it may be of
any size; boundary may be real or imaginary,
rigid or flexible
Surroundings everything with which the
system interacts; portion of the universe other
than the system
Types of Thermodynamic Systems
a. Closed system (non-flow) if the boundary
of the system does not permit the transport of
matter; mass of the system is constant; however,
energy transfer (through heat and work) is
allowed
b. Open system (steady-flow) - boundary
allows mass and energy transfer (heat and work)
c. Isolated system boundary does not allow
neither mass nor energy transfer (no heat and
work transfer); it is unaffected by its surroundings

(binding energy) that holds the molecules

together.
4. Heat (Q)
5. Flow work also known as flow energy, is the
energy required to move a mass (thermodynamic
substance) that enters a thermodynamic system
from one point to another. This energy is needed
to maintain a continuous flow of mass in a
thermodynamic system. Flow work could be
steady flow work (for open systems) or non-flow
work (for close systems).
Wflow = PV (why?)

Wflow = FL (F = force to move the substance by

certain lenth L)
Wflow = (PA)(L) = (P)(LA) = PV (ok!, if finite)
We can also use this to determine change in
work or W between two points.
Mathematically, considering a differential dh
travelled by a piston. The work done on the fluid
is (since system is closed, this is non-flow work)
dW = Fdh (but since F=PA)
dW = PAdh (but since V = Ah; dV = Adh; dh =
dV/A)
dW = PAdV/A
W

Forms of Energy (Unit Joules or

1. Kinetic energy - introduced by Lord Kelvin in
1856, energy due to motion; KE = mv2/2
2. Potential energy - energy due to position;
PE = mgh
Note: PE and KE are forms of energy resulted
from the position and motion of a system as a
whole and are regarded as external energies
3. Internal Energy, U - referes to the energy of
the molecules making up the substance. The
energy stored in a system in microscopic scale. It
is associated with the random movement of
molecules in a body, the sum of total kinetic
energy due to motion of molecules (vibration,
translation and rotation) and the potential energy

V2

dW = Pd V
0

V1

V2

W = PdV
V1

The addition of (-) sign is to conform to our sign

convention.
When the piston moves into the cylinder
so as to compress the fluid, since work is done
on system, W must be positive. Since the
change in volume is negative, the additional
minus sign is required.
a. For a finite compression/expansion

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W = -P(V2 V1)
b. For differential amount of work, equation is
retained as an integral to be evaluated
V2

W = PdV
V1

Sign convention
If energy leaves the system, it is denoted
negative. This means Q is negative if heat flows
from system to surroundings. W is negative if it is
done by the system e.g. expansion of closed
system.
Q is positive if it is added into the system. W is
positive if it is done on the system e.g.
compression of closed system.
Now that PV work is clear, this gives a better look
at Enthalpy, H as the sum of internal energy and
the PV work.
Thermodynamic State
The thermodynamic state of a system is defined
by specifying values of a set of measurable
properties sufficient to determine all other
properties. For fluid systems, typical properties
are pressure, volume and temperature.
Properties of a System
Properties may be extensive or intensive.
Extensive properties are additive. Thus, if the
system is divided into a number of sub-systems,
the value of the property for the whole system is
equal to the sum of the values for the parts.
Volume is an extensive property.
Intensive properties do not depend on the
quantity of matter present. Temperature and
pressure are intensive properties.
Specific properties properties expressed per
unit mass of the substance e.g. specific heat
capacity, specific volume
Specific properties are intensive because they do
not depend on the mass of the system.
Molar properties properties expressed per
unit mole of the substance e.g. molar volume,
molar enthalpy
Concept of a Process

If the state of a system changes, then it is

undergoing a process. The succession of states
through which the system passes defines the
path of the process. If, at the end of the process,
the properties have returned to their original
values, the system has undergone a cyclic
process or a cycle. Note that even if a system
has returned to its original state and completed a
cycle, the state of the surroundings may have
changed.
State Functions vs Path Functions
State functions - describes the equilibrium
state of a system. For example, internal
energy, enthalpy, and entropy are state
quantities because they describe quantitatively
an equilibrium state of a thermodynamic system,
irrespective of how the system arrived in that
state. Others include P, V and T. The differential
of a state function represents infinitesimal
change in value e.g.
P2

dP=P2P1= P
P1

Path functions - are properties or quantities

whose values depend on the transition of a
system from the initial state to the final state.
The two most common path functions are heat
and work. The differentials of heat and work are
not changes but infinitesimal amounts e.g.

dQ=Q
Heat and work are not properties. They account
for energy changes. They depend on the nature
of the process.
--------------------------------------------------------------------------------Exercises on Energy:
1. An automobile having a mass of 3,000 lbm is
traveling at 55 mi/hr.
a. What is its energy in ft-lbf and in BTU?
b. How much work must be done to bring it to a
stop?
2. The turbines in a hydroelectric power plant are
fed by water falling from a height of 100 ft.
Assuming 95% efficiency for converting the
potential to electric energy and 10% loss of

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resulting power in transmission, how many tons
of water per hour are needed to keep a 100 W
lightbulb burning?
Exercises on Work:
1. Steam is admitted to the cylinder of a steam
engine at a constant pressure of 300psia. The
bore of the cylinder is 8in and the stroke of the
piston is 12in. Identify the type of thermodynamic
system. How much work in ft-lb f is done per
stroke?
2. If 10lbm of water is evaporated at atmospheric
pressure until a volume of 2288.5 ft 3 is occupied,
how much work is done in ft-lbf? Identify the type
of thermodynamic system that can be assumed.
-------------------------------------------------------------------------------Equilibrium
- absence of change or any
tendency towards change on a macroscopic scale
The Phase Rule
Degrees of Freedom (F) the number of
independent variables that must be fixed to
establish the intensive state of any system;
developed by J. William Gibbs in 1875
P + F = 2 + C

(Police force = 2 cops ------ for easy

recall!)

Where P phases*, C components.

*Phase is a homogeneous region of matter;
not necessary continuous.

Basis: The state of a pure homogeneous fluid is

fixed whenever 2 intensive variables are
set at specific values (meaning F = 2 if P
=1,C =1). In contrast if 2 phases are in
equilibrium, the state of system is fixed
when only a single property is specified
(meaning F = 1 if P =2, C=1). If F = 0,
meaning the system is invariant, example
is for the triple point of water at 0.01 oC
and 0.0061 bar where P = 3, C = 1.
--------------------------------------------------------------------------------Exercises on Phase Rule:
1. Determine the degrees of freedom for each of
the following systems:
a. Liquid water in equilibrium with its vapor
b. Liquid water in equilibrium with a mixture of
water vapor and nitrogen
c. A liquid solution of alcohol in water in
equilibrium with its vapor

d. A saturated aqueous salt solution at its boiling

point with excess salt crystals present
-------------------------------------------------------------------------------Reversible and Irreversible Process
During the thermodynamic process, one or more
of the properties of the system like temperature,
pressure, volume, enthalpy or heat, entropy, etc.
changes. The second law of thermodynamics
enables us to classify all the processes under two
main categories: reversible or ideal processes
and irreversible or natural processes.
A. Reversible process - the process in which
the system and surroundings can be restored to
the initial state from the final state without
producing any changes in the thermodynamics
properties. For the system to undergo reversible
change, it should occur infinitely slowly due to
infinitesimal gradient. During reversible process
all the changes in state that occur in the system
are in thermodynamic equilibrium. In actual
practice the reversible process never occurs, thus
it is an ideal or hypothetical process.
A process is reversible when its direction can be
reversed at any point by an infinitesimal change
in external conditions.
A reversible process is
-frictionless
-is never more than differentially removed from
equilibrium
-traverses a succession of equilibrium states
-is driven by forces whose imbalance is
differential in magnitude
-can be reversed at any point by a differential
change in external conditions
-when reversed, retraces its forward path and
restores the initial state of system and
surroundings
-does not produce entropy
Processes that are usually idealized as
reversible include:
-Frictionless movement
-Restrained compression or expansion
-Energy transfer as heat due to infinitesimal
temperature nonuniformity
-Restrained chemical reaction

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-Mixing of two samples of the same substance at
the same state
But if reversible processes are merely ideal
and does not occur, why should we care?
Reversible processes represent the limit to the
performance of actual processes (like in work) but
is never fully realized/achieved. Combined with
certain efficiency this gives us an approximation
to the work of an actual process.
Example case: Recall the non-flow,close system
where there is work through compression or
expansion of gas caused by displacement of a
piston.
The work done on the system is given by
the derived equation only when certain
characteristics of the reversible process is
achieved: first the system is no more than
infinitesimally displaced from a state of internal
equilibrium (uniformity or T and P); second
system is no more than infinitesimally displaced
from
mechanical
equilibrium*
with
its
surroundings.
* mechanical equilibrium is the state of a mechanical system
in which the sum of the forces on each particle of the system
is zero. Allows us to substitute F = PA in the piston example.

If these conditions are satisfied we can say

that the process is mechanically reversible.
B. Irreversible processes - occurs due to the
finite gradient between the two states of the
system
- the initial state of the system and surroundings
cannot be restored from the final state.
- During the irreversible process the various
states of the system on the path of change from

initial state to final state are not in equilibrium

with each other.
- During the irreversible process the entropy of
the system increases decisively and it cannot be
reduced back to its initial value
Processes that are irreversible include:
-Movement with friction
-Energy transfer as heat due to large temperature
non uniformities
-Spontaneous chemical reaction
-Mixing of matter of different composition or state
--------------------------------------------------------------------------------Comparison of work of an irreversible and
reversible process
A horizontal piston arrangement is placed in a
constant-temperature bath. The piston slides 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
0.03m3. The external force on the piston is
reduced gradually and the gas expands
isothermally as its volume doubles.
a. If the volume of the gas is related to its
pressure so that the product PV T (PV at const. T)
is constant, what is the work done by the gas in
moving the external force?
b. How much work would be done if the external
force were suddenly reduced to half its initial
value instead of being gradually reduced?
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