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Thermodynamics deals with transformations of energy of all kinds

from one form to another. The general restrictions within which all
such transformations are observed to occur are known as the first

and second laws of thermodynamics.

Using Thermodynamics, the chemical engineer can

• heat and work requirements for physical and
chemical processes,
• equilibrium conditions for chemical reactions,
• transfer of chemical species between phases.
• A system is defined as a quantity of matter or a region in space
chosen for study.
• The mass or region outside the system is called the
• The real or imaginary surface that separates the system from its
surroundings is called the boundary


2 kg
3 m3

2 kg
Moving boundary 1 m3

Fixed boundary

A closed system with moving boundary

• An open system (control volume) is a properly selected
region in space enclosing a device in which there is mass
flow in and out. Both mass and energy can cross the

Mass Yes
Hot volume

Water Energy Yes

An open system ( a control volume) with Both mass and energy can cross the
one inlet and one exit boundaries of a control volume
Energy can exist in numerous forms. The total energy of a system
(E) is made up of macroscopic and microscopic forms. The
macroscopic forms are those a system possesses as a whole w.r.t.
some outside reference frame , such as kinetic (KE) and potential
(PE) energies.
Macroscopic E = KE + PE

• The sum of all microscopic forms of energy is called the internal

energy (U) of the system.
• It accounts for internal motions of the molecules which move
around with some velocity (transnational motion), vibrate about
each other (Vibrational motion), and rotate about an axis during
their random motion (rotational motion) .
• Total E = U + KE + PE
1. Push-Pull work
work is done whenever a force acts through a distance
W   F .dl

2. Pv work V
dW  F .dl  P. A.d ( )  P.dV

W   P.dV

3. Electrical work
W  Q(Coulomb).V (volt)
W  I (ampere).V (volt). ( s )
Work (cont.)

4. Surface tension work:

W    dA

5. Elastic work
F  K S . y (deflectio n, m) Hooke' s law

 y1  y22 
KS 2
W   K S . ydy 
• Energy 1
Ek  mu 2
• If a body of mass m is acted upon by the force F 2
during a differential interval of time dt, the W  Ek
displacement of the body is dl:

• If a body of mass m is raised from an initial F  m.a  m.g

elevation z1 to a final elevation z2, an upward W  F .( z  z )  m.g.z
force at least equal to the weight of the body 2 1

must be exerted on it, and this force must

move through the distance (z2-z1):
It concerns energy conservation and states that:

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.
In other words; energy cannot be created or destroyed; it can
only change forms.
This law applies to the system & surroundings:

 (energy of system) +  (energy of surroundings) = 0

Intensive properties are independent of the quantity
of material such as T & P.
, kg/m3

, m3/kg

e, kJ/kg

u, kJ/kg

Intensive properties are independent of the size of

the system.
Extensive properties depend on the quantity of material in
the system such as U & V. U & V become intensive properties if we
consider a unit mass ( specific U & V), or a mole (molar U & V)
Example 2.1
m ½m ½m
Extensive properties
V ½V ½V


P P P Intensive properties

  

Criteria to differentiate intensive and extensive properties

A system at two different states.

m = 2 kg
T2 = 20 oC
V2 = 3 m3

m = 2 kg
T1 = 20 oC
V1 = 1.5 m3
Final state

Process path
Initial state


The P-V diagram of a compression process.

The first law of thermodynamics concerns energy
conservation and states that:
Energy cannot be created or destroyed; it can only
change forms.

The second law of thermodynamics asserts that:

Energy has quality as well as quantity, and actual
processes occur in the direction of decreasing
quality of energy.
Constant V and constant P Processes

For closed system:

d (nU )  dQ  dW n is the number of moles
dW  -Pd(nV) mechanical ly reversible , nonflow process
d(nU)  dQ - Pd(nV)

Q  nU (constant volume)

nH  nU  P(nV)
Q  nH (constant pressure)
Heat Capacity
It may define as: C
 dU 
CV   
 dT V
 dH 
CP   
 dT  P
Q  n  CV dT (constant volume)
Q  n  C P dT (constant pressure)

First law