Introduction to Chemical

Engineering Thermodynamics
Contents
1-introduction
-dimensions and units
-special definitions, force, temperature,
pressure, work, energy and heat
2-first law of thermodynamics
-internal energy
-enthalpy
-steady state flow process
-phase rule
-reversible process
-constant volume and constant pressure
processes
-heat capacity
3-volumetric properties of pure fluid
-pvt behavior of pure fluid
-varial equation
-Ideal gases
-application of virile equation
-cubic equations of state
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-generalize equations for gases

-generalize correlations for liquids
4-second law of thermodynamics
-heat engine
-carnot cycle for an ideal gas
-entropy and entropy change of an ideal
gas
5- Thermodynamics properties of fluids.
- Relationships among thermodynamics
properties for a homogenous phase of
constant composition.
-residual properties
-two phase systems
-table of thermodynamics properties
6-thermodynamics of flow processes
-flow in pipes
-expansion processes
-compression processes
7-system of variables compositions,
ideal behavior
-ideal gas mixture
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-ideal solution
- Raoults law
8-systems of variables compositions,
non-ideal behavior
-partial properties
-fugacity and fugacity coefficients
- fugacity and fugacity coefficients for
species I in solutions
-generalize correlations for the fugacity
coefficient
-activity coefficient
9-chemical reaction equilibrium
-effect of temperature on the
equilibrium constant
-evaluate of equilibrium constant
-relation between equilibrium constants
and compositions
- Calculation of equilibrium
conversation for single and multiple
reactions.

References
1-introducton to chemical engineering
thermodynamics by: J. M. Smith, forth
edition
2-chemical engineering thermodynamics
By: jack Winnick
3-Foundamental of engineering
thermodynamics, By: Moran M.J.
4-Chemical thermodynamics of
materials by: Stolen
5- Foundamental of engineering
thermodynamics By: Sonntag

Units and Dimensions

MKS

The MKS system is what is used by SI. It stands

for meter, kilogram, second, as base units
The base unites are:
Base Quantity

Name Symbol
meter
m
kilogram
kg
second
s
ampere
A

length
mass
time
electric current
thermodynamic
temperature
amount of a substance
luminous intensity

Base Quantity
length
mass
volume
power
time
temperature

kelvin

mole
candela

mol
cd

Name
inch, foot, yard, mile
ounce, pound
Fluid ounce, pint, quart,
gallon
horsepower, BTU/hr
second, minute, hour
degrees Fahrenheit
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English System

CGS
Stands for centimeter, gram, second.
Generally used where small quantities
are measured.
Length:
1m=100cm=3.28ft=39.37in

Mass:
1kg=1000gm=2.2 Ib mas

Force:
1 N= 1 kg m/s2 =100000dyne=0.2248 Ib force

Pressure:
1atm= 1bar = 105 Pa =100kPa = 14.5 psi
=760mm Hg
Volume
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1 m3 =106 cm3

Energy:
1 J= 1 N m = 0.239 cal = 9.47*10-4 Btu

Pressure
Pressure is defined as force per unit area. It is
usually more convenient to use pressure rather
than force to describe the influences upon fluid
behavior. The standard unit for pressure is the
Pascal, which is a Newton per square meter.

Static Fluid Pressure

The pressure exerted by a static fluid depends
only upon the depth of the fluid, the density of
the fluid, and the acceleration of gravity.
The pressure in a static fluid arises from the
weight of the fluid and is given by the expression
= m/V = fluid density
Pstatic fluid = gh where g = acceleration of gravity
h = depth of fluid

The pressure from the weight of a column of liquid

of area A and height h is

Gauge Pressure

Heat and Work

Heat and work are both forms of energy. They
are also related forms, in that one can be
transformed into the other. Heat energy (such as
steam engines) can be used to do work (such as
pushing a train down the track). Work can be
transformed into heat, such as might be
experienced by rubbing your hands together to
warm them up.
Work and heat can both be described using the
same unit of measure. Sometimes the calorie is
the unit of measure, and refers to the amount of
heat required to raise one (1) gram of water one
(1) degree Celsius. Heat energy is measured in
kilocalories, or 1000 calories. Typically, we use
the SI units of Joules (J) and kilojoules (kJ).
One calorie of heat is equivalent to 4.187 J. You
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will also encounter the term specific heat, the

heat required to raise one (1) gram of a material
one (1) degree Celsius. Specific heat, given by
the symbol "C", is generally defined as:

Where:
C = specific heat in calories/gram-degrees
Celsius
q = heat added in calories,
M = mass in grams
delta T = rise in temperature of the material in
degrees Celsius.
The value of C for water is 1.00 calories/gramdegrees Celsius.
Example: If a 2.34 g substance at 22 degrees
celsius with a specific heat of 3.88 cal/gC is
heated with 124 cal of energy, what is the new
temperature of the substance?

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Work
When work is done by a thermodynamic system,
it is usually a gas that is doing the work. The
work done by a gas at constant pressure is:
Example

For non-constant pressure, the work can be

visualized as the area under the pressure-volume
curve which represents the process taking place.
The more general expression for work done is:

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Constant Pressure Work

The definition of work
becomes W=Fd for a constant
force F along a distance d.
Using the definition of
pressure:

For the circular piston shown

for the case of constant
pressure:

Kinetic Energy
Kinetic energy is energy of motion. The kinetic energy
of an object is the energy it possesses because of its
motion. The kinetic energy* of a point mass m is
given by
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m= mass or mass flow rate

u = velocity

Potential Energy
Gravitational potential energy is energy an
object possesses because of its position in a
gravitational field.

Ep = m g z
m= mass or mass flow rate
g = acceleration
Z=height
The total energy of a system
consists of the kinetic, potential,
and internal energies and is
expressed as

E = U + KE + PE = U + m V2 /2+
mgz
THE FIRST LAW OF
THERMODYNAMICS
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So far, we have considered various

forms of energy such as heat Q,
work W, and total energy E
individually, and no attempt is made
to relate them to each other during
a process. The first law of
thermodynamics, also known as the
conservation of energy principle,
provides a sound basis for studying
the relationships among the various
forms of energy and energy
interactions. Based on experimental
observations, the first law of
thermodynamics states that energy
can be neither created nor
destroyed during a process; it can
only change forms. Therefore, every
bit of energy should be accounted
for during a process.
The net change (increase or
decrease) in the total energy of the
system during a process is equal to
the difference between the total
energy entering and the total
energy leaving the system during
that process.
Ein - Eout = Esystem

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PE = mg(z2 - z1 )
KE = 1/2 m(V22- V 21 )
U = m(u2 - u1 )
Most systems encountered in practice
are stationary, that is, they do not
involve any changes in their velocity or
elevation during a process (Fig.
244). Thus, for stationary systems, the
changes in kinetic and potential
energies are zero (that is, KE , PE = 0

Mechanisms of Energy
Transfer, Ein and Eout
Energy can be transferred to or
from a system in three forms: heat,
work, and mass flow. Energy
interactions are recognized at the
system boundary as they cross it,
and they represent the energy
gained or lost by a system during a
process. The only two forms of
energy interactions associated with
a fixed mass or closed system are
heat transfer and work.
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1. Heat Transfer, Q Heat transfer to

a system (heat gain) increases the
energy of the molecules and thus
the internal energy of the system,
and heat transfer from a system
(heat loss) decreases it since the
energy transferred out as heat
comes from the energy of the
molecules of the
system.
2. Work Transfer, W An energy
interaction that is not caused by a
temperature difference between a
system and its surroundings is
work. A rising piston, a rotating
shaft, and an electrical wire
crossing the system boundaries are
all associated with work
interactions. Work transfer to a
system (i.e., work done on a
system) increases the energy of the
system, and work transfer from a
system (i.e., work done by the
system) decreases it since the
energy transferred out as work
comes from the energy contained in
the system. Car engines and
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hydraulic, steam, or gas turbines

produce work while compressors,
pumps, and mixers consume work.
3. Mass Flow, m Mass flow in and
out of the system serves as an
additional mechanism of energy
transfer. When mass enters a
system, the
energy of the system increases
because mass carries energy with it
(infact, mass is energy). Likewise,
when some mass leaves the system,
the energy contained within the
system decreases because the
leaving mass takes out some energy
with it. For example, when some hot
water is
taken out of a water heater and is
replaced by the same amount of
cold water, the energy content of
the hot-water tank (the control
volume) decreases as a result of
this mass interaction
Ein _ Eout _ 1Qin _ Qout 2 _ 1Win _
Wout 2 _ 1Emass,in _ Emass,out 2 _
Esystem

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where the subscripts in and out

denote quantities that enter and
leave the system, respectively. All
six quantities on the right side of
the equation represent amounts,
and thus they are positive
quantities. The direction of any
energy transfer is described by the
subscripts in and out. .The heat
transfer Q is zero for adiabatic
systems, the work transfer W is
zero for systems that involve no
work interactions, and the energy
transport with mass Emass is zero
for systems that involve no mass
flow across their boundaries (i.e.,
closed systems).

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