ChE 323 - Chemical Engineering Thermodynamics I

Chapter 1 – Introduction and Basic Concepts of Thermodynamics

Basic Concepts Basic Principles of Thermodynamics

Results (Interpretation) Chemical Engineering Problems:

Practical Problems (Simple) and
Complex Problems
Thermodynamics
Original meaning
 thermo - heat dynamics - motion
 heat power (power developed from heat)

Present meaning
As a fully developed science, thermodynamics deals with:
 energy in all its forms
 the conversion of energy from one form to another
 the transfer of energy and effects on the physical properties of substances

Applications of Thermodynamics in Chemical Engineering

1. Determination of whether a given process (physical or chemical) is possible or not.
2. Determination of equilibrium conditions for chemical reactions and mass transfer between phases
3. Determination of heat and work requirements for physical and chemical processes

Limitations of Thermodynamics
1. Thermodynamics cannot determine the mechanism of either a physical or chemical process.
2. Thermodynamics alone is not sufficient for the determination of the rates of physical and chemical
processes. Driving forces can be determined by thermodynamic methods but not resistances.
3. Adequate thermodynamic data are known only for a relatively few substances.

Basic and Derived Quantities

The Seven Basic or Fundamental Quantities (SI units) “Fundamental dimensions of science’’
Time (s), length (m), mass (kg), temperature (K), amount of substance (mol), electric current (A),
luminous intensity (cd)

The second is the duration of 9192631770 cycles of radiation associated with a specified transition
of the cesium atom.
The meter is the fundamental unit of length, defined as the distance light travels in a vacuum during
1/299792458 of a second.
The kilogram is the mass of a platinum/iridium cylinder kept at the International Bureau of Weights
and Measures at Serves, France.
The kelvin is equal to 1/273.16 of the thermodynamic temperature of the triple point of water.

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Derived Quantities
(a) volume
(b) density - mass per unit volume
(c) specific volume - reciprocal of density ( ) molar volume – ( )
(d) force
Newton's Second Law of Motion - The acceleration (a) of a particular mass (m) is directly
proportional to the resultant force (F) acting on it and inversely proportional to its mass.

a  F/m

gc = proportionality constant
gc is 1 (kg-m/s2) /N (SI) and 32.2 (lbm-ft/s2)/ lbf (Eng)

Example 1.1
An astronaut weighs 730 N in Houston, Texas, where the local acceleration of gravity is g = 9.792 m/s 2.
What are the astronaut's mass and weight on the moon, where g = 1.67 m/s2?

Problem 1.10/p. 17
An instrument to measure the acceleration of gravity on Mars is constructed of a spring from which is
suspended a mass of 0.40 kg. At a place on earth where the local acceleration of gravity is 9.81 m/s 2, the
spring extends 1.08 cm. When the instrument package is landed on Mars, it radios the information that the
spring is extended 0.40 cm. What is the Martian acceleration of gravity?

(e) pressure

 The pressure of a fluid on a surface is the normal force exerted by the fluid per unit
area of the surface.

(N/m2) 1 N/m2 = 1 Pa

 At STP, Pgas is 1 atm = 101325 Pa = 101.325 kPa = 1.01325 bar

= 760 mmHg = 29.92”Hg = 14.7 psi = 760 Torr

 Absolute pressure – actual pressure at a given position

Gauge pressure and vacuum pressure – pressures relative to the

atmospheric pressure.

(Pressure is above atmospheric pressure)

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 (Pressure is below atmospheric pressure)

P absolute

P gauge
P atmospheric/barometric

P vacuum
P absolute

 Pressure of a column of fluid

U-Tube Manometer – a device used to measure pressures

Barometer – measures the atmospheric pressure

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 Dead-weight gauge

Example 1.2
A dead-weight gauge with a 1-cm diameter piston is used to measure pressures very accurately. In a
particular instance a mass of 6.14 kg (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?

Example 1.3
At 27oC the reading on a manometer filled with mercury is 60.5 cm. The local acceleration of gravity is
9.784 m/s2. To what pressure does this height of mercury correspond?

Problem 1.14/p. 17
A gas is confined in a 0.47 m diameter cylinder by a piston, on which rests a weight. The mass of the
piston and the weight together is 150 kg. The local acceleration of gravity is 9.813 m/s2, and atmospheric
pressure is 101.57 kPa.
(a) What is the force in newtons (N) exerted on the gas by the atmosphere, the piston and the weight,
assuming no friction between the piston and cylinder?
(b) What is the pressure of the gas in kPa?
(c) If the gas in the cylinder is heated, it expands, pushing the piston and weight upward. If the piston
and weight are raised by 0.83 m, what is the work done by the gas in kJ? What is the change in the
potential energy of the piston and weight?

System and Surroundings

System – a certain quantity of matter or a certain region in space which is enclosed by specified boundaries.
It interacts and exchanges energy with its surroundings.

The system may be of any size depending on the particular conditions, and its boundaries maybe real or
imaginary, rigid or flexible. The equations of thermodynamics are written with reference to a particular well-
defined system.
Transformation of energy may occur within the system. Mass and/or energy may pass through the
boundaries of the system.

Surroundings – Everything not included in the system.

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Types of Systems

Path Functions and State Functions

A State Function is a function in which the value only depends on the initial and final states of the
system and NOT on the pathway taken. Ex. P, V, T, U, H, S, G
A Path Function is dependent on the process of the system. The process is the path by which the system
arrives at a given thermodynamic state. Ex. Heat and Work

State of a System: The state of a system is established by particular values of two independent properties
(state functions)

(1) Internal energy is a state function and is therefore a property of the system. Since state functions can be
expressed as function of temperature or pressure, their values can be identified as points on a graph. Work
and heat are not state functions and cannot be identified with points on a graph, but rather are represented
by areas.

(2) The differential of a state function is an infinitesimal change in the property. Integration results in a
finite difference between two values of the property.

∫ ∫

The differential of heat and work are not referred to as changes but are regarded as infinitesimal
quantities of heat and work. When integrated, these differentials give not a finite change but a finite
quantity. Thus:
∫ and ∫
(3) A state function represents a property of a system and always has a value. Work and heat appear only
when changes are caused in a system by a process which requires time.

Intensive and Extensive Properties

Intensive Properties – properties such as temperature and pressure are independent of the quantity of
material making up the system.
Extensive Properties – Volume and internal energy whose values depend on the quantity of material
involved.

Although the total volume, total internal energy are extensive properties, specific and molar volume (or
density) and specific and molar internal energy are intensive properties.

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Joule’s Experiment
James P. Joule (1818-1889)

Q
H2O H2O
W
WUQ
T1  T2 T2  T1

o Joule found that a fixed amount of work was required per unit mass of water for every
degree of temperature rise caused by the stirring.
o The original temperature of the fluid can be restored by the transfer of heat through the
simple contact with a cooler object.
o What happens to the energy between its addition to and transfer from water?

The energy is added as work and stored as internal energy and removed from the water as
heat.

Work and heat are transit energy while internal energy is a stored energy.

Internal Energy (U) – the energy of a substance due to the configuration and activity of its molecules, atoms
and subatomic units.
(1) internal kinetic energy – energy contributed by:
(a) chaotic motion of gas molecules
(b) rotational motion of molecules or group of atoms which are free to move within a
molecule.
(c) internal vibration of atoms within the molecule
(d) motion of electrons within the atom

(2) internal potential energy due to interactions of the force fields of molecules, atoms, electrons and
nuclear particles.

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Enthalpy (H)
By definition:

(equal to 0 at constant V) (equal to 0 at constant P)

( ) ( ) ( ) ( )

Note: you cannot measure the absolute value of the internal energy of a system but you can measure
changes in the internal energy. Same with enthalpy.

or constant
or CP and CV

where CV = constant-volume heat capacity (specific heat or molar heat capacity at constant volume)
CP = constant-pressure heat capacity (specific heat or molar heat capacity at constant pressure)

Heat capacity at constant volume Cv : the energy required to raise the temperature of a unit quantity of a
substance by one degree as the volume is maintained constant. ( )

Heat capacity at constant pressure Cp : the energy required to raise the temperature of a unit quantity of a
substance by one degree as the pressure is maintained constant. ( )

For Ideal Gases: CP = CV + R For Solids and Liquids (incompressible): CP = CV

Heat (Q) – is defined as the form of energy that is transferred between a system and its surroundings due to
temperature difference. It always flows from a higher temperature to a lower one. A hot body brought in
contact with a cold object becomes cooler, whereas the cold object becomes warmer.

For a constant volume process with , the following must be true

For a constant pressure process with: and

Example Problems: CP = f(T)

1. What is the heat (in kJ) required when 10 mol of ethylene is heated from 200 to 1,100oC at
approximately atmospheric pressure in a steady-state flow heat exchanger? Ans. 798.5 kJ
– where T is in K
2. What is the final temperature when heat in the amount of 1,100 kJ is added to 30 mol of SO2 initially
at 300oC in a steady-state flow heat exchanger at approximately atmospheric pressure? Ans. 1273 K
– where T is in K

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Work (W) – Work is performed whenever a force acts through a distance. It is the product of the force (F) in
the surroundings acting on the system and the displacement (l) caused by the action of that force.
By definition: W is + when force and displacement are of the same direction.
W is – when force and displacement are in opposite directions

Pressure-Volume Work (PV Work)

Constant opposing pressure: –

Variable opposing pressure: The relationship between the opposing pressure and the volume of the gas
must be known. If the Pop-V relationship can be expressed by a simple equation, the integration can be
made algebraically.
Example Problems:
1. A gas expands against a variable opposing pressure given by P = 10/V where V is the volume (L) of the
gas at each stage of the expansion and P is the pressure in atm, Find the work done by the gas on expansion
from 10 to 100 liters (in Joules). Ans. -2333J
2. The path followed by a gas during a particular mechanically reversible process is described by the
equation:

where a and c are constants. In the initial state, P1 = 60 bar and V1 = 0.002 m3; in the final state, P2 = 20 bar
and V2 = 0.004 m3. Calculate the work for the process. Ans. -8000 J
Energy in Transit
Work and heat exist only as energy in transit. When work is done on a body, the work becomes part of
energy (internal) of a body. When heat is added to a body, it is stored not as heat but as kinetic and
potential energy of the atoms, ions and molecules making up the body.

Q + absorbed by system from surroundings

− transferred from system to surroundings
W + done on system by surroundings
− done by system on surroundings

Reversible Process and Irreversible Process

Reversible Process – A process is reversible when its direction can be reversed at any point by an
infinitesimal change in external conditions.
A process is reversible if at all times the pressure of the gas (Pg) and the opposing pressure (Pop) differ
only by an infinitesimal amount. Thus in the equation for work dW = -PopdV, the pressure of the gas can
replace Pop.
Reversible Process dWrev = -PgdV
Irreversible Process dW = -PopdV

Example Problem:
One mole of an ideal gas is confined in a 0.3-m diameter cylinder by a piston on which rests a 100-kg
weight. The mass of the piston is 50 kg. The gas expands isothermally at 25 oC after the removal of weight.
Calculate the work done required for each of the following:
(a) The 100-kg weight is removed in one step.
(b) The 100-kg weight is removed in two steps, 50 kg/step.
(c) The 100-kg weight is removed in four steps, 25 kg/step.

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 (d) The weight is replaced by a pile of sand (100 kg) and the grains of sand are removed one at a time.

Energy – the ability to do work

Types of Energy
(1) Kinetic Energy – energy of motion

(2) Potential Energy – energy of position and configuration

Stored energy is available to be converted into work or some other forms of energy.
Forms of Energy: mechanical, electrical, chemical, thermal, nuclear, etc.
Energy may be transformed from one form to another.
Example 1.4
An elevator with a mass of 2,500 kg rests at a level 10 m above the base of an elevator shaft. It is raised
to 100 m above the base of the shaft, where the cable holding it breaks. The elevator falls freely to the base
of the shaft and strikes a strong spring. The spring is designed to bring the elevator to rest and, by means of
a catch arrangement, to hold the elevator at the position of maximum spring compression. Assuming the
entire process to be frictionless and taking g – 9.8 m/s2, calculate:
(a) The potential energy of the elevator in its initial position relative to the base of the shaft.
(b) The work done in raising the elevator.
(c) The potential energy of the elevator in its highest position relative to the base of the shaft.
(d) The velocity and kinetic energy of the elevator just before it strikes the spring.
(e) The potential energy of the compressed spring.
(f) The energy of the system consisting of the elevator and spring (1) at the start of the process, (2)
when the elevator reaches its maximum height, (3) just before the elevator strikes the spring, (4)
after the elevator has come to rest.

PROBLEM 1.17
The turbines in a hydroelectric plant are fed by water falling from a 50-m height. Assuming 91%
efficiency for conversion of potential to electrical energy, and 8% loss of the resulting power in transmission,
what is the mass flowrate of water required to power a 200-watt light bulb?

Power
Power is the rate at which work is done by or upon the system or the rate at which heat energy is
absorbed or released.

Power unit: Watt (W) = Joule/second (J/s)

1 kW = 1.341 hp
1 hp = 0.746 kW

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