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You are on page 1of 237

Definitions of Thermodynamics:

can be defined as the science of ENERGY

ENERGY :

might be difficult to define precisely, but

we can view it as AN ABILITY TO

CAUSE CHANGES

11/3/2017 1

Engineering, Thermodynamics (GEC 221)

Thermodynamics stems from the greek word

therme (heat) and dynamis (dynamic/power)

Heat Power

CONVERT HEAT INTO POWER

aspects of energy and energy transformation;

including power generation, refrigeration, and

relationships among the properties of matter.

11/3/2017 2

Engineering, Thermodynamics (GEC 221)

One of the fundamental law of nature is

Conservation of energy principle

change from one form to another but the total

amount of energy remains constant, that is,

energy can neither be created nor destroyed.

11/3/2017 3

Engineering, Thermodynamics (GEC 221)

Example 1: A rock on a cliff

PE = 10 units picks up speed as its P.E.

KE = 0

changes to K.E. as it falls to

the ground.

PE = 7 units

KE = 3 units

11/3/2017 4

Engineering, Thermodynamics (GEC 221)

Example 2:

than energy output (exercise) will gain weight

(stores energy in form of fat), and a person

who has smaller energy input than output

looses weight

11/3/2017 5

Engineering, Thermodynamics (GEC 221)

It follows then that:

The change in energy content of a body or any

other system is equal to the difference between

the energy input and the energy output, and the

energy balance is given as

Human being, 1

unit energy storage

5 units 4 units

to grow fatter

Covenant University, Dept. of Chemical

11/3/2017 6

Engineering, Thermodynamics (GEC 221)

The Two Laws of Thermodynamics

The 1st law expresses the conservation of

energy principle, and it assets that energy is a

thermodynamic property

The 2nd law asserts that energy has quality as

well as quantity, and actual processes occur in

the direction of decreasing quality of energy.

11/3/2017 7

Engineering, Thermodynamics (GEC 221)

An example of the second law is a cup of hot

coffee left on a table which eventually cools,

but a cup of cool coffee in the same room

never gets hot by itself.

Hot cold

decreasing quality

11/3/2017 8

Engineering, Thermodynamics (GEC 221)

At high temp., energy of coffee is degraded

(transformed into a less useful form at a lower

temp.) once it is transferred to the surrounding

air.

The 1st and 2nd laws emerged simultaneously

in 1850s from the works of William Rankine,

Rudolph Clausius, Lord Kelvin.

11/3/2017 9

Engineering, Thermodynamics (GEC 221)

NOTE

Substances consists of large number of

particles called MOLECULES. The properties

of the substance naturally depend on the

behaviour of these particles (the molecules).

e.g. The pressure of a gas in a container is the

result of momentum transfer between the

molecules and the walls of the container. It

will be sufficient to attach a pressure gauge to

the container to determine the pressure in the

container rather than trying to know the

behaviour of the gas particles to determine the

pressure.

Covenant University, Dept. of Chemical

11/3/2017 10

Engineering, Thermodynamics (GEC 221)

Approaches to Thermodynamics

Classical Thermodynamics

It is the macroscopic approach that does not

require a knowledge of the behaviour of

individual particle.

It is observation driven

Focus is on bulk energy flow

Interest includes: energy transfer, energy

transformation and energy storage

Covenant University, Dept. of Chemical

11/3/2017 11

Engineering, Thermodynamics (GEC 221)

Approaches to Thermodynamics

Statistical Thermodynamics

It is a more elaborate approach, based on the

average behaviour of large groups of

individual particles.

It is a microscopic approach.

Focus includes structures of matter and

molecular interaction

It is theory driven

Covenant University, Dept. of Chemical

11/3/2017 12

Engineering, Thermodynamics (GEC 221)

Application Areas of Thermodynamics

1. Human Existence

Human Body

(rejection)

(Heart)

11/3/2017 13

Engineering, Thermodynamics (GEC 221)

Heart pumps blood continuously to all parts of

the body.

Energy conversions occur in trillions of body

cells.

Body heat generated is constantly rejected to

the environment.

The body comfort is closely tied to the rate of

this metabolic heat rejection.

We control the heat transfer rate by adjusting

our clothing to the environmental conditions.

11/3/2017 14

Engineering, Thermodynamics (GEC 221)

Application Areas of Thermodynamics

designed in whole or in part by using the

principles of thermodynamics e.g. heating or

air conditioning systems, the refrigerator, the

humidifiers, the pressure cooker, the water

heater, the shower, the iron.

11/3/2017 15

Engineering, Thermodynamics (GEC 221)

Application Areas of Thermodynamics

major role in the design and analysis of

automobile engines, rockets, jet engines,

conventional or nuclear power plant, and

design of vehicles from ordinary car to

airplanes.

11/3/2017 16

Engineering, Thermodynamics (GEC 221)

DIMENSIONS AND UNITS

Any physical quantity can be characterised by

dimensions.

The magnitude (size) assigned to the

dimensions are called units.

Basic dimensions : mass (m), length (L), time

(t) and Temperature (T) are selected as

primary or fundamental units.

11/3/2017 17

Engineering, Thermodynamics (GEC 221)

Velocity (V), energy (E), and volume (V) are

expressed in terms of the primary dimensions

and are called secondary dimensions or

derived dimensions.

11/3/2017 18

Engineering, Thermodynamics (GEC 221)

Common Unit Systems in Science and

Engineering

numerical base, various units in the system

are related to each other rather arbitrarily

12 inch = 1 ft.

1 mile = 5280 ft.

4 quint = 1 gallon

11/3/2017 19

Engineering, Thermodynamics (GEC 221)

The metric SI system : This is a simple and

logical system based on a decimal relationship

between various units.

11/3/2017 20

Engineering, Thermodynamics (GEC 221)

Dimensions SI units

Length metre, m

Mass kilogram, (kg)

Time Second, (s)

Temperature kelvin (K)

Electric current ampere (A)

Amount of matter mole, (mol)

Amount of light (luminous intensity) Candela (cd)

11/3/2017 21

Engineering, Thermodynamics (GEC 221)

Convention in Writing Units

Do not capitalise fundamental units like

metre, kilogram, and second : 20 M is wrong,

instead 20 m, 20 kg NOT 20 Kg, 20 Min

instead, write 20 min

Units having proper names e.g. SI unit of force

named after Sir Isaac Newton is 20 newton

(not Newton) but if you abbreviate, you write

20 N

11/3/2017 22

Engineering, Thermodynamics (GEC 221)

Dont write 5 ms but you can write 5 metres.

Also is wrong to write 5 metre, but 5 m is

correct.

No full stop after writing the unit e.g. 5 m not

5 m.

There is always a space between the number

and unit

e.g. 5 m not 5m

Space

11/3/2017 23

Engineering, Thermodynamics (GEC 221)

SI units English system

kg Ibm (pound-mass)

m ft (foot)

s s (second)

O.45359 kg 1 Ibm

0.3048 m 1 ft

11/3/2017 24

Engineering, Thermodynamics (GEC 221)

Note that weight is a force, it is the gravitational

force applied to a body, and its magnitude is

determined from Newtons 2nd law

W = mg (N)

The mass of a body remains the same regardless

of its location in the universe. Its weight, however

changes with a change in gravitational

acceleration.

A body weighs less on top of a mountain since g,

decreases with altitude.

On the surface of the moon, an astronaut weighs

about 1/6th of what she or he normally weighs on

earth

Covenant University, Dept. of Chemical

11/3/2017 25

Engineering, Thermodynamics (GEC 221)

At locations below sea level, the value of g

(gravitational acceleration) increases with

distance from the sea level, reaches a

maximum at about 4500 m, and then starts

decreasing.

g, varies with location from 9.8295 m/s2 at

4500 m below sea level to 7.3218 m/s2 at

100,000 m above sea level.

At altitude up to 30,000 m variation of g from

the sea level value of 9.807 m/s2 is less than

1%

Covenant University, Dept. of Chemical

11/3/2017 26

Engineering, Thermodynamics (GEC 221)

Exercises

Read about prefixes for multiples of various

units e.g. tera, giga, deci, nano, pico.

What is the difference between pound-mass

and pound-force.

Determine the mass and the weight of the air

contained in a room whose dimensions are 6 m

x 6 m x 8 m. Assume the density of the air is

1.16 kg/m3.

Convert 100 Ibf/in2 to N/m2. Given that 1 Ibf =

4.4482 N, 1 m = 39.37 in

11/3/2017 27

Engineering, Thermodynamics (GEC 221)

Dimensional Homogeneity

In science and engineering, all equations must

be dimensionally homogeneous ( every term

in an equation must have the same unit)

fufu + pickles = stomach upset.

Checking dimensions can serve as a valuable

tool to spot errors in engineering analysis.

Covenant University, Dept. of Chemical

11/3/2017 28

Engineering, Thermodynamics (GEC 221)

Basic Concepts of Thermodynamics

System

A system is a region in space, delineated

(chosen) for study.

Surroundings

The mass or region outside the system.

Boundary

The real or imaginary surface that separates

the system from its surroundings.

Covenant University, Dept. of Chemical

11/3/2017 29

Engineering, Thermodynamics (GEC 221)

NOTE

The boundary is the contact surface shared by

both the system and the surroundings.

Mathematically speaking, the boundary has zero

thickness, and thus it can neither contain any

mass nor occupy any volume in space.

SURROUNDINGS

BOUNDARY

11/3/2017 30

Engineering, Thermodynamics (GEC 221)

Types of System

1. Closed system (also known as control mass):

Consists of a fixed amount of mass, and no

mass can cross its boundary, i.e. no mass can

enter or leave a closed system.

But energy, in the form of heat or work, can

cross the boundary; and the volume of a closed

system does not have to be fixed.

2. If, as a special case, even energy is not

allowed to cross the boundary, that system is

called an Isolated system.

Covenant University, Dept. of Chemical

11/3/2017 31

Engineering, Thermodynamics (GEC 221)

3. Open system (a control volume): Is a

properly selected region in space. It usually

encloses a device that involves mass flow such

as a compressor, turbine, or nozzle. Both mass

and energy can cross the boundary of a

control volume.

Most engineering problems involve mass flow

in and out of the system and, therefore, are

modelled as control volumes. A water heater, a

car radiator, a turbine, a compressor all involve

mass flow and should be analysed as control

volumes (open systems) instead of as control

masses (closed systems)

Covenant University, Dept. of Chemical

11/3/2017 32

Engineering, Thermodynamics (GEC 221)

Open

Isolated

E, M

X E, M

E

Closed

X M

11/3/2017 33

Engineering, Thermodynamics (GEC 221)

Properties of a system

Something that describes a system. Any

characteristic of a system is called a property.

Examples are pressure P, temperature T,

volume V, and mass m.

Less familiar ones include such as viscosity,

thermal conductivity, modulus of elasticity,

thermal expansion coefficient, electric

resistivity, and even velocity and elevation.

11/3/2017 34

Engineering, Thermodynamics (GEC 221)

Properties are considered to be either

Intensive or Extensive

Properties that are independent of the mass

of a system are intensive properties e.g.

temperature, pressure, density, heat/energy in

transit, heat capacity (Cv and Cp). They are

also called thermodynamic properties or state

properties.

Extensive properties are those whose values

depend on the size (or extent ) of the system

e.g. total mass, total volume, total

momentum.

Covenant University, Dept. of Chemical

11/3/2017 35

Engineering, Thermodynamics (GEC 221)

Extensive properties per unit mass are called

specific properties, e.g., specific volume (V/m)

and specific total energy (E/m).

11/3/2017 36

Engineering, Thermodynamics (GEC 221)

Volume: A measure of size, on the same basis

as mass and mole.

Total volume: is a defined quantity given as

the product of three lengths. Total volume

may be divided by the mass or number of

moles of the system to yield specific volume

Specific volume: is the volume of a unit mass.

Mass: Is a primitive, without definition but

well understood.

11/3/2017 37

Engineering, Thermodynamics (GEC 221)

Specific volume

V Vt/m or Vt = mV 1

Molar volume

V = Vt/n or Vt = nV 2

= V-1 3

11/3/2017 38

Engineering, Thermodynamics (GEC 221)

V (specific volume), , Temperature, pressure

and composition are examples of intensive

properties that are independent of size.

11/3/2017 39

Engineering, Thermodynamics (GEC 221)

Pressure

It is defined as a normal force exerted by a

fluid per unit area. We speak of pressure only

when we deal with a gas or a liquid. In solids

we talk of normal stress.

P = F/A = (Fxl)/ (Axl) 4

= W/V 5

P (pressure), F (Force), A (Area), l (Length), W

(Work), V (Specific volume)

11/3/2017 40

Engineering, Thermodynamics (GEC 221)

But work W, is a form of energy E,

Therefore, P = E/V 6

Equation 6 defines pressure as energy

required to introduce a fluid into a space of

specific volume, V. Equation 6 can also be

written as

PV = E 7

Implying that at a given value of pressure P,

energy will vary with specific pressure.

.

11/3/2017 41

Engineering, Thermodynamics (GEC 221)

Equation 6 also implies that an addition of a

given specific volume of a fluid V, using energy

E, will lead to a given increase of pressure,

each time. This is the principle of pumping of

liquids or compression of vapour and gases.

11/3/2017 42

Engineering, Thermodynamics (GEC 221)

A gauge for measuring pressure in a

reaction vessel

Gauge

11/3/2017 43

Engineering, Thermodynamics (GEC 221)

Heat

Heat is a form of energy which, when

transferred to or from a system makes it

hotter or colder, respectively.

Heat and work are energy in transit, between

a system and its surroundings.

Heat is the most primordial (earliest) form of

energy. Friction between any two matters,

even electrons transform to heat.

Energy interaction is heat only if it takes place

because of temperature difference.

Covenant University, Dept. of Chemical

11/3/2017 44

Engineering, Thermodynamics (GEC 221)

There cannot be any heat transfer between two

systems that are at the same temperature.

Heat is recognized only as it crosses the

boundary of a system.

For example, a hot baked potato contains

energy, but the energy is heat transfer only as it

passes through the skin of the potato (system

boundary) to reach the air. Once in the

surroundings, the transferred heat becomes

part of the internal energy of the surroundings.

11/3/2017 45

Engineering, Thermodynamics (GEC 221)

In other words, in thermodynamics, the term

heat means heat transfer. A process during

which there is no heat transfer is called an

adiabatic process.

2 kJ thermal NOTE: Energy is

SURROUNDING AIR

energy recognized as heat

HEAT

transfer only as it

crosses the system

2 kJ boundary

Heat

2 kJ thermal

energy System boundary

11/3/2017 46

Engineering, Thermodynamics (GEC 221)

System boundary

Q=0

ADIABATIC

AA

SYSTEM

Insulation

exchanges no heat with its surroundings

Covenant University, Dept. of Chemical

11/3/2017 47

Engineering, Thermodynamics (GEC 221)

Heat Capacity

Everybody has capacity (ability) for heat, as it

(heat) passes through it.

The smaller the temperature change in a body

resulting from the transfer of a given quantity

of heat, the greater its capacity, C. Thus, the C

can be defined by Eq 8,

C = dQ/dT 8

11/3/2017 48

Engineering, Thermodynamics (GEC 221)

Specific Heat

Like the relationship between total volume

and specific volume, specific and molar heat

are heat per unit mass or per unit mole,

respectively. It can be at constant pressure or

constant volume

11/3/2017 49

Engineering, Thermodynamics (GEC 221)

Temperature

It is defined as a measure of its thermal state

considered in reference to its power to

transfer heat to or from other bodies.

By analogy, from Eq. 6, we can write

T = E/Cp 8a

11/3/2017 50

Engineering, Thermodynamics (GEC 221)

where Cp is the thermal capacity per unit

mass per unit temperature, at constant

pressure

Equation 8a can be seen to imply that an

addition of a unit quantity of Cp to a system

increases its temperature by one unit of

temperature

11/3/2017 51

Engineering, Thermodynamics (GEC 221)

Other Concepts

Energy

Energy is difficult to define. Many define it as

ability to do work. It is beyond this. Suffice to

say that energy exists as heat, mechanical

(potential, volume, kinetic), chemical,

magnetic, nuclear, and electrical forms.

11/3/2017 52

Engineering, Thermodynamics (GEC 221)

The sum of these numerous forms of energy

constitutes the total energy, E of a system.

In thermodynamics, we consider the various

forms of energy that make up the total

energy of a system in two groups:

1. Macroscopic : forms of energy a system

possesses as a whole with respect to some

outside reference frame, such as kinetic and

potential energies (the macroscopic energy of

an object changes with velocity and elevation)

11/3/2017 53

Engineering, Thermodynamics (GEC 221)

2. Microscopic forms of energy are those related

to the molecular structure of a system and

the degree of the molecular activity, and the

are independent of outside reference frames.

The sum of all the microscopic forms of

energy is called the internal energy of a

system.

11/3/2017 54

Engineering, Thermodynamics (GEC 221)

The macroscopic energy of a system is related

to motion and the influence of some external

effects such as gravity, magnetism, electricity,

and surface tension.

The energy that a system possesses as a result

of its motion relative to some reference frame

is called kinetic energy (KE).

The energy that a system possesses as a result

of its elevation in a gravitational field is called

potential energy (PE).

11/3/2017 55

Engineering, Thermodynamics (GEC 221)

Sensible heat

At the molecular level, the portion of the

internal energy of a system associated with

the kinetic energies of the molecules is called

sensible heat.

The average velocity and the degree of activity

of the molecules are proportional to the

temperature of, for example, a gas. Therefore,

at higher temperatures, the molecules

possess higher kinetic energies, as a result

the system has a higher internal energy

Covenant University, Dept. of Chemical

11/3/2017 56

Engineering, Thermodynamics (GEC 221)

Equilibrum

The kinetic theory states that matter is in

continuous state of motion, as a result of

inherent energy.

However, when the relative motion of the

component matter in a system is in exact

balance and there is no tendency to change,

equilibrium is attained.

Under this condition, T and P are uniform in

the system and only infinitesimally different

from those of its surroundings.

Covenant University, Dept. of Chemical

11/3/2017 57

Engineering, Thermodynamics (GEC 221)

Types of equilibrium

Thermodynamics deals with equilibrium states.

The word equilibrium implies a state of balance.

There are many types of equilibrium, and a

system is not in thermodynamic equilibrium

unless the conditions of all the relevant types of

equilibrium are satisfied.

The condition of a system in which all

competing influences are balanced.

11/3/2017 58

Engineering, Thermodynamics (GEC 221)

Examples on Equilibrium

11/3/2017 59

Engineering, Thermodynamics (GEC 221)

Covenant University, Dept. of Chemical

11/3/2017 60

Engineering, Thermodynamics (GEC 221)

Thermal equilibrium : temperature is the

same throughout the entire system. That is,

the system involves no temperature

differential, which is the driving force for heat

flow.

Before After

50oC 23oC

33oC 33oC

40oC 30oC

35oC 33oC 33oC

33oC

44oC 20oC

11/3/2017 61

Engineering, Thermodynamics (GEC 221)

Mechanical equilibrium

This is related to pressure, and a system is in

mechanical equilibrium if there is no change

in pressure at any point of the system with

time.

However, pressure may vary within the system

with elevation as a result of gravitational

effects.

The variation of pressure as a result of gravity

in most thermodynamic systems is relatively

small and usually disregarded.

Covenant University, Dept. of Chemical

11/3/2017 62

Engineering, Thermodynamics (GEC 221)

wall

11/3/2017 63

Engineering, Thermodynamics (GEC 221)

Phase equilibrium

A system involving two phases reaches

equilibrium when the mass of each phase

reaches an equilibrium level and stays there.

11/3/2017 64

Engineering, Thermodynamics (GEC 221)

Chemical equilibrium

A system is in chemical equilibrium if its

chemical composition does not change with

time, that is, no chemical reaction occurs.

relevant equilibrium criteria are satisfied.

Covenant University, Dept. of Chemical

11/3/2017 65

Engineering, Thermodynamics (GEC 221)

Reversibility

Reversibility conceives of a closed system

process whose direction can be reversed at

any point by an infinitesimal change in

external conditions. It means both the system

and the surroundings are returned to their

initial states at the end of the reverse

process.

It means the process can be reversed without

leaving any trace on the surroundings.

11/3/2017 66

Engineering, Thermodynamics (GEC 221)

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

11/3/2017 67

Engineering, Thermodynamics (GEC 221)

Reversible processes

Quasi-equilibrium expansion

and compression of a gas

Frictionless pendulum

11/3/2017 68

Engineering, Thermodynamics (GEC 221)

A reversible process is possible only if the net

heat and net work exchange between the

system and the surroundings is zero for the

combined (original and reverse) process.

Processes that are not reversible are called

irreversible processes. Once a cup of hot

coffee cools, it will not heat up by retrieving

the heat it lost from the surroundings. If it

could, the surroundings, as well as the system

(coffee), would be restored to their original

condition, and this would be a reversible

process.

Covenant University, Dept. of Chemical

11/3/2017 69

Engineering, Thermodynamics (GEC 221)

Friction

Causes the transformation of mechanical

energy to internal energy --- Resident energy

Note that transformations other than

mechanical to heat occur.

For example as heat flows when a

temperature difference exists, electricity flows

under an electromotive force, chemical

reactions occur because of a chemical

potential exists.

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Engineering, Thermodynamics (GEC 221)

In summary, a reversible process ;

Is frictionless.

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.

Covenant University, Dept. of Chemical

11/3/2017 71

Engineering, Thermodynamics (GEC 221)

The reversible process is ideal in that it

provides the best results. The reversible work

as a limiting value can be combined with an

appropriate efficiency to yield a reasonable

approximation to the work of an actual

process.

Note that friction renders a process

irreversible. Other factors include

unrestrained expansion, mixing of two fluids,

heat transfer across a finite temperature

difference, electric resistance, inelastic

deformation of solids, and chemical reactions.

Covenant University, Dept. of Chemical

11/3/2017 72

Engineering, Thermodynamics (GEC 221)

Enthalpy

Its a combination property. The enthalpy, H,

defined as:

H U + PV 9

where H, U and V are molar or unit mass values.

Gotten from the Greek word enthalpien

( which means to heat).

Recall that the product P x V has energy units.

11/3/2017 73

Engineering, Thermodynamics (GEC 221)

Q = nH = nCpdT and W = -nPdV

Only for mechanically reversible, constant

pressure conditions.

11/3/2017 74

Engineering, Thermodynamics (GEC 221)

Conservation

Conservation is a very general concept. It states

that when any change takes place, the overall

effect is zero, i.e. the total quantity of matter

and energy, before and after any change

remains constant. It applies to :

Single matter or/and surroundings

Isolated, closed or open systems

Single or multistep processes

Single or multi-component processes/ system

Units

Covenant University, Dept. of Chemical

11/3/2017 75

Engineering, Thermodynamics (GEC 221)

Under any of these conditions, the total

amount of matter or/and energy remain

constant, for a process or/and system as

changes take place from one state to the

other.

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Engineering, Thermodynamics (GEC 221)

Application to system

B

SYSTEM

A C

A+CB=0 10

By convention, input to system is +ve

and output is ve.

Covenant University, Dept. of Chemical

11/3/2017 77

Engineering, Thermodynamics (GEC 221)

Technical Definition of Thermodynamics

On the basis of the our discussions so far,

thermodynamics can be defined as the

science that considers the relationship

between a quantity of energy that causes/

accompanies a change of state from 1 to 2,

and the properties in State 1 and State 2.

(E) = f( P1, P1, P1 P2, P2, P2) 11

finite (countable) changes in the quantities

enclosed in brackets.

11/3/2017

Covenant University, Dept. of Chemical

78

Engineering, Thermodynamics (GEC 221)

The First Law of Thermodynamics

It is usually expressed in many forms:

1. Although energy assumes many forms, the

total quantity of energy is constant, and

when energy disappear in one form, it

appears simultaneously in other forms. It

applies to a system and its surrounding.

Surroundings) = 0 12

11/3/2017 79

Engineering, Thermodynamics (GEC 221)

Energy containable and storable in the system

may be internal, potential or/ and kinetic.

Work and heat energy are said to be energy

in transit, across the boundary dividing the

system and its surroundings.

Writing each energy term in Eq. 12 in terms

of its properties, it turns out in the form of Eq.

11.

On these bases, Eq. 12 will be developed for

various practical applications:

11/3/2017 80

Engineering, Thermodynamics (GEC 221)

Energy Balance for Closed Systems

In a closed system, only energy in transit can

cross the boundary of the system.

Since matter cannot cross the boundary,

energy associated with matter internal

energy, potential and kinetic energy also can

not cross.

Therefore all energy exchange between a

closed system and its surroundings are only

heat and work. Thus the second term in Eq 12

may be replaced by

Covenant University, Dept. of Chemical

11/3/2017 81

Engineering, Thermodynamics (GEC 221)

Heat (Energy of Surroundings) = Q W

Heat and work always refer to the system,

and the choice of signs used with these

quantities depends on which direction the

energy is transferred, with respect/reference

to the system.

When it is to or out of the system, it is positive

(+) or negative (-) respectively.

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Engineering, Thermodynamics (GEC 221)

Q into system is +ve

Q out of system is ve

W into system is +ve

W out of system is ve

into the system from the surroundings:

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NOTE:

Heat and Work are path functions (their

magnitude depends on the path followed

during a process as well as the end states; e,g

states 1 to 2).

Path functions have inexact differential (in

our case designated as d e.g. dW or dQ, and

also as delta)

State properties are point functions (they

depend on the state only, and not how a

system reaches that state). They are exact

differentials (designated as )

Covenant University, Dept. of Chemical

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Therefore, the second term of Eq. 12 may be

replaced by;

(Energy of surroundings) = Qsurr + Wsurr

=-Q-W

which makes Eq 12 become

(Energy of system) = Q + W 13

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The interpolation of Eq. 13 is that total energy

change of a closed system equals the net

energy transferred into it as heat and work.

But closed systems undergo processes during

which only the internal energy of the system

changes. For such processes Eq. 13 reduces to:

Ut = Q + W 14

where Ut = mU or Ut = nU

Equation 14 is for a finite closed system

Covenant University, Dept. of Chemical

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For differential changes:

dUt = dQ + dW 15

For closed system of n moles, Eq. 14 and Eq. 15

may be written as

(nU) = n U = Q + W 16

d(nU) = ndU = dQ + dW 17

Note that Q and W are extensive properties and

not thermodynamic properties. They depend

on their history. Thermodynamic properties

are unique, not ambiguous i.e. not dependent

on path. dW and not W

Covenant University, Dept. of Chemical

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What makes Eq. 17 a thermodynamic

equation is that the LHS of the equation is a

thermodynamic property - the beginning and

end conditions are specified irrespective of

the paths.

The fact that the factors on the RHS are not

thermodynamic properties implies that the

specific conditions have to be specified for

thermodynamic states to be met.

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When n =1, Eq. 16 and Eq. 17 become;

U = Q + W and dU = dQ + dW, for the

intensive state of the system.

Equation 17 is the ultimate source of all

property relations that connect the internal

energy to measurable quantities.

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It is also important to note that;

The differential of a state function represents

an infinitesimal change in its value. Integration

of such a differential results in finite difference

between two of its values, e.g.

= P2 P1 = P and

= V2 V1 = V

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The differentials of heat and work are not

changes, but are infinitesimal amounts.

When integrated, these differentials give not

finite changes, but finite amounts. Thus,

dQ = Q and dW = W

work is not a property and systems do not

possess work at a state.

Smith, Van Ness and Abbott.

Covenant University, Dept. of Chemical

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For a closed system undergoing the same

change in state by several processes,

experience shows that the amounts of heat

and work required differ for differential

processes, but that the sum of Q + W is the

same for all processes.

This is the basis for identification of internal

energy as a state function. The same amount

of Ut is given by equation 14 regardless of

the process, provided only that the change in

the system is between the same initial and

final states.

Covenant University, Dept. of Chemical

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Phases of a pure substance

A substance that has a fixed chemical

composition throughout is called a pure

substance. Water, nitrogen, helium, and

carbon dioxide, for example, are all pure

substances.

A mixture of various chemical elements or

compounds also qualifies as a pure substance

as long as the mixture is homogeneous.

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Substances exist in different phases (at room

temperature, copper is solid, mercury is liquid,

and nitrogen is gas). Under different

conditions, each may appear in a different

phase.

A substance may also have several phases

within a principal phase, each with a different

molecular structure. For example, carbon may

exist as graphite or diamond in the solid

phase.

Covenant University, Dept. of Chemical

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A phase is identified as having a distinct

molecular arrangement that is homogeneous

throughout and separated from the others by

easily identifiable boundary surfaces. The two

phases of H2O in ice water represent an

example.

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The state of a pure homogeneous fluid is

fixed whenever two intensive thermodynamic

properties are set at specific values.

In contrast, when two phases are in

equilibrium, the state of the system is fixed

when only a single property is specified. For

example a mixture of steam and liquid water,

in equilibrium at 101.33 kPa can exist only at

100 oC.

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For multi phase systems, the number of

independent variables that must be arbitrarily

fixed to establish its intensive state is given by

Gibbs phase rule equation,

F = 2+N 18

= number of phases

N = Number of chemical species

F = Degrees of freedom of the system

Equ. 18 holds only for non-reacting systems at

equilibrium.

Covenant University, Dept. of Chemical

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A phase is a homogeneous region of matter.

Examples are;

Mixture of gas

A liquid or liquid solution

Bubbles of gas dispersed in a liquid

Fine particles dispersed in gas or liquid

Liquid droplets dispersed in another

Liquid with which its immiscible

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For solutions, note that the compositions are

not independent; for these, the phase rule

gives the minimum number of variables from

the set of fractional compositions, that must

be fixed.

Study and understand

Examples 2.5 in Smith,

Van Ness and Abbott.

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Constant V and Constant P Processes

For a homogeneous fluid contained in a closed

system, the energy balance is

d (nU) = dQ + dW 17

dW = -P d (nV) 19

dW = F dl = P A dl

= P A d (V/A)

=P dV for constant A

Combination of Eqs. 17 and 19 give

d (nU) = dQ - Pd (nV) 20

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Constant V Process

For constant volume

0

d(nU)= dQ-Pd(nV) OR

dQ = d (nU)v 21

and Q = n U 22

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Constant P Process

Making dQ subject in Eq. 17 yields

dQ = d (nU) + P d (nV)

for constant pressure

dQ = d (nU) + d (nPV)

= d [ n (U + PV)]

But H = U + PV 9

dQ = d (nH) constant P 23

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and Q = n H constant P 24

From Eq. 9,

dH = dU + d (PV) 25

and H = U + (PV) 26

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Heat Capacity at Constant Volume

Heat capacity, as defined by equation 8 is not

a thermodynamic property, since Q (process

dependent), is not a thermodynamic property.

However heat capacity at constant volume is a

thermodynamic property.

Relating Eq. 22 with Eq. 8 suggest the constant

volume heat capacity as;

Cv 27

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C applied to both molar and specific cases. For

the particular case of closed system Equation

27 can be written as;

dU = Cv dT ( constant V) 28

Integration yields

U = (constant V) 29

reversible, constant volume process gives:

Q = nU = n (constant V)

30

Covenant University, Dept. of Chemical

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The specific, here, of mechanical reversibility

is essential since, that is what makes Q = n U.

This establishes the fact that;

For the calculation of property changes, an

actual process may be replaced by any other

process which accomplishes the same change

in state.

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Heat Capacity at Constant Pressure

The constant pressure heat capacity is

defined as:

Cp 31

specific heat capacities just as we have for Cv,

corresponding with the specification of H.

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For a constant pressure, closed system,

Equation 31 translates to

dH = Cpdt (constant p) 32

and H = ( constant P) 33

process, this result may be combined with

Equation 24

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Q = nH = n (constant P) 34

in Smith, Van Ness and Abbott.

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Mass and Energy Balances for Open Systems

The closed system is a special type of open

system

Measures of Flow

Mass flow rate

Molar flow rate

Volumetric flow rate q

Velocity u

= M , q = uA 35

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= uA 36

= uA 37

A = cross sectional area, = density.

Although velocity is a vector quantity, its scalar

magnitude, u is used as the average speed of a

stream in the direction normal to A.

Note that all the flow rates represent measure

of quantity per unit time, however, u does not

suggest the magnitude of flow.

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MASS BALANCE FOR OPEN SYSTEMS

1 CONTROL VOLUME

dmcv/dt

CONTROL

2

SURFACE

in control volume

Covenant University, Dept. of Chemical

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The application of the law of conservation

for mass in this system is mass balance.

For Figure 1, it is

38

is the accumulation

(if depletion, its negative) of mass.

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fs represents the following streams.

The conservation applied is in +ve for inflows,

-ve for outflows, with respect to the system.

On basis the second term in Eq. 38 is

=

When is written in terms of Eqs. 36, 37 and

38 becomes

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39

This is the CONTINUITY EQUATION.

At steady state, there is neither accumulation

nor consumption while flows are still taking

place, by which

= 0 40

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Therefore ( )fs = 0

With only one single entrance and outlet, with

equal in both

= Constant = 41 =

can be written as:

= = = 42

This form of continuity equation is frequently

used.

Covenant University, Dept. of Chemical

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THE GENERAL ENERGY BALANCE

The law of conservation is as equally applicable

to energy as it is for mass.

For a fluid in motion as in Figure 2 below:

E1 E2

Covenant University, Dept. of Chemical

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The total energy, E, for mass of fluid is given by the

equation.

43

system consists of three parts for a non-

flowing fluid (U, K.E., P.E.) and four parts for a

flowing fluid (flow energy/ flow work : Pv, U,

K.E.,P.E). v, is volume/mass

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From Figure 2, consider some fluid flowing from

Point 1 to Point 2.

Between these two points, let an amount of

heat energy, Q, be added to the fluid as

shown.

Let an amount of work W1 be done on the

fluid and the fluid do an amount of work W2

on its surrounding.

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An energy balance can be written for fluid either

as;

Or as 44

If no work, in form of pumping say, is done on

the system, a combination of Equations 43

and 44 yields;

m -m

= Q - (PV) m 45

Covenant University, Dept. of Chemical

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H = U + PV, Eq. 45 becomes

46

This equation is applicable to a situation of

steady state flow (the fluid properties at an

inlet or exit remain constant, i.e. do not

change with time), with internal friction in the

fluid but no shaft work done.

Eq. 46 may have been obtained from over

simplification of the conditions applied in

Figure 2

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For more practical purposes, other types of

work such as stirring, etc. may have gone into

the system. With stirring, for example Eq. 46

becomes

kinetic energies become negligible with

respect to enthalpy changes, we may have,

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= + 48

And unit mass basis

48

Where are on unit mass basis.

Smith, Van Ness and Abbott.

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Examples of steady-flow engineering devices

Nozzles and Diffusers

cause large changes in fluid velocities and thus

kinetic energies

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A nozzle is a device that increases the velocity

of a fluid at the expense of pressure.

A diffuser is a devise that increases the

pressure of a fluid by slowing it down.

It follows that nozzles and diffusers perform

opposite tasks. They are commonly utilized in

jet engines, rockets, spacecraft, and even

garden hoses.

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Other examples include;

Turbine and Compressors

Throttling Valves

Mixing Chambers, Heat Exchangers

Pipe and Duct flow

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A FLOW CALORIMETER FOR ENTHALPY MEASUREMENTS

such as P, T, V, etc can be measured either

directly with meters or indirectly.

non thermodynamic properties such as Q,

W etc. can also be measured indirectly using a

calorimeter and a tachometer respectively.

W can also be measured directly with a

dynamometer.

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However, properties such as enthalpy, entropy

etc. can only be obtained by relating them

with some other directing measurable

parameters such as P, V and T.

An experimental set up such as presented in

Figure 3 below can be arranged for the

measurement of enthalpy.

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Flow calorimeter

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The essential features are

an electric resistance heater immersed in a

flowing fluid

minimal velocity and elevation changes from

section 1 to section 2, implying minimal

changes in kinetic and potential energy.

With no shaft work entering the system, Eq.

48

reduces to

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49

The rate of heat transfer to the fluid is

determined from the resistance of the heater

and the current passing through it.

Measurements of the heat rate and flow rate

allow calculation of the change between

sections 1 and 2.

The constant temperature water bath is filled

with a mixture of crushed ice and water to

maintain a temperature of 0 oC

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The temperature and pressure at section 2 are

measured by suitable instruments.

From Eq. 49; H = Q, values of water for

various conditions at section 2 are given by

H2 = H1 + Q where

flowing and H1 is assumed, for practical

purposes to remain as a constant value, with

the stipulated conditions.

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NOTE: Absolute values of enthalpy or internal

energy are unknown. Absolute value is actual

value at a given position, e.g. we have

absolute pressure, absolute temperature.

Therefore, an arbitrary value may be assigned

to H1 as the basis for all other enthalpy values.

makes

H2 = H1 + Q = 0 + Q = Q

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On this basis, enthalpy values can be obtained

for a range of temperatures and pressures

existing at section 2.

Similarly, specific volumes measurements

made at these conditions may be used to

calculate values of internal energy, U, from Eq.

9, H = U + PV

are compiled over the entire useful range of

conditions.

Covenant University, Dept. of Chemical

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The most widely used of such tabulations for

water and is known as the Steam Tables. Tables

for various other substances are found in the

literature.

Property tables such as steam tables provide very

accurate information about the properties, but

they are bulky and vulnerable to typographical

errors.

A more practical and desirable approach is to

have some simple relations among the properties

that are sufficiently general and accurate.

Study and understand Examples 2.15 to 2.17 in

Smith, Van Ness and Abbott.

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SUMMARY

measurement and real understanding of the

meaning of total volume

and specific or molar volume,

pressure and temperature have been

presented.

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the application of Phase Rule to the definition

of thermodynamics, as presented in Eq. 11,

gives the least complex model/equation

relating pressure, molar volume and

temperature as

PV = RT 50

The equation is for an ideal gas. This is the

simplest best known equation of state for

substances in the gas phase. The equation

predicts the P-v-T behaviour of a gas quite

accurately within some properly selected

region.

Covenant University, Dept. of Chemical

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However, industrial processes for which

thermodynamics are intended for applications go

beyond ideal gases to pure and mixture of gases,

liquids and solids.

They also go beyond PVT relations to others from

which properties such as enthalpy, H, entropy, S

etc can be obtained.

Accordingly, equations of state, which Eq. 50

represents, can be developed for virtually all

industrial conditions.

The variations of properties during phase-change

processes are best studied and understood with

the help of property diagrams/relations.

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PVT Behaviour of Pure Substances

1.P-T Relation (Figure 4)

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The P-T relation is often called the phase diagram

since all three phases are separated from each

other by three lines.

Sublimation line separates the S-V regions.

Vaporization line separates the L-V regions.

Fusion/melting line separates S-L regions.

The three lines meet at the triple point, where all

three phases coexist in equilibrium.

The vapourization line ends at the critical point

because no distinction can be made between

liquid and vapour phases above the critical point.

Substances that expand and contract on freezing

differ only in the melting line on the P-T diagram

Covenant University, Dept. of Chemical

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P-V relation for a pure substance (Figure 5)

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From Figure 5b (P-V with constant T),

BC is saturated liquid line

C is the critical point

CD is saturated vapour line

The doom, i.e. BCD is the saturated L-V region.

Beyond the dash lines is the superheated

vapour region.

The left side of the doom is the compressed

liquid region.

Figure 5a is the general P-V relation which is for

a substance that contracts on freezing

Covenant University, Dept. of Chemical

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PT at specific constant V (Figure 6)

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Single phase region

It was pointed out that we should be able to

calculate all the properties of a system at any

state once two independent, intensive

properties are available.

For properties that cannot be measured

directly such as internal energy, enthalpy, and

entropy, we can get them measured from the

knowledge of the intensive properties.

The calculation of these properties from

measurable ones depends on the availability

of simple and accurate relations between the

two groups.

Covenant University, Dept. of Chemical

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PVT relations in each of the single phases in

Figures 5 and 6 is relatively simpler than

between any of two phases.

This suggests that relatively simple PVT

equations can be established for each of the

single phase regions.

For example, an equation of state can be

formulated for any of P, V or T as subject, with

the other two as variable, in accordance with

the phase rule.

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51

In practice, each of the partial derivatives has

physical meaning.

of volumetric expansion is a measure of

the change in volume with temperature

at constant pressure)

53 is

Isothermal compressibility

Covenant University, Dept. of Chemical

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A combination of Eqs. 51, 52 and 53 yields

Figure 5 shows that they are almost straight

down and are very close pack. This means that

V is relatively invariant with T and P, hence

the usual idealistic claim that liquids are

incompresssible.

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and with this assumption, from equ 54 after

integration,

= 55

Examples 3.1 in Smith, Van

Ness and Abbott.

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EQUATIONS OF STATE

Any equation that relates the pressure, temperature,

and specific volume of a substance is called an

equation of state.

There are several equations of state, some simple

and others complex.

The simplest and best known equation of state for

substances in the gas phase is the ideal-gas

equation of state.

It predicts the PVT behaviour of a gas quite

accurately within some properly selected region.

Covenant University, Dept. of Chemical

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VIRIAL EQUATIONS OF STATE

Examination of Figure 5b shows that P is

inversely proportional to V, such that the

product PV for a given T should be about

constant and can be represented as a function

of P.

It also suggests that PV for an isotherm can be

represented by a power series in P:

PV = a + bP + cp2 + .

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If b = aBI, c = aCI, etc then

PV = a(1 + BIP + CIp2 + DIp3 + ..) 56

where a, BI, CI .. are constants for a given

temperature and a given chemical species.

The coefficients can be determined experimentally

or theoretically from statistical mechanics.

As the pressure approaches zero, all the virial

coefficients will vanish and the equation will

reduce to an ideal gas equation of state.

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The PVT behaviour of a substance can be

represented accurately with the virial

equation of state over a wider range by

including a sufficient number of terms.

an infinite series. However, experience shows

that at low pressures, truncation after two

terms often provides satisfactory results.

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Ideal Gas Temperatures; Universal Gas Constant

It has been established empirically that while

parameters BI, CI etc are functions of

temperature and species, parameter, a, is a

function only of temperature for all chemical

species ( in some text, a is replaced with RT).

This is demonstrated by the plot of PV versus P

for four chemical species as in Figure 7, where

the limiting value of PV as P 0 is the same

for all the gases. In this limit (denoted by

asterisk), Eq. 56 becomes

Covenant University, Dept. of Chemical

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Covenant University, Dept. of Chemical

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This property of gases is the basis for

establishing an absolute temperature scale.

What is required is to arbitrarily assign the

functional relationship and also assign a value

for a single point on the scale. The procedure

assigned is that which defines the Kelvin scale

and

Makes (PV)* directly proportional to T, with R

as the constant of proportionality

57

Covenant University, Dept. of Chemical

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Assigns the value of 273.16K to the

temperature of the triple point of water

(denoted by subscript t):

= R .. 58

Division of Eq. 57 by Eq. 58 gives:

or

59

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Eq. 59 established the Kelvin temperature

scale throughout the temperature range for

which values of (PV)* are experimentally

accessible.

The state of a gas at the limiting condition

where P 0 ,

The molecules become so far apart

The unit molecular volume became

negligible in comparison with the total volume

occupied by a unit mass of the gas.

Intermolecular forces approach zero.

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These conditions define the ideal gas state

and Eq. 59 establishes the ideal gas

temperature scale.

The proportionality constant, R, is defined as

the universal gas constant. Its numerical value

is given by Eq. 58 from experimental PVT data:

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In reality, this data is difficult to measure. This

notwithstanding, the internationally accepted

value of is 22,711.8cm3 bar mol-1

leading to the following value of R:

= 83.1447c K-1

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Two Forms Of The Viral Equation

Modification of eq. 56 introduces a property

as

transforms Eq. 56

An alternative expression for is also in

common use,

Covenant University, Dept. of Chemical

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= 1 + +

compressibility factor. Eq. 61 and 62 are also

called virial equations and the parameters BI,

CI, DI etc. and B, C, D, etc. are called virial

coefficients. BI and B are second virial

coefficients, CI and C are third virial

coefficients, etc.

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For a given gas, the virial coefficients are

functions of temperature only.

The two sets of coefficients in Eq. 61 and 62

are related as follows:

BI = .. 63

CI = 64

DI = 65

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Many other equations of state have been

proposed for gases, but the virial equations

are the only ones firmly based on statistical

mechanics, which provide physical significance

to the virial coefficients.

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Thus, for the expansion in , the term arises

on account of interactions between pairs of

molecules, the , on account of three-body

interactions, etc.

Because two-body interactions are many times

more common than three-body interactions

and three-body interactions are many time

more numerous than four-body interactions,

etc. the contributions to of the successively

higher-ordered terms decrease rapidly.

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The terms etc. of the virial expansion

(Eq. 62), arise by reason of molecular

interactions. Otherwise the virial coefficients

B,C, etc. would be zero in the absence of such

interactions and the virial expansion would

reduce to

or PV = RT

In reality, molecular interactions do exist and

influence the observed behavior of real gases.

However, as pressure is reduced at constant

temperature, V increases and the

contributions of the terms

in Eq. 62 decrease 165

For P0, approaches unity, not because of

any change in virial coefficients, but because V

becomes infinite.

Thus in the limit, as P0, the equation of

state reduces to the same simple form as for

the hypothetical case of B = C = = 0,

that is

or PV = RT

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From the phase rule, that internal energy of a real

gas is a function of pressure and temperature.

This pressure dependency varies from molecular

interactions of the gas. In the absence of

molecular interactions, internal energy would

depend on temperature only and no energy

would be required to bring about pressure and

volume changes. These concepts of the behavior

of a hypothetical gas in which no intermolecular

forces exist and of a real gas in the limit as

pressure approaches zero lead to the definition of

an ideal gas as one whose macroscopic behavior

is characterized by

11/3/2017 167

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The equation of state

PV = RT (ideal) ...66

An internal energy that is a function of

temperature only

U = U(T) (ideal gas) 67

11/3/2017 168

Engineering, Thermodynamics (GEC 221)

Equations For Process Calculations For Ideal Gases

It has been noted earlier that very common

parameters required in any process are heat

and work.

Further, for a mechanically reversible closed

system process

dW = - PdV 19

And for an ideal gas

dQ + dW = CVdT .17, 28

11/3/2017 169

Engineering, Thermodynamics (GEC 221)

substituting for dW and solution for dQ yields

an equation valid for an ideal gas in any

mechanically reversible closed-system

process.

dQ = CVdT + PdV . 67

This equation contains the variables P, V and T,

only two of which are independent.

Working equations are obtained by using the

equation to reduce the Eq. 67 to just

two independent variables.

11/3/2017 170

Engineering, Thermodynamics (GEC 221)

With

dQ = CVdT + 68

Substituting 68 into 17,

dW = - RT . 69

with

11/3/2017 171

Engineering, Thermodynamics (GEC 221)

dQ = Cp dT - . 70

and dW = - R dT + RT . 71

with

work is simply

dW = - P dV and

dQ = dP + P dV . 72

11/3/2017 172

Engineering, Thermodynamics (GEC 221)

These equations (68, 70, and 72) may be applied

for ideal gases to various kinds of processes

that are closed and mechanically reversible, as

follows:

Isothermal Processes

At constant temperature,

U = = 0

and H = = 0

Similarly write Eqs. 68 and 70,

Covenant University, Dept. of Chemical

11/3/2017 173

Engineering, Thermodynamics (GEC 221)

=

=

Note that Q = -W, a result which also follows

from Eq. 14

Q = -W =

(const. T)

11/3/2017

.. 73

Covenant University, Dept. of Chemical

174

Engineering, Thermodynamics (GEC 221)

Isobaric Process

From previous equations

U = and H =

Q = and W = -R(T2 T1)

Note that Q = H

Q = H = (const. P) .. 74

11/3/2017 175

Engineering, Thermodynamics (GEC 221)

Isochoric Process (Constant V)

From previous equations

U = and H =

equation,

Q = and W = - PdV = 0

Note that Q = H,

Q = U = Const. V . 75

Covenant University, Dept. of Chemical

11/3/2017 176

Engineering, Thermodynamics (GEC 221)

Adiabatic Process; Constant Heat Capacities

An adiabatic process is one for which there is

no exchange of heat between the system and

the surroundings,

may therefore be set to zero. Integration with

and constant gives,

From Eq. 68, =-

Covenant University, Dept. of Chemical

11/3/2017 177

Engineering, Thermodynamics (GEC 221)

=

=

and =

= constant . 76a

11/3/2017 178

Engineering, Thermodynamics (GEC 221)

= constant .. 76b

and = constant .. 76c

given that .. 77

11/3/2017 179

Engineering, Thermodynamics (GEC 221)

2nd Law of Thermodynamic

The 1st law was applied to processes involving

closed and open systems.

It was shown that a process must satisfy the

first law to occur. However, to further our

discussions, satisfying the first law alone does

not ensure that the process will actually take

place.

We know that the amount of heat loss by a

hot cup of coffee is equal to amount of heat

gain by the surrounding air.

Covenant University, Dept. of Chemical

11/3/2017 180

Engineering, Thermodynamics (GEC 221)

But the hot coffee getting hotter in a cooler

room as a result of heat transfer from the

room air never takes place.

Doing the reverse of the process would not

violate the first law as long as the amount of

energy lost by the air is equal to the amount

gained by the coffee.

Therefore, it is cleared that processes proceed

in a certain direction and not in the reverse

direction.

11/3/2017 181

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The 1st law places no restriction on the

direction of a process, but satisfying the first

law does not ensure that the process can

occur.

The inadequacy of the first law to identify

whether a process can take place is corrected

by another general principle, the 2nd law of

thermodynamics.

The reverse process of hot cup of coffee

getting hotter from cold air violates the

second law of thermodynamics.

11/3/2017 182

Engineering, Thermodynamics (GEC 221)

The violation is easily detected by a property

called entropy.

It follows therefore that a process must satisfy

both the first and second laws of

thermodynamics to proceed.

The 2nd law is not limited in identifying the

direction of processes. It also asserts that

energy has quality as well as quantity. The 1st

law is concerned with the quantity of energy

and the transformation of energy from one

form to another with no regard to its quality.

Covenant University, Dept. of Chemical

11/3/2017 183

Engineering, Thermodynamics (GEC 221)

Preserving the quality of energy is a major

concern to engineers, and the second law

provides the necessary means to determine

the quality as well as the degree of

degradation of energy during a process.

The second law is also used in determining the

theoretical limits for the performance of

commonly used engineering systems, such as

heat engines and refrigerators, as well as

predicting the degree of completion of

chemical reactions.

Covenant University, Dept. of Chemical

11/3/2017 184

Engineering, Thermodynamics (GEC 221)

Thermal energy reservoir (or just a reservoir)

It is a hypothetical (assumed) body with a

relatively large thermal energy capacity (mass

x specific heat).

It can absorb or supply finite amounts of heat

without undergoing any change in

temperature.

Large bodies of water such as oceans, lakes,

and rivers as well as atmospheric air can be

modeled accurately as thermal energy

reservoir because of their large thermal

energy storage capabilities or thermal masses.

Covenant University, Dept. of Chemical

11/3/2017 185

Engineering, Thermodynamics (GEC 221)

The atmosphere does not warm up as a result

of heat losses from residential buildings

during winter.

A body does not have to be very large to be

considered a reservoir.

Any physical body whose thermal capacity is

large relative to the amount of energy it

supplies or absorbs can be modeled as a

reservoir.

11/3/2017 186

Engineering, Thermodynamics (GEC 221)

experience shows that;

Whereas work can be transformed to heat

with 100% efficiency, the reverse is not the

same.

Heat can be transformed from a hot body to a

cold body, but the reverse is not true.

These suggest that different forms of energy

may possess different quality. In this case,

work is of a higher quality than heat and

further, heat at a higher temperature is at a

higher quality than heat at a lower

temperature.

Covenant University, Dept. of Chemical

11/3/2017 187

Engineering, Thermodynamics (GEC 221)

The second law of thermodynamics are

expressed in the following statements;

Statement 1 : No apparatus can operate in

such a way that its only effect

-that being the only thing happening (in

system and surroundings) is to convert heat

absorbed by a system completely into work

done by the system.

OR

11/3/2017 188

Engineering, Thermodynamics (GEC 221)

Statement 1a; It is impossible by a cyclic

process to convert the heat absorbed by a

system completely into work done by a

system.

Statement 2: No process is possible which

consists solely (at being the only thing

happening) in the transfer of heat from one

temperature level to a higher one.

11/3/2017 189

Engineering, Thermodynamics (GEC 221)

These observations are addressed by the

second law of thermodynamics and they are

very well demonstrated by the principles and

practice of heat engine and heat pump.

11/3/2017 190

Engineering, Thermodynamics (GEC 221)

A reservoir that supplies energy in the form of

heat is called a SOURCE, and one that absorbs

energy in the form of heat is called a SINK.

Thermal energy reservoirs are often referred

to as heat reservoir since they supply or

absorbs energy in the form of heat.

11/3/2017 191

Engineering, Thermodynamics (GEC 221)

Thermal energy

SOURCE

HEAT

HEAT

Thermal energy

SINK

absorbs it Covenant University, Dept. of Chemical

11/3/2017 192

Engineering, Thermodynamics (GEC 221)

Heat engines

Work can easily be converted to other forms

of energy, but converting other forms of

energy to work is not that easy

Work No Work

Heat

completely, but the reverse is not true

Covenant University, Dept. of Chemical

11/3/2017 193

Engineering, Thermodynamics (GEC 221)

The mechanical work done by the shaft as

shown is first converted into internal energy of

the water.

This energy may then leave the water as heat.

Attempt to reverse this process will fail.

Transferring heat to the water does not cause

the shaft to rotate.

From this we conclude that work can be

converted to heat directly and completely, but

converting heat to work requires the use of

some special devises. These devises are called

heat engines Covenant University, Dept. of Chemical

11/3/2017 194

Engineering, Thermodynamics (GEC 221)

Heat Engines (HE)

11/3/2017 195

Engineering, Thermodynamics (GEC 221)

Heat Engines differ considerably from one another.

They are all can be characterized by the following

They receive heat from a high-temperature

source (solar energy, oil furnace, nuclear

reactor, etc)

They convert part of this heat to work (usually

in the form of a rotating shaft).

They reject the remaining waste heat to a low-

temperature sink (the atmosphere, rivers, etc)

They operate in a cycle.

11/3/2017 196

Engineering, Thermodynamics (GEC 221)

TH

QH

Qc

Tc

Figure 10. The principle of heat engines

Covenant University, Dept. of Chemical

11/3/2017 197

Engineering, Thermodynamics (GEC 221)

A heat engine is a system which converts heat QH

drawn from a higher temperature TH, to work, W,

and discharges residual heat Qc, at a lower

temperature Tc.

The principle of the heat engine is illustrated in

Figure 10.

The practice of a heat engine requires that a heat

exchanger brings about heat exchange between a

reservoir at each of hot and cold ends, where the

heat exchange takes place through a fluid called a

working fluids, as presented in Figure 11.

11/3/2017 198

Engineering, Thermodynamics (GEC 221)

Heat engines and other cyclic devices usually

involve a fluid to and from which heat is

transferred while undergoing a cycle. This fluid

is called the working fluid.

11/3/2017 199

Engineering, Thermodynamics (GEC 221)

QH

Heat engine

Boiler

W Pump Turbine W

Condenser

Figure 11. Practice of heat engines Qc

Covenant University, Dept. of Chemical

11/3/2017 200

Engineering, Thermodynamics (GEC 221)

Thermodynamic representation of Heat Engine

P

1 2

Constant Entropy & Enthalpy

Constant Entropy

4 3

Figure 12 H

Covenant University, Dept. of Chemical

11/3/2017 201

Engineering, Thermodynamics (GEC 221)

The term heat engine is often used in broader

sense to include work producing devices that do

not operate in a thermodynamic cycle.

Engines that involve internal combustion such as

gas turbines and car engines fall into this

category. These devises operate in a mechanical

cycle but not in a thermodynamic cycle since the

working fluid (the combustion gases) does not

undergo complete cycle. Instead of being cooled

to the initial temperature, the exhaust gases are

purged and replace by fresh air-and-fuel mixture

at the end of the cycle.

Covenant University, Dept. of Chemical

11/3/2017 202

Engineering, Thermodynamics (GEC 221)

The work producing device that best fit into

the definition of a heat engine is the steam

power plant, which is an external combustion

engine. That is, combustion takes place

outside the engine, and the thermal energy

released during the process is transferred to

the steam as heat.

Schematic of a basic steam power plant is

shown in figure 11.

11/3/2017 203

Engineering, Thermodynamics (GEC 221)

Figure 12 represents the Rankine cycle of the

system just described in Figure 11, on a

pressure enthalpy diagram for the said fluid.

Point 1 on the diagram represents a sub-

cooled liquid entering the boiler in Figure 11.

step 1 2 represents the isothermal boiling of

the fluid.

point 2 representing saturated vapour coming

out of the boiler.

The quantity of heat QH absorbed by the

boiler is given by

Covenant University, Dept. of Chemical

11/3/2017 204

Engineering, Thermodynamics (GEC 221)

QH = H2 H1 , Where H is the enthalpy.

Step 2 3 represents the operation in the

turbine, in which saturated steam at point 2

expands from a high to low pressure at

constant entropy.

The quantity of work W, yielded is represented

by

W = H2 H3

11/3/2017 205

Engineering, Thermodynamics (GEC 221)

Step 3 4 represents isothermal condensation

where the quantity of heat Qc removed for

this purpose is given by

Qc = H3 H4

Thus operation is at isothermal condition at Tc

The lifting of saturated liquid from point 4 to 1

is isentropic, i.e. constant entropy and

enthalpy.

11/3/2017 206

Engineering, Thermodynamics (GEC 221)

Thermal Efficiency of Heat Engine

The net work output of a heat engine is always

less than the amount of heat input.

It means only part of the heat transferred to

the heat engine is converted to work.

The fraction of the heat input that is

converted to net work output is a measure of

the performance of a heat engine and is called

the thermal efficiency.

11/3/2017 207

Engineering, Thermodynamics (GEC 221)

It is important to note that the system obeys

the first law.

For example, from figure 11,

W = Q H Qc

But the thermal efficiency of the engine, is

given as

= =

= =

11/3/2017 208

Engineering, Thermodynamics (GEC 221)

Qc and QH are defined as magnitudes and

therefore are positive quantities.

The thermal efficiency of a heat engine is

always less than unity since both Qc and QH

are defined as positive quantities.

Thermal efficiency is a measure of how

efficiently a heat engine converts heat that it

receives to work.

Engineers are constantly trying to improve

the efficiencies of these devices since

increased efficiencies means less fuel

consumption and thus lower fuel bills and less

pollution. Covenant University, Dept. of Chemical

11/3/2017 209

Engineering, Thermodynamics (GEC 221)

The thermal efficiencies of work producing

devices are relatively low. Ordinary spark-

ignition automobile engines have a thermal

efficiency of 25%. That is, an automobile

engine converts about 25% of the chemical

energy of the gasoline to mechanical work. In

diesel engines and large gas-turbine plants it is

40%. For large combined gas-steam plants it is

as high as 60%.

Therefore, for most efficient heat engines

available today almost one-half of the energy

supplied ends up in the rivers, lakes, or the

atmosphere as wastes or useless energy.

Covenant University, Dept. of Chemical

11/3/2017 210

Engineering, Thermodynamics (GEC 221)

Furnace

TH

QH = 100 MJ

HEAT W = 55 MJ

ENGINE

Qc = 45 MJ

Tc The atmosphere

The most efficient heat engines reject almost one-half of the

energy they receive as waste heat.

Covenant University, Dept. of Chemical

11/3/2017 211

Engineering, Thermodynamics (GEC 221)

For to be unity, i.e. net work produced be

equal to the heat responsible for the

production of the work, i.e. efficiency 100%,

Qc must be zero!

No engine has ever been built that

approaches this result; heat is always rejected

to the cold reservoir.

This observation from engineering experience

is the basis for statement 1 and 1a of the

second law.

11/3/2017 212

Engineering, Thermodynamics (GEC 221)

If a thermal efficiency of 100% is not possible

for heat engines, what then determines the

upper limit? A heat engine operating in a

completely reversible mode the Carnot

engine should serve this purpose.

NOTE: A heat engine cycle cannot be

completed without rejecting some heat to a

low temperature sink. That is, cyclic devices

such as steam power plants cannot run

continuously unless the cycle is completed.

11/3/2017 213

Engineering, Thermodynamics (GEC 221)

The theoretical heat engine that operates on

the Carnot cycle is called Carnot heat engine.

The Carnot engine is composed of four

reversible processes. Two isothermal and two

adiabatic. These can be executed either in

closed or a steady flow system.

The net work, thus the cycle efficiency of a

heat engine, can be maximized by using

processes that require the least amount of

work and deliver the most, that is, by

reversible processes.

Covenant University, Dept. of Chemical

11/3/2017 214

Engineering, Thermodynamics (GEC 221)

Carnot Cycle

The four steps that make up a Carnot cycle are as

follows

Step 1-2: Reversible Isothermal Expansion

Isothermal reversible process when the system

absorbs heat QH from the reservoir at TH.

A reversible adiabatic process that brings the

temperature back to Tc

Covenant University, Dept. of Chemical

11/3/2017 215

Engineering, Thermodynamics (GEC 221)

Step 3-4: Reversible Isothermal Compression

A reversible isothermal process while the

system maintains contact with the cold

reservoir at temperature Tc, that returns the

system to its initial state with rejection of heat

Qc.

A reversible adiabatic process from a cold

reservoir at Tc to a hot reservoir at TH .

11/3/2017 216

Engineering, Thermodynamics (GEC 221)

This set of processes can in principle be

performed on any kind of system and some of

practical interest will be described.

In overall,

W = QH Qc

11/3/2017 217

Engineering, Thermodynamics (GEC 221)

Carnot Theorem

In general the thermal efficiency of a Carnot

engine depends only on the temperature

levels and upon neither the working

substance nor the hard wares of the engine

i.e.

and as a result

11/3/2017 218

Engineering, Thermodynamics (GEC 221)

Two conclusions pertain to the thermal efficiency

of reversible and irreversible heat engines, and they

are known as the Carnot principles expressed as

follows:

1. The efficiency of an irreversible heat engine is

always less than the efficiency of a reversible

one operating between the same two reservoir.

2. The efficiencies of all reversible heat engines

operating between the same two reservoirs are

the same.

These two statements can be proved by

demonstrating that the violation of either

statement results in the violation of the 2nd law.

Covenant University, Dept. of Chemical

11/3/2017 219

Engineering, Thermodynamics (GEC 221)

1 2 3

Irrev. Rev. Rev.

HE HE HE

1<2 2=3

Covenant principles

University, Dept. of Chemical

Engineering, Thermodynamics (GEC 221)

220

ENTROPY

It is of great interest to compare the quantities

of heat transferred from and into the two

reservoirs, in the Carnot engine thus

system.

Covenant University, Dept. of Chemical

11/3/2017 221

Engineering, Thermodynamics (GEC 221)

Thus, by convention, and are considered

positive and negative respectively.

Thus,

= 0

a Carnot engine, the two quantities Q/T

associated with the absorption and rejection

of heat by the working fluid of the engine sum

to zero

Covenant University, Dept. of Chemical

11/3/2017 222

Engineering, Thermodynamics (GEC 221)

The working fluid of a cyclic engine

periodically returns to its initial state, and its

properties e.g. temperature, pressure, and

internal energy, return to their initial values,

being a primary characteristic of a property.

Thus for a Carnot cycle, Eg. T suggests the

existence of a property whose changes are

given by the quantities Q/T. The property is

called entropy.

11/3/2017 223

Engineering, Thermodynamics (GEC 221)

For reversible Carnot heat engine systems

operated in small (differential) steps,

=

or = and

11/3/2017 224

Engineering, Thermodynamics (GEC 221)

Question

A steam engine, using water as working fluid,

operates between boiler and condenser temperatures

of 2800C and 1200C, respectively.

[a] Illustrate the system with indications of areas of

energy intakes and rejections and the corresponding

conditions of operation on a P H diagram for a

Rankine cycle.

[b] What is the temperature drop in the system.

[c] Calculate the Rankine thermal efficiency of the

heat engine.

[d] Calculate the Carnot thermal efficiency of the

engine.

[e] Calculate the effectiveness of the heat engine,

with respect to a Carnot heat engine. 225

Solution

[a]

QH

P TH

1 Isothermal Boiling 2

W

4 Isothermal Condensation 3 3I

Tc

QH

11/3/2017

Covenant University, Dept. of Chemical

Engineering, Thermodynamics (GEC 221)

H 226

Solution

[b] The temperature drop of the heat engine is the

temperature difference between the boiler and condenser

2800C 1200C = 1600C

[c] The Rankine thermal efficiency, , of the system,

work done H2 H3

= = where

heat obtained H2 H1

H is enthalpy of water

Figure subscripts indicate points in the engines cycle of

operation

H2 = saturation enthalpy of water vapour at 2800C

S2 = saturation entropy (S) of water vapour at 2800C

Since operation 2 3 is isentropic, S3 = S2.

Covenant University, Dept. of Chemical

11/3/2017 227

Engineering, Thermodynamics (GEC 221)

solution

H4 = the saturation enthalpy of liquid water at 1200C

Since Operation 4 1 is isenthalpic, H4 = H1.

S3I = entropy of saturated vapour at point 3I (1200C).

From Steam tables,

H2 = 2780.4 kJ/kg

S2 = 5.8586 kJ/kg.K

S3 = 5.8586 kJ/kg.K

H4 = 503.7 kJ/kg

H1 = 503.7 kJ/kg

S3I = 7.1293 kJ/kg.K

S4 = 1.5276 kJ/kg.K

H3I = 2706 kJ/kg

Covenant University, Dept. of Chemical

11/3/2017 228

Engineering, Thermodynamics (GEC 221)

Solution

Calculation of H3

If an enthalpy balance is to be carried out along the

equilibrium temperature of 1200C, i.e 4 3 3I, on

the Heat Engine cycle, the vapour or water quality

of the wet vapour at point 3 is not known.

However, the entropies at points 3 and 3I and 4 are

known. Thus, an entropy balance, will give the

quality of the vapour at point 3,

11/3/2017 229

Engineering, Thermodynamics (GEC 221)

solution

Thus if the vapour quality at point 3 is x

S3 = xS3I + (1 x)S4

S3 = xS3I + S4 xS4

x =

5.8586 1.5276

=

7.1293 1.5276

4.331

=

5.6017

= 0.77316

Covenant University, Dept. of Chemical

11/3/2017 230

Engineering, Thermodynamics (GEC 221)

solution

Enthalpy balance

H3 = x H3I + (1 - x) H4

= 0.77316(2706) + (1 - 0.77316)503.7

= 2092.17 + 114.259

= 2206.429 kJ/kg

H2 H3 2780.4 2206.43

= =

H2 H1 2780.4 503.7

573.97

=

2276.7

= .

Covenant University, Dept. of Chemical

11/3/2017 231

Engineering, Thermodynamics (GEC 221)

Solution

[d] Carnot Efficiency depends on temperature only, thus

=

273.1 + 280 120 + 273.1

=

273.1 + 280

553.1 393.1

=

553.1

160

=

553.1

= .

[e] Heat Engine Effectiveness (HEE), Carnot (HEE)C

(HEE)C =

0.252

=

0.289

= .

Covenant University, Dept. of Chemical

11/3/2017 232

Engineering, Thermodynamics (GEC 221)

Example

The data listed below are claimed for a power cycle

operating between reservours at 527 C and 27 C. In

each case determine if any principles of

thermodynamics would be violated

a) QH = 700 kJ, Wcycle = 400 kJ, QC = 300 kJ

b) QH = 640 kJ, Wcycle = 400 kJ, QC = 240 kJ

c) QH = 640 kJ, Wcycle = 400 kJ, QC = 200 kJ

Solution

TH = 527 C = (527 + 273) K = 800 K

TC = 27 C = (27 + 273) K = 300 K

Principles of thermodynamics would be violated once the

efficiency is greater than that of Carnot engine or conservation

of energy principle is violated

a) Q H = 700 kJ, Wcycle = 400 kJ, Q C = 300 kJ

= 1 where

300

=1 = 0.625

800

400

= = = 0.5714

700

Since , principle of thermodynamics is

not violated

solution

b) QH = 640 kJ, Wcycle = 400 kJ, QC = 240 kJ

= 1 where

300

=1 = 0.625

800

400

= = = 0.625

640

Since = obtained, principle of

thermodynamics is violated

Covenant University, Dept. of Chemical

11/3/2017 235

Engineering, Thermodynamics (GEC 221)

solution

c) Q H = 700 kJ, Wcycle = 400 kJ, Q C = 200 kJ

The principle of energy conservation says

Q H = Wcycle + Q

but

700 kJ 400 kJ + 200 kJ

hence

The principle of thermodynamics is violated

11/3/2017 236

Engineering, Thermodynamics (GEC 221)

Exercise

Obtain the Heat Engine Effectiveness (HEE) of the

given Rankine cycle

QH

P TH = 26 C

1 Isothermal Boiling 2

W

4 Isothermal Condensation 3 3I

Tc = 1 C

QH

11/3/2017

Covenant University, Dept. of Chemical

Engineering, Thermodynamics (GEC 221)

H 237

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