CHEMICAL ENGINEERING THERMODYNAMICS-II (CH.

E 307)

By Muhammad Asif Akhtar imasif@uet.edu.pk

CONTENTS
Introduction Fundamental Concepts Basic Laws Applications Property Diagrams

INTRODUCTION The name thermodynamics stems from the Greek words Therme: means heat Dynamics: means power

Thermodynamics can be defined as the science of energy

3

INTRODUCTION

Today the same name is broadly interpreted to include all aspects of energy and energy transformations, including power generation, refrigeration, and relationships among the properties of matter.

Classical Thermodynamics:
The macroscopic approach to the study of thermodynamics that does not require a knowledge of the behavior of individual particles is called classical thermodynamics. It provides a direct and easy way to the solution of engineering problems. Statistical Thermodynamics: A more elaborate approach, based on the average behavior of large groups of individual particles
5

Thermodynamics in Chemical Engineering

THE CHEMICAL ENGINEERING copes with particularly wide variety of problems. Among them are:
Calculation of heat & work requirement for physical & chemical processes Determination of equilibrium conditions for chemical reactions Transfer of chemical species between phases

HISTORY
The science of thermodynamics was born in nineteenth century of the need to describe the operation of steam engines and to set forth the limits of what they can accomplish. Thus the name thermodynamics itself denotes POWER DEVELOPED FROM HEAT, with obvious application to heat engines/steam engine. Working of these heat engines is governed by principles, named First & Second Law of Thermodynamics.

Thermodynamics Systems
Thermodynamics system is defined as a quantity of matter or region in space chosen for study The mass or region outside the system is called the surroundings System boundary is the real and imaginary surface that separates the system from the surrounding. Boundary can be fixed or movable May be closed or open

Closed System/Control Mass

A system of fixed mass is called a closed system, or control mass The closed system boundary does not have to be fixed

No mass can cross the closed system boundary

Energy in the form of heat and work can cross the closed system boundary If even energy is not allowed to cross we have an isolated system

Closed System/Control Mass

Energy, not mass, crosses closed-system boundaries

Closed system with moving boundary

Open System / Control Volume

A system that involves mass transfer across its boundaries is called an open system, or control volume.

The boundary of a control volume is called control surface.

Energy in the form of heat and work as well as mass can cross the control boundaries

Open System / Control Volume

Mass and Energy Cross Control Volume Boundaries

PROPERTIES OF A SYSTEM

Any characteristic of a system is called a property.

Intensive properties are those that are independent of the mass of a system, such as temperature, pressure, and density. Extensive properties are those whose values depend on the sizeor extentof the system. Total mass, total volume, and total momentum are some examples of extensive properties.
13

Thermodynamic Equilibrium

Thermodynamics deals with Equilibrium States

A system is said to be in thermodynamic equilibrium if it maintains thermal, mechanical, phase, and chemical equilibrium. Thermal Equilibrium => Temperature is the same throughout the system Mechanical Equilibrium => Pressure is the same throughout the system Phase Equilibrium => No phase change process in the system Chemical Equilibrium => No chemical reactions

QUASI-EQUILIBRIUM PROCESS

When a process proceeds in such a manner that the system remains infinitesimally close to an equilibrium state at all times, it is called a quasiequilibrium, process. A quasi-equilibrium process can be viewed as a sufficiently slow process that allows the system to adjust itself internally so that properties in one part of the system do not change any faster than those at other parts.

15

QUASI-EQUILIBRIUM PROCESS

It should be pointed out that a quasi-equilibrium process is an idealized process and is not a true representation of an actual process. Engineers are interested in quasi equilibrium processes for two reasons. First, they are easy to analyze; Second, work-producing devices deliver the most work when they operate on quasi equilibrium processes. Therefore, quasi-equilibrium processes serve as standards to which actual processes can be compared.
16

P-V Diagram Of A Compression Process Of A Gas

The process path indicates a series of equilibrium states through which the system passes during a process and has significance for quasi equilibrium processes only.

For non quasi-equilibrium processes, we are not able to characterize the entire system by a single state, and thus we cannot speak of a process path for a system as a whole.
17

Process, Path and Cycle

Process - Any change that a system undergoes from one equilibrium state to another is called a process.

Path - The series of state through which a system passes during a process is called a path. Cycle - A process with identical end states is called a cycle.

1st Law of Thermodynamics

The first law of thermodynamics is simply an expression of the conservation of energy principle, and it asserts that energy is a thermodynamic property.

THE GENERAL ENERGY EQUATION

Energy In = Energy Out

or
U2 - U1 = Q W

where U1: internal energy of the system at the beginning U2: internal energy of the system at the end Q : net heat flow into the system W : net work done by the system

A cup of hot coffee left on a table eventually cools, but a cup of cool coffee in the same room never gets hot by itself.
The high-temperature energy of the coffee is degraded (transformed into a less useful form at a lower temperature) once it is transferred to the surrounding air.

21

2nd Law of Thermodynamics

The second law of thermodynamics asserts that energy has quality as well as quantity, and actual processes occur in the direction of decreasing quality of energy.

2nd Law of Thermodynamics

Identify the direction of a process. (ex: Heat can only transfer from a hot object to a cold object, not the other around) Can be used to determine the Quality of the energy. (ex: A high-temperature energy source has a higher quality since it is easier to extract energy from it to deliver useable work.)

Determine the theoretical limits for the performance of engineering systems. (ex: A Carnot engine is theoretically the most efficient heat engine and its performance can be used to set as a standard for other practical machines)
23

2nd Law of Thermodynamics

A process can not happen unless it satisfies both the first and second laws of thermodynamics. The first law characterizes the balance of energy which defines the quantity of energy. The second law defines the direction in which the process can take place and its quality

24

Applications of Thermodynamics

Thermal Power Plant

POWER PLANT

Solar-thermal Power Plant

Applications of Thermodynamics

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 pure substance does not have to be of a single chemical element or compound, however. A mixture of various chemical elements or compounds also qualifies as a pure substance as long as the mixture is homogeneous.

30

PURE SUBSTANCE

A mixture of two or more phases of a pure substance is still a pure substance as long as the chemical composition of all phases is the same.
A mixture of ice and liquid water, for example, is a pure substance because both phases have the same chemical composition.
31

PHASE-CHANGE PROCESSES OF PURE SUBSTANCES

There are many practical situations where two phases of a pure substance coexist in equilibrium. Water exists as a mixture of liquid and vapor in the boiler and the condenser of a steam power plant. The refrigerant turns from liquid to vapor in the freezer of a refrigerator.
32

Compressed Liquid and Saturated Liquid

Subcooled Liquid

it is not about to vaporize.

Saturated Liquid A liquid that is about to vaporize State 2 is a saturated liquid state.

33

Saturated liquidvapor mixture since the liquid and vapor phases coexist in equilibrium at these states.

A vapor that is about to condense is called a saturated vapor. Therefore, state 4 is a saturated vapor state.
34

SUPERHEATED VAPOR

A vapor that is not about to condense (i.e., not a saturated vapor) is called a superheated vapor. Therefore, water at state 5 is a superheated vapor.

35

T-v diagram for the heating process of water at constant pressure

36

Saturation Temperature and Saturation Pressure

At a given pressure, the temperature at which a pure substance changes phase is called the saturation temperature Tsat. At a given temperature, the pressure at which a pure substance changes phase is called the saturation pressure Psat.

At a pressure of 101.325 kPa, Tsat is 99.97C. Conversely, at a temperature of 99.97C, Psat is 101.325 kPa.

37

Liquidvapor Saturation Curve

Tsat f (Psat). A plot of Tsat versus Psat, such as the one given for water in is called a liquidvapor saturation curve. A curve of this kind is characteristic of all pure substances.
38

39

 PROPERTY DIAGRAMS FOR PHASECHANGE PROCESSES

40

The T-v Diagram

Let us add weights on top of the piston until the pressure inside the cylinder reaches 1 MPa. At this pressure, water has a somewhat smaller specific volume than it does at 1 atm pressure. As heat is transferred to the water at this new pressure, the process follows a path that looks very much like the process path at 1 atm pressure.
41

The T-v Diagram

Water starts boiling at a much higher temperature (179.9C) at this pressure.

Second, the specific volume of the saturated liquid is larger and the specific volume of the saturated vapor is smaller than the corresponding values at 1 atm pressure. That is, the horizontal line that connects the saturated liquid and saturated vapor states is much shorter. As the pressure is increased further, this saturation line continues to shrink, and it becomes a point when the pressure reaches 22.06 MPa for the case of water. This point is called the critical point, and it is defined as the point at which the saturated liquid and saturated vapor states are identical.

42

The T-v Diagram

43

The T-v Diagram

The saturated liquid states in can be connected by a line called the saturated liquid line, and saturated vapor states in the same figure can be connected by another line, called the saturated vapor line. These two lines meet at the critical point, forming a dome.

All the compressed liquid states are located in the region to the left of the saturated liquid line, called the compressed liquid region.

All the superheated vapor states are located to the right of the saturated vapor line, called the superheated vapor region. In these two regions, the substance exists in a single phase, a liquid or a vapor. All the states that involve both phases in equilibrium are located under the dome, called the saturated liquidvapor mixture region, or the wet region.
44

T-V DIAGRAM OF A PURE SUBSTANCE.

45

P-V DIAGRAM OF A PURE SUBSTANCE

46

P-T DIAGRAM

47