If we consider a given mass of water, we recognize that this water can exist in various forms. If it is a liquid initially, it may become a vapor when it is heated or a solid when it is cooled. Thus, we speak of the different phases of a substance. A phase is defined as a quantity of matter that is homogeneous throughout. When more than one phase is present, the phases are separated from each other by the phase boundaries. In each phase the substance may exist at various pressures and temperatures or, to use the thermodynamic term, in various states. The state may be identified or described by certain observable, macroscopic properties; some familiar ones are temperature, pressure, and density. In later chapters, other properties will


Be introduced. Each of the properties of a substance in a given state has only one definite value, and these properties always have the same value for a given state, regardless of how the substance arrived at the state. In fact, a property can be defined as any quantity that depends on the state of the system and is independent of the path (that is, the prior history) by which the system arrived at the given state. Conversely, the state is specified or described by the properties. Later we will consider the number of independent properties a substance can have, that is, the minimum number of properties that must be specified to fix the state of the substance. Thermodynamic properties can be divided into two general classes: intensive and extensive. An intensive property is independent of the mass; the value of an extensive property varies diectly with the mass.

Thus, if a quantity of matter in a given state is divided into two equal parts, each part will have the same value of intensive properties as the original and half the value of the extensive properties. Pressure, temperature, and density are examples of intensive properties. Mass and total volume are examples of extensive properties. Extensive properties per unit mass, such as specific volume, are intensive properties. Frequently we will refer not only to the properties of a substance but also to the properties of a system. When we do so, we necessarily imply that the value of the property has significance for the entire system, and this implies equilibrium.

For example, if the gas that composes the system (control mass) in Fig. 1.4 is in thermal equilibrium, the temperature will be the same throughout the entire system, and we may speak of the temperature as a property of the system. We may also consider mechanical equilibrium, which is related to pressure. If a system is in mechanical equilibrium, there is no tendency for the pressure at any point to change with time as long as the system is isolated from the surroundings. There will be variation in pressure with elevation because of the influence of gravitational forces, although under equilibrium conditions there will be no tendency for the pressure at any location to change. However, in many thermodynamic problems, this variation in pressure with elevation is so small that it can be neglected. Chemical equilibrium is also important and will be considered in Chapter 14. When a system is in equilibrium regarding all possible changes of state, we say that the system is in thermodynamic equilibrium.

Example of a control mass

Example of a control mass

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Thermodynamic system

A thermodynamic system is a device or combination of devices containing a quantity of matter that is being studied. To define this more precisely, a control volume is chosen so that it contains the matter and devices inside a control surface. Everything external to the


Schematic diagram of a steam power plant     Schematic diagram of a steam power plant


control volume is the surroundings, with the separation provided by the control surface. The surface may be open or closed to mass flows, and it may have flows of energy in terms of heat transfer and work across it. The boundaries may be movable or stationary. In the case of a control surface that is closed to mass flow, so that no mass can escape or enter the control volume, it is called a control mass containing the same amount of matter at all times.


Schematic diagram of a refrigerator                                                                Schematic diagram of a refrigerator


Selecting the gas in the cylinder of Fig. 1.4 as a control volume by placing a control surface around it, we recognize this as a control mass. If a Bunsen burner is placed under the cylinder, the temperature of the gas will increase and the piston will move out. As the piston moves, the boundary of the control mass also changes. As we will see later, heat and work cross the boundary of the control mass during this process, but the matter that composes the control mass can always be identified and remains the same.


An isolated system

An isolated system is one that is not influenced in any way by the surroundings so that no mass, heat, or work is transferred across the boundary of the system. In a more typical case, a thermodynamic analysis must be made of a device like an air compressor which has a flow of mass into and out of it, as shown schematically in Fig. 1.5. The real system includes possibly a storage tank, as shown later in Fig. 1.20. In such an analysis, we specify a control volume that surrounds the compressor with a surface that is called the control surface, across which there may be a transfer of mass, and momentum, as well as heat and work.


Example of a control mass                                                                                         Example of a control mass


Thus, the more general control surface defines a control volume, where mass may flow in or out, with a control mass as the special case of no mass flow in or out. Hence, the control mass contains a fixed mass at all times, which explains its name. The general formulation of the analysis is considered in detail in Chapter 4. The terms closed system (fixed mass) and open system (involving a flow of mass) are sometimes used to make this distinction. Here, we use the term system as a more general and loose description for a mass, device, or combination of devices that then is more precisely defined when a control volume is selected. The procedure that will be followed in presenting the first and second


Example of a control volume                                                                       Example of a control volume


laws of thermodynamics is first to present these laws for a control mass and then to extend the analysis to the more general control volume.

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Introduction to Fundamentals of Thermodynamics

Introduction and Preliminaries

Fundamental Physical Constants

Avogadro                                                       N0 = 6.0221415×1023 mol−1

Boltzmann                                                        k = 1.3806505×10−23 JK−1

Planck                                                               h = 6.6260693×10−34 Js

Gas Constant                                                  R = N0 k=8.314472 J mol−1 K−1

Atomic Mass Unit                                       m0 = 1.66053886×10−27 kg

Velocity of light                                               c = 2.99792458×108 ms−1

lectron Charge                                               e = 1.60217653×10−19 C

Electron Mass                                            me = 9.1093826×10−31 kg

Proton Mass                                              mp = 1.67262171×10−27 kg

Gravitation (Std.)                                          g = 9.80665 ms−2

Stefan Boltzmann                                        σ = 5.670400×10−8 Wm−2 K−4

Mol here is gram mol.

Fundamental Physical Constants


                                     10−1                  deci                d

                                     10−2               centi                 c

                                     10−3               milli                  m

                                     10−6               micro                μ

                                     10−9               nano                 n

                                   10−12             pico                     p

                                   10−15             femto                 f

                                      101            deka                    da

                                      102            hecto                    h

                                      103               kilo                     k

                                     106             mega                    M

                                     109             giga                       G

                                  1012            tera                         T

                                  1015             peta                       P


The field of thermodynamics is concerned with the science of energy focusing on energy storage and energy conversion processes. We will study the effects on different substances, as we may expose a mass to heating/cooling or to volumetric compression/expansion. .During such processes we are transferring energy into or out of the mass, so it changes its conditions expressed by properties like temperature, pressure, and volume. We use several processes similar to this in our daily lives; we heat water to make coffee or tea or cool it in a refrigerator to make cold water or ice cubes in a freezer. In nature, water evaporates from oceans and lakes and mixes with air where the wind can transport it, and later the water may drop out of the air as either rain (liquid water) or snow (solid water). As we study these processes in detail, we will focus on situations that are physically simple and yet typical of real-life situations in industry or nature.


By a combination of processes, we are able to illustrate more complex devices or complete systems—for instance, a simple steam power plant that is the basic system that generates the majority of our electric power. A power plant that produces electric power and hot water for district heating burns coal, as shown in Fig. 1.1. The coal is supplied by ship, and the district heating pipes are located in underground tunnels and thus are not visible. A more technical description and a better understanding are obtained from the simple schematic of the power plant, as shown in Fig. 1.2. This includes various outputs from the plant as electric power to the net, warm water for district heating, slag from burning coal, and other materials like ash and gypsum; the last output is a flow of exhaust gases out of the chimney.

Another set of processes forms a good description of a refrigerator that we use to cool food or apply it at very low temperatures to produce a flow of cold fluid for cryogenic surgery by freezing tissue for minimal bleeding. A simple schematic for such a system is shown in Fig. 1.3. The same system can also function as an air conditioner with the dual purpose of cooling a building in summer and heating it in winter; in this last mode of use, it is also called a heat pump. For mobile applications, we can make simple models for gasoline and diesel engines typically used for ground transportation and gas turbines in jet engines used in aircraft, where low weight and volume are of prime concern. These are just a few examples of familiar systems that the theory of thermodynamics allows us to analyze. Once we learn and understand the theory, we will be able to extend the analysis to other cases we may not be familiar with.

Beyond the description of basic processes and systems, thermodynamics is extended to cover special situations like moist atmospheric air, which is a mixture of gases, and the combustion of fuels for use in the burning of coal, oil, or natural gas, which is a chemical and energy conversion process used in nearly all power-generating devices. Many other extensions are known; these can be studied in specialty texts. Since all the processes engineers deal with have an impact on the environment, we must be acutely aware of the ways in which we can optimize the use of our natural resources and produce the minimal amount of negative consequences for our environment. For this reason, the treatment of efficiencies for processes and devices is important in a modern analysis and is required knowledgeforacompleteengineeringconsiderationofsystemperformanceandoperation. Before considering the application of the theory, we will cover a few basic concepts and definitions for our analysis and review some material from physics and chemistry that we will need.