The system is the part of the physical world that is the object of a thermodynamic calculation. It may be a fixed amount of material inside a tank, a gas compressor with the associated inlet and outlet streams, or an entire chemical plant. Once the system is defined, anything that lies outside the system boundaries belongs to the surroundings. Together system and surroundings constitute the universe. A system can interact with its surroundings by exchanging mass, heat, and work. It is possible to construct the system in such way that some exchanges are allowed while others are not. If the system can exchange mass with the surroundings it called open, otherwise it is called closed. If it can exchange heat with the surroundings it is called diathermal, otherwise it is called adiabatic. A system that is prevented from exchanging either mass, heat, or work is called isolated. The universe is an isolated system.
A simple system is one that has no internal boundaries and thus allows all of its parts to be in contact with each other with respect to the exchange of mass, work, and heat. An example would be a mole of a substance inside a container. A composite system consists of simple systems separated by boundaries. An example would be a box divided into two parts by a firm wall. The construction of the wall would determine whether the two parts can exchange mass, heat, and work. For example, a permeable wall would allow mass transfer, a diathermal wall would allow heat transfer, and so on.
Figure 1-5: Examples of systems (see Example 1.2). The system is indicated by the dashed line. (a) Closed tank that contains some liquid and some gas. (b) The liquid portion in a closed, thermally insulated tank that also contains some gas. (c) Thermally insulated condenser of a laboratory-scale distillation unit.
It is an empirical observation that a simple system left undisturbed, in isolation of its surroundings, must eventually reach an ultimate state that does not change with time. Suppose we take a rigid, insulated cylinder, fill half of it with liquid nitrogen at atmospheric pressure and the other half with hot, pressurized nitrogen, and place a wall between the two parts to keep them separate. Then, we rupture the wall between the two parts and allow the system to evolve without any disturbance from the outside. For some time the system will undergo changes as the two parts mix. During this time, pressure and temperature will vary, and so will the amounts of liquid and vapor. Ultimately, however, the system will reach a state in which no more changes are observed. This is the equilibrium state.
Equilibrium in a simple system requires the fulfillment of three separate conditions:
- Mechanical equilibrium: demands uniformity of pressure throughout the system and ensures that there is no net work exchanged due to pressure differences.
- Thermal equilibrium: demands uniformity of temperature and ensures no net transfer of heat between any two points of the system.
- Chemical equilibrium: demands uniformity of the chemical potential and ensures that there is no net mass transfer from one phase to another, or net conversion of one chemical species into another by chemical reaction.
The chemical potential will be defined in Chapter 7.
Although equilibrium appears to be a static state of no change, at the molecular level it is a dynamic process. When a liquid is in equilibrium with a vapor, there is continuous transfer of molecules between the two phases. On an instantaneous basis the number of molecules in each phase fluctuates; overall, however, the molecular rates to and from each phase are equal so that, on average, there is no net transfer of mass from one phase to the other.
If we place two systems into contact with each other via a wall and isolate them from the rest of their surroundings, the overall system is isolated and composite. At equilibrium, each of the two parts is in mechanical, thermal, and chemical equilibrium at its own pressure and temperature. Whether the two parts establish equilibrium with each other will depend on the nature of the wall that separates them. A diathermal wall allows heat transfer and the equilibration of temperature. A movable wall (for example, a piston) allows the equilibration of pressure. A selectively permeable wall allows the chemical equilibration of the species that are allowed to move between the two parts. If a wall allows certain exchanges but not others, equilibrium is established only with respect to those exchanges that are possible. For example, a fixed conducting wall allows equilibration of temperature but not of pressure. If the wall is fixed, adiabatic, and impermeable, there is no exchange of any kind. In this case, each part establishes its own equilibrium independently of the other.
Extensive and Intensive Properties
In thermodynamics we encounter various properties, for example, density, volume, heat capacity, and others that will be defined later. In general, property is any quantity that can be measured in a system at equilibrium. Certain properties depend on the actual amount of matter (size or extent of the system) that is used in the measurement. For example, the volume occupied by a substance, or the kinetic energy of a moving object, are directly proportional to the mass. Such properties will be called extensive. Extensive properties are additive: if an amount of a substance is divided into two parts, one of volume V1 and one of volume V2, the total volume is the sum of the parts, V1 + V2. In general, the total value of an extensive property in a system composed of several parts is the sum of its parts. If a property is independent of the size of the system, it will be called intensive. Some examples are pressure, temperature, density. Intensive properties are independent of the amount of matter and are not additive.
As a result of the proportionality that exists between extensive properties and amount of material, the ratio of an extensive property to the amount of material forms an intensive property. If the amount is expressed as mass (in kg or lb), this ratio will be called a specific property; if the amount is expressed in mole, it will be called a molar property. For example, if the volume of 2 kg of water at 25 °C, 1 bar, is measured to be 2002 cm3, the specific volume is
and the molar volume is
In general for any extensive property F we have a corresponding intensive (specific or molar) property:
The relationship between specific and molar property is
where Mm is the molar mass (kg/mol).
State of Pure Component
Experience teaches that if we fix temperature and pressure, all other intensive properties of a pure component (density, heat capacity, dielectric constant, etc.) are fixed. We express this by saying that the state of a pure substance is fully specified by temperature and pressure. For the molar volume V, for example, we write
which reads “ V is a function of T and P.” The term state function will be used as a synonym for “thermodynamic property.” If eq. (1.5) is solved for temperature, we obtain an equation of the form
which reads “T is a function of P and V.” It is possible then to define the state using pressure and molar volume as the defining variables, since knowing pressure and volume allows us to calculate temperature. Because all properties are related to pressure and temperature, the state may be defined by any combination of two intensive variables, not necessarily T and P. Temperature and pressure are the preferred choice, as both variables are easy to measure and control in the laboratory and in an industrial setting. Nonetheless, we will occasionally consider different sets of variables, if this proves convenient.
State of Multicomponent Mixture
The state of a multicomponent mixture requires the specification of composition in addition to temperature and pressure. Mixtures will be introduced in Chapter 8. Until then the focus will be on single components.
Process and Path
The thermodynamic plane of pure substance is represented by two axes, T and P. A point on this plane represents a state, its coordinates corresponding to the temperature and pressure of the system. The typical problem in thermodynamics involves a system undergoing a change of state: a fixed amount of material at temperature TA and pressure PA is subjected to heating/cooling, compression/expansion, or other treatments to final state (TC, PC). A change of state is called a process. On the thermodynamic plane, a process is depicted by a path, namely, a line of successive states that connect the initial and final state (see Figure 1-6). Conversely, any line on this plane represents a process that can be realized experimentally. Two processes that are represented by simple paths on the TP plane are the constant-pressure (or isobaric) process, and the constant-temperature (or isothermal) process. The constant-pressure process is a straight line drawn at constant pressure (path AB in Figure 1-6); the constant-temperature process is drawn at constant temperature (path BC ). Any two points on the TP plane can be connected using a sequence of isothermal and isobaric paths.
Figure 1-6: Illustration of two different paths (ABC, AB′C ) between the same initial (A)and final (C) states. Paths can be visualized as processes (heating/cooling, compression/expansion) that take place inside a cylinder fitted with a piston.
Processes such as the constant-pressure, constant-temperature, and constant-volume process are called elementary. These are represented by simple paths during which one state variable (pressure, temperature, volume) is held constant. They are also simple to conduct experimentally. One way to do this is using a cylinder fitted with a piston. By fitting the piston with enough weights we can exert any pressure on the contents of the cylinder, and by making the piston movable we allow changes of volume due to heating/cooling to take place while keeping the pressure inside the cylinder constant. To conduct an isothermal process we employ the notion of a heat bath, or heat reservoir. Normally, when a hot system is used to supply heat to a colder one, its temperature drops as a result of the transfer of heat. If we imagine the size of the hot system to approach infinity, any finite transfer of heat to (or from) another system represents an infinitesimal change for the large system and does not change its temperature by any appreciable amount. The ambient air is a practical example of a heat bath with respect to small exchanges of heat. A campfire, for example, though locally hot, has negligible effect on the temperature of the air above the campsite. The rising sun, on the other hand, changes the air temperature appreciably. Therefore, the notion of an “infinite” bath must be understood as relative to the amount of heat that is exchanged. A constant-temperature process may be conducted by placing the system into contact with a heat bath. Additionally, the process must be conducted in small steps to allow for continuous thermal equilibration. The constant-volume process requires that the volume occupied by the system remain constant. This can be easily accomplished by confining an amount of substance in a rigid vessel that is completely filled. Finally, the adiabatic process may be conducted by placing thermal insulation around the system to prevent the exchange of heat.
We will employ cylinder-and-piston arrangement primarily as a mental device that allows us to visualize the mathematical abstraction of a path as a physical process that we could conduct in the laboratory.
At equilibrium, pressure and temperature are uniform throughout the system. This ensures a well-defined state in which, the system is characterized by a single temperature and single pressure, and represented by a single point on the PT plane. If we subject the system to a process, for example, heating by placing it into contact with a hot source, the system will be temporarily moved away from equilibrium and will develop a temperature gradient that induces the necessary transfer of heat. If the process involves compression or expansion, a pressure gradient develops that moves the system and its boundaries in the desired direction. During a process the system is not in equilibrium and the presence of gradients implies that its state cannot be characterized by a single temperature and pressure. This introduces an inconsistency in our depiction of processes as paths on the TP plane, since points on this plane represent equilibrium states of well-defined pressure and temperature. We resolve this difficulty by requiring the process to take place in a special way, such that the displacement of the system from equilibrium is infinitesimally small. A process conducted in such manner is called quasi static. Suppose we want to increase the temperature of the system from T1 to T2. Rather than contacting the system with a bath at temperature T2, we use a bath at temperature T1 + δT, where δT is a small number, and let the system equilibrate with the bath. This ensures that the temperature of the system is nearly uniform (Fig. 1-7). Once the system is equilibrated to temperature T1 + δT, we place it into thermal contact with another bath at temperature T2 +2δT, and repeat the process until the final desired temperature is reached. Changes in pressure are conducted in the same manner. In general, in a quasi-static process we apply small changes at a time and wait between changes for the system to equilibrate. The name derives from the Latin quasi (“almost”) and implies that the process occurs as if the system remained at a stationary equilibrium state.
Figure 1-7: (a) Typical temperature gradient in heat transfer. (b) Heat transfer under small temperature difference. (c) Quasi-static idealization: temperatures in each system are nearly uniform and almost equal to each other.
Quasi Static is Reversible
A process that is conducted in quasi-static manner is essentially at equilibrium at every step along the way. This implies that the system can retrace its path if all inputs (temperature and pressure differences) reverse sign. For this reason, the quasi-static process is also a reversible process. If a process is conducted under large gradients of pressure and temperature, it is neither quasi static nor reversible. Here is an exaggerated example that demonstrates this fact. If an inflated balloon is punctured with a sharp needle, the air in the balloon will escape and expand to the conditions of the ambient air. This process is not quasi static because expansion occurs under a nonzero pressure difference between the air in the ballon and the air outside. It is not reversible either: we cannot bring the deflated balloon back to the inflated state by reversing the action that led to the expansion, i.e., by “de-puncturing” it. We can certainly restore the initial state by patching the balloon and blowing air into it, but this amounts to performing an entirely different process. The same is true in heat transfer. If two systems exchange heat under a finite (nonzero) temperature difference, as in Figure 1-7(a), reversing ΔT is not sufficient to cause heat to flow in the reverse direction because the temperature gradient inside system 1 continues to transfer heat in the original direction. For a certain period of time the left side of system 1 will continue to receive heat until the gradient adjusts to the new temperature of system 2. Only when a process is conducted reversibly is it possible to recover the initial state by exactly retracing the forward path in the reverse direction. The quasi-static way to expand the gas is to perform the process against an external pressure that resists the expansion and absorbs all of the work done by the expanding gas. To move in the forward direction, the external pressure would have to be slightly lower than that of the gas; to move in the reverse direction, it would have to be slightly higher. In this manner the process, whether expansion or compression, is reversible. The terms quasi static and reversible are equivalent but not synonymous. Quasi static refers to how the process is conducted (under infinitesimal gradients); reversible refers to the characteristic property that such process can retrace its path exactly. The two terms are equivalent in the sense that if we determine that a process is conducted in a quasi-static manner we may conclude that it is reversible, and vice versa. In practice, therefore, the two terms may be used interchangeably.