Scope and Language of Thermodynamics
Chemical processes involve streams undergoing various transformations. One example is shown in Figure 1-1: raw materials are fed into a heated reactor, where they react to form products. The effluent stream, in this case a liquid, contains the products of the reaction, any unreacted raw materials, and possibly other by-products. This stream is pumped out of the reactor into a heat exchanger, where it partially boils. The vapor/liquid mixture is fed into a tank, which collects the vapor at the top, and liquid at the bottom. The streams that exit this tank are finally cooled down and sent to the next stage of the process. Actual processes are generally more complex and may involve many streams and several interconnected units. Nonetheless, the example in Figure 1-1 contains all the basic ingredients likely to be found in any chemical plant: heating, cooling, pumping, reactions, phase transformations.
It is the job of the chemical engineer to compute the material and energy balances around such process: This includes the flow rates and compositions of all streams, the power requirements of pumps, compressors and turbines, and the heat loads in the heat exchangers. The chemical engineer must also determine the conditions of pressure and temperature that are required to produce the desired effect, whether this is a chemical reaction or a phase transformation. All of this requires the knowledge of various physical properties of a mixture: density, heat capacity, boiling temperature, heat of vaporization, and the like. More specifically, these properties must be known as a function of temperature, pressure, and composition, all of which vary from stream to stream. Energy balances and property estimation may appear to be separate problems, but they are not: both calculations require the application of the same fundamental principles of thermodynamics.
The name thermodynamics derives from the Greek thermotis (heat) and dynamiki (potential, power). Its historical roots are found in the quest to develop heat engines, devices that use heat to produce mechanical work. This quest, which was instrumental in powering the industrial revolution, gave birth to thermodynamics as a discipline that studies the relationship between heat, work, and energy. The elucidation of this relationship is one of the early triumphs of thermodynamics and a reason why, even today, thermodynamics is often described as the study of energy conversions involving heat. Modern thermodynamics is a much broader discipline whose focus is the equilibrium state of systems composed of very large numbers of molecules. Temperature, pressure, heat, and mechanical work, as manifested through the expansion and compression of matter, are understood to arise from interactions at the molecular level. Heat and mechanical work retain their importance but the scope of the modern discipline is far wider than its early developers would have imagined, and encompasses many different systems containing huge numbers of “particles,” whether these are molecules, electron spins, stars, or bytes of digital information. The term chemical thermodynamics refers to applications to molecular systems. Among the many scientists who contributed to the development of modern thermodynamics, J. Willard Gibbs stands out as one whose work revolutionized the discipline by providing the tools to connect the macroscopic properties of thermodynamics to the microscopic properties of molecules. His name is now associated with the Gibbs free energy, a thermodynamic property of fundamental importance in phase and chemical equilibrium.
Figure 1-1: Typical chemical process.
Figure 1-2: J. W. Gibbs.
Chemical engineering thermodynamics is the subset that applies thermodynamics to processes of interest to chemical engineers. One important task is the calculation of energy requirements of a process and, more broadly, the analysis of energy utilization and efficiency in chemical processing. This general problem is discussed in the first part of the book, Chapters 2 through 7. Another important application of chemical engineering thermodynamics is in the design of separation units. The vapor-liquid separator in Figure 1-1 does more than just separate the liquid portion of the stream from the vapor. When a multicomponent liquid boils, the more volatile (“lighter”) components collect preferentially in the vapor and the less volatile (“heavier”) ones remain mostly in the liquid. This leads to partial separation of the initial mixture. By staging multiple such units together, one can accomplish separations of components with as high purity as desired. The determination of the equilibrium composition of two phases in contact with each other is an important goal of chemical engineering thermodynamics. This problem is treated in the second part of the book and the first part is devoted to the behavior of single-component fluids. Overall then, the chemical engineer uses thermodynamics to
- Perform energy and material balances in unit operations with chemical reactions, separations, and fluid transformations (heating/cooling, compression/ expansion),
- Determine the various physical properties that are required for the calculation of these balances,
- Determine the conditions of equilibrium (pressure, temperature, composition) in phase transformations and chemical reactions.
These tasks are important for the design of chemical processes and for their proper control and troubleshooting. The overall learning objective of this book is to provide the undergraduate student in chemical engineering with a solid background to perform these calculations with confidence.
1.1 Molecular Basis of Thermodynamics
All macroscopic behavior of matter is the result of phenomena that take place at the microscopic level and arise from force interactions among molecules. Molecules exert a variety of forces: direct electrostatic forces between ions or permanent dipoles; induction forces between a permanent dipole and an induced dipole; forces of attraction between nonpolar molecules, known as van der Waals (or dispersion) forces; other specific chemical forces such as hydrogen bonding. The type of interaction (attraction or repulsion) and the strength of the force that develops between two molecules depends on the distance between them. At far distances the force is zero. When the distance is of the order of several Å, the force is generally attractive. At shorter distances, short enough for the electron clouds of the individual atoms to begin to overlap, the interaction becomes very strongly repulsive. It is this strong repulsion that prevents two atoms from occupying the same point in space and makes them appear as if they possess a solid core. It is also the reason that the density of solids and liquids is very nearly independent of pressure: molecules are so close to each other that adding pressure by any normal amounts (say 10s of atmospheres) is insufficient to overcome repulsion and cause atoms to pack much closer.
The force between two molecules is a function of the distance between them. This force is quantified by intermolecular potential energy, Φ(r), or simply intermolecular potential, which is defined as the work required to bring two molecules from infinite distance to distance r. Figure 1-3 shows the approximate intermolecular potential for CO2. Carbon dioxide is a linear molecule and its potential depends not only on the distance between the molecules but also on their relative orientation. This angular dependence has been averaged out for simplicity. To interpret Figure 1-3, we recall from mechanics that force is equal to the negative derivative of the potential with respect to distance:
That is, the magnitude of the force is equal to the slope of the potential with a negative sign that indicates that the force vector points in the direction in which the potential decreases. To visualize the force, we place one molecule at the origin and a test molecule at distance r. The magnitude of the force on the test molecule is equal to the derivative of the potential at that point (the force on the first molecule is equal in magnitude and opposite in direction). If the direction of force is towards the origin, the force is attractive, otherwise it is repulsive. The potential in Figure 1-3 has a minimum at separation distance r* = 4.47 Å. In the region r > r* the slope is negative and the force is attractive. The attraction is weaker at longer distances and for r larger than about 9 Å the potential is practically flat and the force is zero. In the region r < r* the potential is repulsive and its steep slope indicates a very strong force that arises from the repulsive interaction of the electrons surrounding the molecules. Since the molecules cannot be pushed much closer than about r ≈ r*, we may regard the distance r* to be the effective diameter of the molecule.1 Of course, even simple molecules like argon are not solid spheres; therefore, the notion of a molecular diameter should not be taken literally.
Figure 1-3: Approximate interaction potential between two CO2 molecules as a function of their separation distance. The potential is given in kelvin; to convert to joule multiply by the Boltzmann constant, kB = 1.38 × 10−23 J/K. The arrows show the direction of the force on the test molecule in the regions to the left and to the right of r*.
The details of the potential vary among different molecules but the general features are always the same: Interaction is strongly repulsive at very short distance, weakly attractive at distance of the order of several Å, and zero at much larger distances. These features help to explain many aspects of the macroscopic behavior of matter.
Temperature and Pressure
In the classical view of molecular phenomena, molecules are small material objects that move according to Newton’s laws of motion, under the action of forces they exert on each other through the potential interaction. Molecules that collide with the container walls are reflected back, and the force of this collision gives rise to pressure. Molecules also collide among themselves,2 and during these collisions they exchange kinetic energy. In a thermally equilibrated system, a molecule has different energies at different times, but the distribution of energies is overall stationary and the same for all molecules. Temperature is a parameter that characterizes the distribution of energies inside a system that is in equilibrium with its surroundings. With increasing temperature, the energy content of matter increases. Temperature, therefore, can be treated as a measure of the amount of energy stored inside matter.
where m is the mass of the molecule, v is the magnitude of the velocity, T is absolute temperature, and kB is the Boltzmann constant. The fraction of molecules with velocities between any two values v1 to v2 is equal to the area under the curve between the two velocities (the total area under the curve is 1). The velocity vmax that corresponds to the maximum of the distribution, the mean velocity , and the mean of the square of the velocity are all given in terms of temperature:
The Maxwell-Boltzmann distribution is a result of remarkable generality: it is independent of pressure and applies to any material, regardless of composition or phase. Figure 1-4 shows this distribution for water at three temperatures. At the triple point, the solid, liquid, and vapor, all have the same distribution of velocities.
The minimum of the potential represents a stable equilibrium point. At this distance, the force between two molecules is zero and any small deviations to the left or to the right produce a force that points back to the minimum. A pair of molecules trapped at this distance r* would form a stable pair if it were not for their kinetic energy, which allows them to move and eventually escape from the minimum. The lifetime of a trapped pair depends on temperature. At high temperature, energies are higher, and the probability that a pair will remain trapped is low. At low temperature a pair can survive long enough to trap additional molecules and form a small cluster of closely packed molecules. This cluster is a nucleus of the liquid phase and can grow by further collection to form a macroscopic liquid phase. Thus we have a molecular view of vapor-liquid equilibrium. This picture highlights the fact that to observe a vapor-liquid transition, the molecular potential must exhibit a combination of strong repulsion at short distances with weak attraction at longer distances. Without strong repulsion, nothing would prevent matter from collapsing into a single point; without attraction, nothing would hold a liquid together in the presence of a vapor. We can also surmise that molecules that are characterized by a deeper minimum (stronger attraction) in their potential are easier to condense, whereas a shallower minimum requires lower temperature to produce a liquid. For this reason, water, which associates via hydrogen bonding (attraction) is much easier to condense than say, argon, which is fairly inert and interacts only through weak van der Waals attraction.
Figure 1-4: Maxwell-Boltzmann distribution of molecular velocities in water.
Figure 1-3 shows that at distances larger than about 10 Å the potential of carbon dioxide is fairly flat and the molecular force nearly zero. If carbon dioxide is brought to a state such that the mean distance between molecules is more than 10 Å we expect that molecules would hardly register the presence of each other and would largely move independently of each other, except for brief close encounters. This state can be reproduced experimentally by decreasing pressure (increasing volume) while keeping temperature the same. This is called the ideal-gas state. It is a state—not a gas—and is reached by any gas when pressure is reduced sufficiently. In the ideal-gas state molecules move independently of each other and without the influence of the intermolecular potential. Certain properties in this state become universal for all gases regardless of the chemical identity of their molecules. The most important example is the ideal-gas law, which describes the pressure-volume-temperature relationship of any gas at low pressures.