(Parte 1 de 15)
The First Law
This chapter introduces some of the basic concepts of thermodynamics. It concentrates on the conservation of energy—the experimental observation that energy can be neither created nor destroyed—and shows how the principle of the conservation of energy can be used to assess the energy changes that accompany physical and chemical processes. Much of this chapter examines the means by which a system can exchange energy with its surroundings in terms of the work it may do or the heat that it may produce. The target concept of the chapter is enthalpy, which is a very useful book-keeping property for keeping track of the heat output (or requirements) of physical processes and chemical reactions at constant pressure. We also begin to unfold some of the power of thermodynamics by showing how to establish relations between different properties of a system. We shall see that one very useful aspect of thermodynamics is that a property can be measured indirectly by measuring others and then combining their values. The relations we derive also enable us to discuss the liquefaction of gases and to establish the relation between the heat capacities of a substance under different conditions.
The release of energy can be used to provide heat when a fuel burns in a furnace, to produce mechanical work when a fuel burns in an engine, and to generate electrical work when a chemical reaction pumps electrons through a circuit. In chemistry, we encounter reactions that can be harnessed to provide heat and work, reactions that liberate energy which is squandered (often to the detriment of the environment) but which give products we require, and reactions that constitute the processes of life. Thermodynamics, the study of the transformations of energy, enables us to discuss all these matters quantitatively and to make useful predictions.
The basic concepts
For the purposes of physical chemistry, the universe is divided into two parts, the system and its surroundings. The system is the part of the world in which we have a special interest. It may be a reaction vessel, an engine, an electrochemical cell, a biological cell, and so on. The surroundingscomprise the region outside the system and are where we make our measurements. The type of system depends on the characteristics of the boundary that divides it from the surroundings (Fig. 2.1). If matter can be transferred through the boundary between the system and its surroundings the system is classified as open. If matter cannot pass through the boundary the system is classified as closed. Both open and closed systems can exchange energy with their surroundings. For example, a closed system can expand and thereby raise a weight in the surroundings; it may also transfer energy to them if they are at a lower temperature.
The basic concepts
2.1Work, heat, and energy 2.2The internal energy 2.3Expansion work 2.4 Heat transactions 2.5 Enthalpy
I2.1Impact on biochemistry and materials science: Differential scanning calorimetry
2.6 Adiabatic changes
2.7Standard enthalpy changes
I2.2Impact on biology: Food and energy reserves
2.8Standard enthalpies of formation
2.9 The temperature-dependence of reaction enthalpies
State functions and exact differentials
2.10Exact and inexact differentials 2.11Changes in internal energy 2.12The Joule–Thomson effect
Checklist of key ideas Further reading
Further information 2.1: Adiabatic processes
Further information 2.2: The relation between heat capacities
Discussion questions Exercises Problems
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Fig. 2.1(a) An open system can exchange matter and energy with its surroundings. (b) A closed system can exchange energy with its surroundings, but it cannot exchange matter. (c) An isolated system can exchange neither energy nor matter with its surroundings.
An isolated system is a closed system that has neither mechanical nor thermal contact with its surroundings.
The fundamental physical property in thermodynamics is work: work is motion against an opposing force. Doing work is equivalent to raising a weight somewhere in the surroundings. An example of doing work is the expansion of a gas that pushes out a piston and raises a weight. A chemical reaction that drives an electric current through a resistance also does work, because the same current could be driven through a motor and used to raise a weight.
The energy of a system is its capacity to do work. When work is done on an otherwise isolated system (for instance, by compressing a gas or winding a spring), the capacity of the system to do work is increased; in other words, the energy of the system is increased. When the system does work (when the piston moves out or the spring unwinds), the energy of the system is reduced and it can do less work than before.
Experiments have shown that the energy of a system may be changed by means other than work itself. When the energy of a system changes as a result of a temperature diﬀerence between the system and its surroundings we say that energy has been transferred as heat. When a heater is immersed in a beaker of water (the system), the capacity of the system to do work increases because hot water can be used to do more work than the same amount of cold water. Not all boundaries permit the transfer of energy even though there is a temperature diﬀerence between the system and its surroundings.
An exothermic process is a process that releases energy as heat into its surroundings. All combustion reactions are exothermic. An endothermic processis a process in which energy is acquired from its surroundings as heat. An example of an endothermic process is the vaporization of water. To avoid a lot of awkward circumlocution, we say that in an exothermic process energy is transferred ‘as heat’ to the surroundings and in an endothermic process energy is transferred ‘as heat’ from the surroundings into the system. However, it must never be forgotten that heat is a process (the transfer of energy as a result of a temperature diﬀerence), not an entity. An endothermic process in a diathermic container results in energy flowing into the system as heat. An exothermic process in a similar diathermic container results in a release of energy as heat into the surroundings. When an endothermic process takes place in an adiabatic container, it results in a lowering of temperature of the system; an exothermic process results in a rise of temperature. These features are summarized in Fig. 2.2.
Molecular interpretation 2.1Heat and work
In molecular terms, heating is the transfer of energy that makes use of disorderly molecular motion. The disorderly motion of molecules is called thermal motion. The thermal motion of the molecules in the hot surroundings stimulates the molecules in the cooler system to move more vigorously and, as a result, the energy of the system is increased. When a system heats its surroundings, molecules of the system stimulate the thermal motion of the molecules in the surroundings (Fig. 2.3).
In contrast, work is the transfer of energy that makes use of organized motion
(Fig. 2.4). When a weight is raised or lowered, its atoms move in an organized way (up or down). The atoms in a spring move in an orderly way when it is wound; the
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Fig. 2.2(a) When an endothermic process occurs in an adiabatic system, the temperature falls; (b) if the process is exothermic, then the temperature rises. (c) When an endothermic process occurs in a diathermic container, energy enters as heat from the surroundings, and the system remains at the same temperature. (d) If the process is exothermic, then energy leaves as heat, and the process is isothermal.
1The internal energy does not include the kinetic energy arising from the motion of the system as a whole, such as its kinetic energy as it accompanies the Earth on its orbit round the Sun.
Fig. 2.3When energy is transferred to the surroundings as heat, the transfer stimulates random motion of the atoms in the surroundings. Transfer of energy from the surroundings to the system makes use of random motion (thermal motion) in the surroundings.
Fig. 2.4When a system does work, it stimulates orderly motion in the surroundings. For instance, the atoms shown here may be part of a weight that is being raised. The ordered motion of the atoms in a falling weight does work on the system.
electrons in an electric current move in an orderly direction when it flows. When a system does work it causes atoms or electrons in its surroundings to move in an organized way. Likewise, when work is done on a system, molecules in the surroundings are used to transfer energy to it in an organized way, as the atoms in a weight are lowered or a current of electrons is passed.
The distinction between work and heat is made in the surroundings. The fact that a falling weight may stimulate thermal motion in the system is irrelevant to the distinction between heat and work: work is identified as energy transfer making use of the organized motion of atoms in the surroundings, and heat is identified as energy transfer making use of thermal motion in the surroundings. In the compression of a gas, for instance, work is done as the atoms of the compressing weight descend in an orderly way, but the eﬀect of the incoming piston is to accelerate the gas molecules to higher average speeds. Because collisions between molecules quickly randomize their directions, the orderly motion of the atoms of the weight is in eﬀect stimulating thermal motion in the gas. We observe the falling weight, the orderly descent of its atoms, and report that work is being done even though it is stimulating thermal motion.
2.2The internal energy
In thermodynamics, the total energy of a system is called its internal energy, U. The internal energy is the total kinetic and potential energy of the molecules in the system (see Comment 1.3for the definitions of kinetic and potential energy).1We denote by ∆Uthe change in internal energy when a system changes from an initial state i with internal energy Uito a final state f of internal energy Uf:
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An extensive property is a property that depends on the amount of substance in the sample. An intensive property is a property that is independent of the amount of substance in the sample. Two examples of extensive properties are mass and volume. Examples of intensive properties are temperature, mass density (mass divided by volume), and pressure.
The internal energy is a state function in the sense that its value depends only on the current state of the system and is independent of how that state has been prepared. In other words, it is a function of the properties that determine the current state of the system. Changing any one of the state variables, such as the pressure, results in a change in internal energy. The internal energy is an extensive property. That the internal energy is a state function has consequences of the greatest importance, as we start to unfold in Section 2.10.
Internal energy, heat, and work are all measured in the same units, the joule (J). The joule, which is named after the nineteenth-century scientist J.P. Joule, is defined as
A joule is quite a small unit of energy: for instance, each beat of the human heart con-
common in fields other than thermodynamics. Thus, 1 electronvolt (1 eV) is defined as the kinetic energy acquired when an electron is accelerated from rest through a potential diﬀerence of 1 V; the relation between electronvolts and joules is 1 eV ≈ 0.16 aJ (where 1 aJ =10−18J). Many processes in chemistry have an energy of several electronvolts. Thus, the energy to remove an electron from a sodium atom is close to 5 eV. Calories (cal) and kilocalories (kcal) are still encountered. The current definition of the calorie in terms of joules is
1 cal =4.184 J exactly An energy of 1 cal is enough to raise the temperature of 1 g of water by 1°C.
Molecular interpretation 2.2The internal energy of a gas
A molecule has a certain number of degrees of freedom, such as the ability to translate (the motion of its centre of mass through space), rotate around its centre of mass, or vibrate (as its bond lengths and angles change). Many physical and chemical properties depend on the energy associated with each of these modes of motion. For example, a chemical bond might break if a lot of energy becomes concentrated in it.
(Parte 1 de 15)