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# Thermodynamics

Y Y Shan

Chapter 2 The First law of thermodynamics
2.1

Some concepts:

thermodynamic Process, Quasi-static process, Reversible

process
A thermodynamic process may be defined as the energetic evolution of a system
proceeding from an initial state to a final state. These processes, changing from one state
to another, can be classified as the followings depending on their specific conditions:
(i) An isobaric process occurs at constant pressure (Constant pressure process)
(ii) An isovolumetric process is one in which the volume is held constant
(constant volume process)
(iii) An isothermal process occurs at a constant temperature.
(iv) An adiabatic process is a process in which there is no energy added or
subtracted from the system by heating or cooling. The system is said to be thermally
insulated from its environment (surroundings) and its boundary is said to be a thermal
insulator.
(v) An isentropic process occurs at constant entropy. For a reversible process
this is identical to an adiabatic process.
(vi) An isenthalpic process introduces no change in enthalpy in the system.

A process can also be defined as a quasi-static one or a reversible one depending
on its evolution:
A quasistatic process is a process that happens infinitely slowly from one
thermal equilibrium state to another. It often ensures that the system will go through a
sequence of states that are infinitesimally close to equilibrium,
A reversible process (or a reversible cycle if the process is cyclic) is a process
that can be "reversed" by means of infinitesimal changes in some property of the system
without loss or dissipation of energy.
In some cases, it is important to distinguish between reversible and quasistatic
processes. Reversible processes are always quasistatic, but the converse is not always true.
For example, an infinitesimal compression of a gas in a cylinder where there exists

AP3290

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i Where Qi. in the case of "electrical work".1 Work Mechanical work is the amount of energy transferred by a force.Thermodynamics Y Y Shan friction between the piston and the cylinder is a quasistatic. the concept of thermodynamic work is slightly more general than that of mechanical work because it includes other types of energy transfers as well. and cannot be recovered by simply moving the piston infinitesimally in the opposite direction. Polarization work: AP3290 15 . heat has been irreversibly lost due to friction. an electric field does work on charged particles as they move through a medium. For instance. or dW = Fds Where: C is the path or curve traversed by the object. Mechanical work can be taken as a rather general definition of work: . electrical work(moving charge). 2. Qf. One is by doing work and the other is by heat transfer. such as: polarization work(changing polarization of a dielectric solid).2 Energy transfer: Work and Heat There are two ways of exchanging or transferring energies between a system and its surroundings (also called environment. Although the system has been driven from its equilibrium state by only an infinitesimal amount. F is the force vector.2. 2. s is the position vector. measured in joules (symble: J) in SI units. dW = EdQ . It is a scalar quantity. Electrical work: Qf W = ∫Q EdQ. there are many other forms of work. but not reversible process. reservoir). In addition to mechanical work (moving mass). Forms of work that are not evidently mechanical in fact represent special cases of this principle. are the amount of charges for “initial” state and “final” state. etc. magnetization work(changing the magnetization of a paramagnetic solid). In thermodynamics.

are the total polarization of material at “initial” state and “final” state. PV work is often represented by its differential form: Eq2-1 W= work being done onto the system by environment.Thermodynamics Y Y Shan ρf W = ∫ρ Edρ . are the total magnetization of material at “initial” state and “final” state. Mf. dW = BdM . Also. he calculation of work for this case is straightforward: V F Ads = − ∫V PdV . ρf. respecively. Magnetization work: Mf W = ∫M BdM . volume V = As. AP3290 16 . i where Mi. respecively. For the circular piston shown below. dW = Edρ . A PV work can be represented simply by : sf sf i i W = − ∫s Fds = − ∫s f i Vf W = − ∫V PdV i where pressure P = F/A. i where ρi. (a) PV work and PV diagrams for gas PV work occurs when the volume of a gas (a fluid) changes.

or to say that the environment does work to the system. 2. or to say that the system does work to the environment. So system loses energy (ii) isovolumetric process (also called isochoric process. or constant volume process): AP3290 17 . i. dW = − PdV > 0. reservoir). dW = − PdV < 0. Examples of PV work and PV diagrams (i) isobaric process (constant pressure) For a process from state “b” to “a”: Va W = − ∫V PdV = − P (Va − Vb ) > 0. It should be noticed that the W or dW is defined as the work done to the system. V= volume of the system. the system receives negative “work” from surroundings(environment. meaning the volume expands. the system receives “work” from surroundings(environment. dV > 0 .e. reservoir). dV < 0 .e. i. meaning the volume decreases. or system does work to the environment. when 1.Thermodynamics Y Y Shan P= external pressure (which usually equals to the pressure of the system during quasistatic process). b Environment does work to the system. a The environment does negtive work to the system. system obtains energy from environment For a process from state “a” to “b”: Vb W = − ∫V PdV = − P (Vb − Va ) < 0.

in general. This means that there is no PV work done in this process. P and V are used. Therefore. The path here in the discussion is a curve in the Euclidean space. like PV work. The more general expression for work done is: One important conclusion from the above discussion about work (read also Page 5. the PV-diagrams above forms only a 2-D Euclidean state space. AP3290 18 . From a thermodynamic perspective. the volume stays constant. It must be emphasized that all thermodynamic work WC (not just the PV work discussed above). it can be seen that PV work is pathdependent. PV work in general can be visualized in PV-diagram as the area under the pressure-volume curve(PV curve) which represents the process taking place. all thermodynamic work functions are not state function. W=P∆V= 0. The dimension of the Euclidean space is specified by the state coordinates (parameters) of the system. but only depends on the endpoints of the “initial state” and “final state”. is explicitly a function of the path C and depends on every detail of the path C.6): Looking into the above examples of PV work. this fact implies that PV work is not a state function.Thermodynamics Y Y Shan In this process. For e. infinitely many such curves are possible connecting “initial state” and “final state”. because only two state coordinates. ∆V= 0.g.

2. by doing work on it. The temperature of a system (gas in the following example) can be raised either by heating it. symbolized by Q. Here are the examples of mechanical equivalent of Heat. Q is said to be the heat absorbed from the surroundings (environment) by a system. or a combination of the two. Its conventional sign is that: Q>0. is a form of energy.2 Y Y Shan Heat Heat. means a system releases heat into its surroundings. Heat can be transferred between objects by radiation. It is defined as the kind of energy transferred from a high temperature object (system) to a lower temperature object (system). Q<0.Thermodynamics 2. The equivalence of heat and other energy form Heat transfer and work are both ways of transferring energy. means a system absorbs heat from its surroundings. AP3290 19 . conduction and convection. In thermodynamics.

Internal energy. 2. namely the internal energy is introduced. At that time calories were the accepted unit of heat and joules became the accepted unit of mechanical energy. Their relationship is found to be: Joule's apparatus for measuring the mechanical equivalent of heat. Starting from the initial low temperature state to reach the final temperate state does not depend on what specific forms of processes are. It is related to the molecular structure and the degree of molecular activity and may be viewed as the sum of kinetic and potential energies of the molecules AP3290 20 . This fact tells us that we can define a state function to describe the possible states. James Joule showed the energy equivalence of heating and doing work by using the change in potential energy of falling masses to stir an insulated container of water with paddles.Thermodynamics Y Y Shan In a classic experiment in 1843. microscopically defined.3 Internal energy The above examples indicate that a system in a low temperature state can get to a high temperature state (or vise verse) through different thermodynamic processes. Careful measurements showed the increase in the temperature of the water to be proportional to the mechanical energy used to stir the water. a state function. is the sum of all microscopic forms of energy of a system. Therefore. referring to the invisible microscopic energy on the atomic and molecular scale.

1 More discussion and clarification among temperature. is a state function of a system. then energy will flow from the high temperature object to the lower temperature object. and they will approach an equilibrium temperature. Internal energy. a room temperature glass of water sitting on a table has no apparent energy. and the total internal energy of a given system is the difference between the internal energy of the system and the internal energy of the same system at absolute zero temperature. and internal energy From the zeroth law. the total internal energy cannot be precisely measured. Since absolute zero cannot be attained. the internal energy cannot be precisely measured. 2. But on the microscopic scale it is a seething mass of high speed molecules traveling at hundreds of meters per second. we know that when a high temperature object is placed in contact with a low temperature object. and an extensive quantity. When the details of this common-sense scenario are examined. heat.Thermodynamics Y Y Shan For example. AP3290 21 . symbolized by U. it becomes evident that the simple view of temperature is embodied in the commonly used kinetic temperature.3. Strictly speaking. This is because only changes in the internal energy can be measured. either potential or kinetic .

it is not a correct use of the word heat to say that the object "possesses heat". A theoretical definition of temperature says: "Temperature is a measure of the tendency of an object to spontaneously give up energy to its surroundings. The word heat is better reserved to describe the process of transfer of energy from a high temperature object to a lower temperature one. When two objects are in thermal contact. A simplified visualization of the contributions to internal energy can be helpful. Internal energy involves energy on the microscopic scale. the one that tends to spontaneously lose energy is at the higher temperature. Systems with the same temperature do not have the same internal energy: AP3290 22 . you can't tell which mechanism was used to give it that energy. and since the internal energy of a high temperature object resides in random motion of the molecules. With time. transferring energy from the higher temperature to the lower temperature region. Molecules in materials have not only kinetic energy but also potential energy associated with the intermolecular attractive forces.Thermodynamics Y Y Shan The above figures illustrate faster molecules striking slower ones at the boundary will increase the velocity of the slower ones and decrease the velocity of the faster ones. But you can also increase its internal energy by doing work on it. it is better to say that it possesses internal energy as a result of its molecular motion. A higher temperature simply implies higher average kinetic energy. To describe the energy that a high temperature object has. Surely you can take an object at low internal energy and raise it to higher internal energy by heating it. the molecules in the two regions approach the same average kinetic energy (same temperature) and in this condition of thermal equilibrium there is no longer any net transfer of energy from one object to the other.

e.Thermodynamics Y Y Shan Internal Energy Example When the sample of water and copper are both heated up by 1°C.. i. a much larger proportional energy must be added to the potential energy portion of the internal energy. AP3290 23 . So the total energy required to increase the temperature of the water is much larger. But to achieve this increase for water. its specific heat is much larger. since that is what temperature measures. the addition to the kinetic energy is the same.

and identifies heat transfer as a form of energy transfer. or it can be expressed as: dU = δQ + δW . Wsys = −Wenv The differential form of the mathematical statement of the first law is: dU = δQ − δW . the “W” in Eq. and system work.2-2 The first law makes use of the key concepts of internal energy. W: System work( Wsys): work done by the system on the environment.2-3 It is the same law. just that “W” is defined as the work done on the system instead of work done by the system. Environment work (Wenv): work done by the environment on the system. Eq.2-4 if δW denotes the “system work”. AP3290 24 . of course. It is typical to see in other references the following expression of the first law: ∆U = Q + W Eq.4 The first law and its differential form The first law of thermodynamics is an expression of the universal law of conservation of energy.2-2 is the Wsys. Clarification of two definitions of work. if δW denotes the “environment work”. The “W” in Eq. heat.2-3 is the Wenv. It is used extensively in the discussion of heat engines. The most common enunciation of the first law of thermodynamics is: “The change in the internal energy of a thermodynamic system is equal to the amount of heat energy added to the system minus the work done by the system on the surroundings” Eq.Thermodynamics Y Y Shan 2.

In other words. there is no function Q or W that can be differentiated to yield δQ or δW AP3290 25 . they are inexact differentials rather than exact differentials.Thermodynamics Y Y Shan Where dU . δQ and δW express the infinitesimal amount. The infinitesimal heat and work are denoted by δ rather than d because. in mathematical terms.