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Thermodynamics

Y Y Shan

Introduction
What is thermodynamics? Thermodynamics is one the four fundamental fields of
theoretical physics, which are :
1. Theoretical mechanics (developed from Newton mechanics)
2. Electrodynamics (developed from electromagnetism)
3. Thermodynamics
4. Quantum mechanics
Thermodynamics, where “thermo” means "heat"(i.e. energy in transit) and
“dynamics”, relates to "movement", is a branch of physics which deals with the energy
and work of a physical system. In essence thermodynamics studies the movement of
energy and how energy instills movement.

Thermodynamics has been developed into two parts, as will be discussed in
this course.

One is Classical thermodynamics, the other is Statistical

thermodynamics.
Classical thermodynamics, being the macroscopic theory, concerns with
macroscopically measurable properties of matters, such as energy, work, and heat, but all
lacks an atomic scale interpretation.

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volume. chemical engineering. phase transitions.Thermodynamics Y Y Shan Statistical thermodynamics. which gives scientific descriptions of phenomena with avoidance of microscopic details. and even black holes. such as engines. which focuses on the derivation of macroscopic results from first principles. chemical reactions. It was found to be very successful and thus is commonly used. The study of thermodynamics is important because many machines and modern devices change heat into work (such as an automobile engine) or turn work into heat (or cooling. thermal energy converts to mechanical energy: Typical thermodynamic system . It can be applied to a wide variety of topics in science and engineering. For e. energy.) from the properties of moving constituent particles and the interactions between them (including quantum phenomena). The results of thermodynamics are essential for other fields of physics and for chemistry. (both not shown) and work is extracted.heat moves from hot (boiler) to cold (condenser). aerospace engineering. statistical thermodynamics is an approach to thermodynamics situated upon statistical mechanics. in this case by a series of pistons. being the microscopic theory. biomedical engineering. mechanical engineering. cell biology. as in a refrigerator). Essentially. pressure. and materials science . etc.g. entropy. AP3290 2 . thermodynamics was given a molecular interpretation. can be thought of as a bridge between macroscopic and microscopic properties of physical systems. It can be opposed to its historical predecessor phenomenological thermodynamics. With the development of atomic and molecular theories in the late 19th century. The statistical approach is to derive all macroscopic properties (temperature. transport phenomena.

and Motive power. was used in William Thomson's paper An Account of Carnot's Theory of the Motive Power of Heat. as a functional term. The first thermodynamic textbook was written in 1859 by William Rankine. The paper outlined the basic energetic relations between the Carnot engine. By 1849.Thermodynamics Y Y Shan Historical notes: Sadi Carnot. the Carnot cycle. power. and engine efficiency. The term thermodynamics was coined by James Joule in 1858 to designate the science of relations between heat and power. the "father of thermodynamics". "thermo-dynamics". This marks the start of thermodynamics as a modern science. originally trained as a physicist and a civil and mechanical engineering professor at the University of Glasgow AP3290 3 . a discourse on heat. who in 1824 published “Reflections on the Motive Power of Fire”.

Four types of thermodynamic systems are distinguished depending on the AP3290 4 . originally called a working substance. etc There are four typical thermodynamic “systems”: Thermodynamics is basically concerned with the flow and balance of energy and matter in a thermodynamic system.Thermodynamics Y Y Shan Part I Classical thermodynamics—The Macroscopic theory Chapter 1 The Zeroth law of thermodynamics and the temperature 1. and solids. for example a piston. A boundary separates the system from the rest of the universe. interactions between substance of large ensembles of objects (such as gas. or a planet. A thermodynamic system. being referred to as the environment or surroundings (sometimes called a reservoir). moveable. Surroundings(environment) and Boundary: In thermodynamics. liquid. heat. Central to this are the concepts of system and surroundings. a solution in a test tube. The possible exchanges of work. whose average motions define its macro properties. Boundaries are of four types: fixed. a living organism. is composed of large number of particles. or matter between the system and the surroundings take place across this boundary. real. and imaginary A system can be anything. molecules) are studied and categorized. which contains large number of atoms.1 Basic concepts: vocabularies associated with thermodynamics (i) System (thermodynamic system).

An extensive quantity (also extensive variable or extensive parameter) is a physical quantity. independently of its surroundings. A thermodynamic system is described by a number of thermodynamic parameters (e. 3. (ii) “State” and State parameters (state coordinates) and function of state for thermodynamic systems. No matter and energy(heat. are therefore called They are all macroscopic physical quantities. namely: Geometrical (such as volume). Examples of intensive quantities include: temperature. T. Closed systems are able to exchange energy (heat and work) but matter may not cross the boundary. That is. Chemical (such as composition or mole). V.etc. State: For a state of a thermodynamic system. such as P. Open systems: exchanging energy (heat and work) and matter with their environment. which can be measurable. chemical potential…. Isolated systems : matter and energy may not cross the boundary. composition. pressure). The number of parameters (or coordinates) needed to describe the system is the dimension of the state space of the system. B. There are five dominant classes of systems: 4. 2. electric field. There are FOUR kinds of state coordinates. E. Mechanical (such as pressure). the macroscopic condition can be described by its particular thermodynamic parameters. temperature. and electromagnetic parameters(such as intensities of electric and magnetic fields) State parameters can also be classified as Intensive and extensive quantities: An intensive quantity (also intensive variable) is a physical quantity whose value does not depend on the amount of the substance. density. such as temperature(T).Thermodynamics Y Y Shan kinds of interaction and energy exchange taking place between the system and its surrounding environment: 1. whose value is proportional to the size of the system it describes. State parameters: These particular parameters thermodynamic state parameters (or state coordinates). Adiabatic Systems – heat must not cross the boundary. AP3290 5 . volume. density. work) exchange with the surrounding. viscosity. pressure(P). any state of any system can be described by a set of parameters. pressure.g. etc.

a system's macro physical properties are. from state “1” at T1. At least two independent state coordinates are needed to describe any thermodynamic system. only dependents on the endpoints of the temperature values. to state”2” at T2. A state function describes the equilibrium state of a system. entropy. (iii) Function of state (or state function): There is an optimal ensemble of independent parameters that uniquely specify thermodynamic state. For example. enthalpy and entropy are state functions.Thermodynamics Examples of extensive quantities include: Y Y Shan mass. They can describe quantitatively an equilibrium state of thermodynamic systems. At the same time. The product f=PV is therefore a state function of the system. AP3290 6 . PV=nRT=f(T). length. a state function is a function that the change of its value between the two states only depends upon the parameters' values at the endpoints of the path. internal differences in the system tend to even out and pressures and temperatures tend to equalize. the change of the function ∆f = ∆ ( PV ) = nR (T2 − T1 ) . heat… etc. an intensive one and an extensive one. we know for ideal gas. (iv) Thermal equilibrium state As time passes in an isolated system. mechanical work and heat are process functions because they describe quantitatively the transition between equilibrium states of thermodynamic system. A system in which all equalizing processes have gone practically to completion. internal energy. and all other state parameters (measurable macroscopic quantities) can be derived from these. volume. Also. by definition. energy. unchanging in time. Those relationships between the derived parameters and the original independent parameters are called Function of State. when a system changes from one state to another continuously. T2 and T1. is considered to be in a state of thermodynamic equilibrium In thermodynamic equilibrium. electrical resistance. For example. as do density differences.

and it forms the basis for comparison of temperatures. they will then maintain a constant temperature. long after the other three laws named as such. 1. AP3290 7 . The objects will approach the same temperature. The law is more fundamental than any of the others.3 Concept of temperature: a unique state parameter (different from the other the four kinds state parameters) Macroscopically. Thermal equilibrium is the subject of the Zeroth Law of Thermodynamics. and in the absence of loss to other objects.2 Y Y Shan Thermal equilibrium and the Zeroth Law of Thermodynamics (i) Thermal equilibrium: It is observed that a higher temperature object which is in contact with a lower temperature object will transfer heat to the lower temperature object. History: The term zeroth law was coined by Ralph H. Practically this means that all three are at the same temperature. (ii) “The Zeroth law”: it states that if two systems are at the same time in thermal equilibrium with a third system. temperature means the sensations of hotness or coldness of an object. However. then A is in thermal equilibrium with B. they are in thermal equilibrium with each other. If A and C are in thermal equilibrium with B.Thermodynamics 1. Fowler. hence the zero numbering. the need to state it explicitly as a law was not perceived until the first third of the 20th century. They are then said to be in thermal equilibrium.

so that thermometers. 1. But for general purposes. i. devices for measuring temperature. the temperatures of the two thermal equilibrium systems are the same. 0. is 0.15 K.Thermodynamics Y Y Shan In the microscopic view. or more informally. they will show the same physical property.e.. temperature is associated with the agitation.00°C. The freezing point of water at one atmosphere pressure.4 Temperature scale.125 K. molecules) inside the macro-object. Temperature measurement and thermometers (i) Temperature scale: The Celsius. The triple point of water is 273. The Kelvin scale is called absolute temperature and the Kelvin is the SI unit for temperature. that we can 'construct a thermometer'. Kelvin. the boiling point is 373. and that is an international standard temperature point.16 K. The Zeroth law is the basis for the definition of temperature. (ii) Temperature measurement and thermometers: Measuring temperature relies on measuring some physical property of a working material that varies with temperature. Some of the thermometers are: (a) Bulb thermometer AP3290 8 . A scientific understanding of the concept of temperature builds upon thermal equilibrium. and Fahrenheit temperature scales are shown in relation to the phase change temperatures of water. This is because when two systems are in thermal equilibrium.01K below that at 273. or 99. have been developed. vibration. It is often claimed (for instance by Max Planck) that the Zeroth law proves that we can define a temperature function. or motion of the micro-particles (atoms. If you want to be really precise about it.75 °C. and this unique physical property is called “temperature”. just 0 °C and 100 °C are precise enough.

As they are almost invariably made of platinum. Disposable liquid crystal thermometers have been developed for home and medical use. are temperature sensors that exploit the predictable change in electrical resistance of some materials with changing temperature. AP3290 9 . i. and they can read body temperature by being placed against someones forehead and are safer than a mercury-in-glass thermometer (c) Resistance thermometers. the change of volume is proportional to the change of temperature (b) liquid crystal thermometer is a type of thermometer that contains heat-sensitive liquid crystals in a plastic strip that change color to indicate different temperatures. Temperature changes can affect the color of a liquid crystal.e. they are often called platinum resistance thermometers.1°C range. which makes them useful for temperature measurement.Thermodynamics Y Y Shan This is based on the fact that the volume of the working matter in the bulb (sometimes colored alcohol or metallic liquid mercury) grows bigger when heated and smaller when cooled. The resolution of liquid crystal sensors is in the 0. also called resistance temperature detectors.

e.Thermodynamics Y Y Shan (d) Semiconductor thermometers: silicon bandgap temperature sensor is an extremely common form of temperature thermometer used in electronic equipment. the object's temperature can be determined. They are sometimes called non-contact thermometers to describe the device’s ability to measure temperature from a distance. (e) Thermocouples: In electronics. By knowing the amount of infrared energy emitted by the object. the temperature patterns across the surface of an object can be recorded and a thermal image related to the spot temperature can be constructed (i. AP3290 10 . (f) Infrared thermometers(or infrared pyrometer): they measure temperature using blackbody radiation (generally infrared) emitted from objects (the radiation is temperature dependent). it will generate a voltage. The principle of the sensor is that the bandgap (and therefore its forward voltage) of a silicon diode is temperature-dependent. which says that when any conductor (such as a metal) is subjected to a thermal gradient. by scanning the infrared thermometer. a subject called Infrared thermography). This effect was discovered by the German-Estonian physicist Thomas Johann Seebeck in 1821. this kind of thermometers is a widely used type of temperature sensor. Its main advantage is that it can be included in a silicon integrated circuit. The principle of operation is based on the thermoelectric effect. A doctor's IR thermometer in use In principle.

Equations of state are useful in describing the properties of gases. y . fluids. which was originally determined empirically and is simply PV = nRT = N A kT AP3290 11 . y can be the volume V and pressure P or other state parameters (macro quantities) of the system.Thermodynamics Y Y Shan A 2D-tempearture pattern constructs a thermographic image of a dog. mixtures of fluids. i.T. solids. volume V. More specifically. such as its temperature. (i) Equation of state for Gas (a) The ideal gas law: equation of state for ideal gas In 1834 Émile Clapeyron combined Boyle's Law and Charles' law into the first statement of the ideal gas law. providing a mathematical relationship between two or more state parameters associated with the matter. A typical equation of state can be written as: f ( x. T ) = 0 x. It is a thermodynamic equation describing the state of matter under a given set of physical conditions. pressure. an equation of state is a formula describing the interconnection between various macroscopically measurable properties of a system. P.e usually an relationship between state parameters(coordinates) and the temperature of the system.5 Equation of state: In thermodynamics. 1.

g. The constant a provides a correction for the intermolecular forces. The van der Waals equation of state approaches the ideal gas law PV=nRT as the values of these constants approach zero.Thermodynamics • • • • • • Y Y Shan n = number of moles R = universal gas constant = 8. T ) = 0 . B. its equation of state has the expression: f ( M . It is usually referred to as the van der Waals equation of state. This works well for dilute gases in many experimental circumstances. van der Waals in 1873 to take into account molecular size and molecular interaction forces. which is typically expressed as the Curie’s Law: AP3290 12 . and there are circumstances where the properties of the molecules have an experimentally measurable effect.617385 x 10-5 eV/K k = R/NA NA = Avogadro's number = 6. A modification of the ideal gas law was proposed by Johannes D. one of the first to perform markedly better than the ideal gas law: The constants a and b have positive values and are characteristic of the individual gas. Constant b is a correction for finite molecular size and its value is the volume of one mole of the atoms or molecules (ii) Equation of state for liquid: Such empirical equations can be found in many references discussing specific liquids (ii) Equation of state for solid: For e.3145 J/mol K N = number of molecules k = Boltzmann constant = 1. But gas molecules are not point masses.38066 x 10-23 J/K = 8.0221 x 1023 /mol (b) The van der Waals equation of state The ideal gas law treats the molecules of a gas as point particles with perfectly elastic collisions. paramagnetic materials..

AP3290 13 . T is absolute temperature. This relation was discovered experimentally (by fitting the results to a correctly guessed model) by Pierre Curie. C is a materialspecific Curie constant. measured in teslas. M is the resulting magnetisation. B is the magnetic flux density of the applied field. measured in kelvins.Thermodynamics Y Y Shan Which relates the magnetization of the material to the applied magnetic field and temperature.