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1. Introduction to thermodynamics 2. Relevance for atmosphere 3. Global perspectives 4. Heat machines & Geophysics From Wikipedia, the free encyclopedia Thermodynamics (from the Greek thermos meaning heat and dynamis meaning power) is a branch of physics that studies the effects of changes in temperature, pressure, and volume on physical systems at the macroscopic scale by analyzing the collective motion of their particles using statistics. Roughly, heat means "energy in transit" and dynamics relates to "movement"; thus, in essence thermodynamics studies the movement of energy and how energy instills movement. Historically, thermodynamics developed out of the need to increase the efficiency of early steam engines. The starting point for most thermodynamic considerations are the laws of thermodynamics, which postulate that energy can be exchanged between physical systems as heat or work. They also postulate the existence of a quantity named entropy, which can be defined for any system. In thermodynamics, interactions between large ensembles of objects are studied and categorized. Central to this are the concepts of system and surroundings. A system is composed of particles, whose average motions define its properties, which in turn are related to one another through equations of state. Properties can be combined to express internal energy and thermodynamic potentials are useful for determining conditions for equilibrium and spontaneous processes. With these tools, thermodynamics describes how systems respond to changes in their surroundings. This can be applied to a wide variety of topics in science and engineering, such as engines, phase transitions, chemical reactions, transport phenomena, and even black holes. The results of thermodynamics are essential for other fields of physics and for chemistry, chemical engineering, cell biology, biomedical engineering, and materials science to name a few.
• • "Thermodynamics is the only physical theory of universal content which, within the framework of the applicability of its basic concepts, I am convinced will never be overthrown." — Albert Einstein "The law that entropy always increases - the Second Law of Thermodynamics - holds, I think, the supreme position among the laws of physics. If someone points out to you that your pet theory of the universe is in disagreement with Maxwell's equations - then so much the worse for Maxwell's equations. If it is found to be contradicted by observation - well, 1.1
you don't understand it at all.• • these experimentalists do bungle things from time to time. there is nothing for it but to collapse in deepest humiliation. except for one or two small points.2 . whose every subtlety only experts in the art of handling Hamiltonians would be able to appreciate?” Pierre Perrot. But if your theory is found to be against the Second Law of Thermodynamics I can give you no hope. bequeathed by past decades." — Arnold Sommerfeld 1. The second time you go through it. you think you understand it. you know you don't understand it. but by that time you are so used to it. The third time you go through it. The first time you go through it. author: “A to Z Dictionary of Thermodynamics” "Thermodynamics is a funny subject. it doesn't bother you any more." — Sir Arthur Eddington “Isn’t thermodynamics considered a fine intellectual structure.
Introduction to (atmospheric) thermodynamics 1. forces.1. The atmosphere constantly exchange heat. and mass between the solid earth surface and the outer space. Many of these play an important role for setting the structure of the atmosphere.3 .1 On the atmosphere The atmosphere is an ever changing fluent layer that circumvents our earth. The atmosphere consists of a number of different gases and materials. The atmosphere mainly 1.
etc.consists of nitrogen gas. Following the fundamental laws of classical thermodynamics. 1. and vertical stabilities in the atmosphere.1. Furthermore. vatten. To a smaller extent there is also carbon dioxide. CO2. Is in constant movement (is not in equilibrium). 1. Mixture of dry air and moisture (luft+ånga=fuktig luft) 4. including convective-equilibrium climate models. Mixture of gases. CH4. they also play an important role for the radiation budget of the earth although they are not important directly for the thermodynamical properties of the atmosphere – which is the subject of this course. Atmospheric thermodynamics forms a basis for cloud microphysics and convection parameterizations in numerical weather models. Is forced thermally at the ground and some heights (by radiation). and is used in many climate considerations. Oxygen. Exchange with ground (and space). ånga). Argon. N2. atmospheric thermodynamics is the study of heat and energy transformations in the earth’s atmospheric system.4 . which exist in its all three phases in the natural environment. water. Pressure decreases with height. A material of special interest for this course is water. the free encyclopedia In the physical sciences. boundary layer meteorology. Ar. Methane. the transition between water vapor and water/ice is very important for many atmospheric processes and describing these transition properties will be one of the main tasks in this course. Ice. Dry air (torr luft) 2. Water in its three phases (aggregationstillstånd). 1. 3. 3. A mixture of moist air and water droplets and/or ice crystals. Notably. formation of clouds. 4. Accordingly. and by burning of fossil fuels and organic material. atmospheric thermodynamics studies such phenomenon as properties of moist air.2 Specific for meteorology There are few things which may be considered to be specific for the atmosphere and how we deal with it from a thermodynamic viewpoint. O2. 2. Atmospheric thermodynamic diagrams are used as tools in the forecasting of storm development. Thermodynamically the following point receive most attention 1. gas (is. including water vapor. These latter gases are strongly affected by biological activity. the concentration of these gases varies significantly with time. atmospheric convection. From Wikipedia.
Thus thermodynamics treats phenomena on a macroscopic scale. From Wikipedia. as opposed to a microscopic scale. Accessible to us and our instruments. rather it deals the description and classification of phenomenon.1. Diathermic Systems . 1. pressures and temperatures tend to equalize.2 Basic thermodynamic stuff Thermodynamic principles are firmly rooted in experiments.1 There are some important concepts in thermodynamics. as do density differences.2. 1. Adiabatic Systems – heat may not cross the boundary. work.heat may cross boundary. or matter between the system and the surroundings take place across this boundary.1. In some regards thermodynamics is phenomenological in the way that it does not try to explain underlying causes in detail. is considered to be in a state of thermodynamic equilibrium. It seeks no explanation at a level below what we can observe directly with our coarse senses and measuring instruments. but which by convention delimits a finite volume. as time goes by. thermodynamics do not rely on the existence of invisible atoms and molecules – they provide a way to explain processes in a different way but the thermodynamic theory would essentially remain unchanged if we discover that the prevailing theory of atoms and molecules were wrong. A system in which all equalizing processes have gone practically to completion. For isolated systems. There are five dominant classes of systems: Isolated Systems – matter and energy may not cross the boundary. Thermodynamics is a science of measurable quantities rather than invisible constructors. 1. The possible exchanges of work. Closed Systems – matter may not cross the boundary.3 This course We will analyze some thermodynamic properties of the atmosphere highlighting the influence of water – and its phase transitions – on the atmosphere. the free encyclopedia An important concept in thermodynamics is the “system”. the atomic and molecular scale. Open Systems – heat. and matter may cross the boundary. internal differences in the system tend to even out. A system is the region of the universe under study. Thus. heat.5 . A system is separated from the remainder of the universe by a boundary which may be imaginary or not. We will also consider the main force balances of the atmosphere in this course and the vertical acceleration of air parcels – this is referred to as “statik”.
A system is in equilibrium with an external contact. by definition. Macro variables. Density. More than a postulate it is a hope that nature is kind to us. 2. All such boundaries are purely mathematic. Mass (m or ∆m). a. for instance can receive energy. i.6 . etc. it can be assumed that each intermediate state in the process is at equilibrium. Potential temperature. virtual temperature. Temperature: Can only be defined as something that is in equilibrium with an external system. Equilibrium: This is an important concept in thermodynamics. dew point. c. System: A system is a well defined volume that we intend to study. Open system: Interacts with the outside world. Systems in equilibrium are much simpler and easier to understand than systems which are not in equilibrium. Often. unchanging in time. There exist very many different meteorological properties defined as temperature. Volume (V or ∆V).). Closed system: Is not in contact with the outside world?? i. Temperature requires equilibrium to be defined and it is a complicated variable to define and measure. Systems can be described relatively well even if there is not a true equilibrium. (ρ=M/V or ρ=∆M/∆V). There are no sharp and impermeable boundaries in nature. a. Internal equilibrium (inre jämvikt. This will also considerably simplify the situation. The total mass of the system is a key variable of the system b. a. potential virtual temperature.In thermodynamic equilibrium. 4. A system that does to exchange any properties with the surrounding is in equilibrium. a system's properties are. when analyzing a thermodynamic process. Density is a commonly used variable in dynamical meteorology. 3. b. In meteorology the volume is often expressed in a different form namely as i. Packets that we will frequently refer to has scales molecules<<package<<system. 1. not a law. a postulate. The postulate of local equilibrium is just that. 1. Thermodynamic processes which develop so slowly as to allow each intermediate step to be an equilibrium state are said to be reversible processes. Requires that a system is relatively close to equilibrium. Thus we will only consider small infinitesimal disturbances. ii. External equilibrium (yttre jämvikt). b.
p= ∆F . 5.7 .15 K. 0oC=273. p + 2 (v − b ) = nR *T . In a gas containing more than one component. Total pressure p = ∑ p k = k ∑ nk Rk* = k n R* T n∑ k k V k n 1. v is molar volume (volume V per mole n. and T. Uses Kelvin scale (K) or Celsius (oC). Micro variables: Molecular speed. b are v constants appropriate for each gas.414 m3/mol for p0=1 atm. number of molecules etc. Alternative form pv = RT . Pressure (p). p. R=R*/M (M=molmassa) is the specific gas constant (specifika eller inviduella gaskonstanten). a. a. α . Unit is Pa=1N/m2. a iii. thus Volume and Temperature are “global” quantities. Avogadros number v=22. each component add to the total pressure (for an ideal gas).) ii. In principle we can always use α instead of V in the thermodynamics relation provided that we change appropriate constants.ii. Pressure implies the presence of a force perpendicular to an area A which equals i. i. An important pile stone of the thermodynamics is that there exist some well described relations between the physical quantities P. Van der Waals equation. T0=273 K). 6. Is relatively complicated. ∆A ii. b. Often used is mbar=102Pa=1hPa. d. pV = nR *T : n is number of moles. Specific volume (α=∆V/∆M). p k V = nk R *T . (in meteorology. c. i. Not really considered in thermodynamics. Temperature (T or θ). Daltons law: A mixture of ideal gases will behave as an ideal gas. T). Equation of state (tillståndsekvationen). T V ii. i. There are a large number of temperature definitions in meteorology. R*(=8. Notably ρα=1. or p = ρRT .3144 J mol-1 K-1) universal gas constant. belongs to statistical mechanics. Is used in the thermodynamic analysis of meteorology. Requires equilibrium to be defined in a proper way. Meteorology: pα = RT . V.
The four laws are: 1. For air: pα = Rd T . thereafter it decreases with height.97 kg/mol. iv.iii. U2 (p.T). Examples of this include Einstein's prediction of spontaneous emission around the turn of the 20th century and current research into the thermodynamics of black holes. α). An important concept is that the relation between state variables can be written F(p. U1. T). c. α. Rd=287. However to avoid naming an incomprehensive number of functions one usually skip the index on the function. 1. The direct implication is that all functions will varies independently on two of the states variables only. i. Air composition is relatively constant up to 100 km. If two variables are known. Figure text: Mean molecular weight versus height for U. U3(p. that is U= U1(α. Hence. T = T(p. U2. the free encyclopedia In thermodynamics. there are four laws of very general validity.T).8 . they can be applied to systems about which one knows nothing other than the balance of energy and matter transfer. T)=0. Notably.3 Laws of thermodynamics From Wikipedia. and as such they do not depend on the details of the interactions or the systems being studied. U3 are three completely different functions. the third can be calculated. Standard Atmosphere. α = α (p.S. We may write p= p (α. T). α). Specific molmass Md=R*/Rd=28.0 J/K.
stating that thermodynamic equilibrium is an equivalence relation. about absolute zero temperature As a system asymptotically approaches absolute zero of temperature all processes virtually cease and the entropy of the system asymptotically approaches a minimum value. For instance o d v2 dz dv v ⋅ m = mge z ⇒ m = mg ⇒ dt 2 dt dt . However.Zeroth law of thermodynamics. If two thermodynamic systems are in thermal equilibrium with a third. Second law of thermodynamics. For system with many particles. can change between the kinetic energy of the point mass (energy of motion) and the potential energy (energy of position). d ( K + P ) = 0 ⇒ K + P = const dt Energy is conserved in a mechanistic system. First law of thermodynamics.9 . about entropy The total entropy of any isolated thermodynamic system tends to increase over time. they are also in thermal equilibrium with each other. 1’st law: Energy is conserved. Consider a balloon filled with water. My view • • 0’th law: Two systems that are in thermal equilibrium with a third are in thermal equilibrium with each other. Third law of thermodynamics. this thus also represent a kinetic energy but may represent internal kinetic energy (or temperature) Ordered mean motions are easily transferred to internal random motions. about the conservation of energy The increase in the energy of a closed system is equal to the amount of energy added to the system by heating. it can be shown that we also consider changes in kinetic and potential energy in the way the mass centre moves (the kinetic energy of a fictious body with mass equal the entire system of point masses and moving with its centre of mass velocity) and in the way the particles move randomly or disorganized. If we drop it will have a certain mean motion before it strikes the floor. minus the amount lost in the form of work done by the system on its surroundings. approaching a maximum value. after hitting the floor the mean motion becomes zero and must 1.
and inexact differentials (denoted d ) that refers to external forcing parameters. proceeding from the familiar to the unfamiliar.have been transferred to disorganized random motion with zero net mass transfer. the work will depend on the exact pathway. all concepts. Thermodynamics is a way to describe these processes with giving an exact description of the entire procedure. This feature is always valid for the atmosphere and is actually well fulfilled in a normal engine. dt dt dα which implies that we dt • It should be noted that we require that ∆x ∆t << v s . (these are dt equal zero for a closed system). dU = dQ + dW • We need to distinguish between exact differentials (denoted d) which refers to state variables. o If a closed system is caused to change from an initial state to a final state by adiabatic means only. scientific or otherwise – is to use them in as many contexts as possible. dU = Q − W . (Whatever than means) The best way to understand energy and entropy – indeed. Conservation of energy implies that internal motion must have increased.e. Q is heating rate. o If there is an exchange of properties between the system and the outside word. In other words mean motion (external) have been transformed into disorganized motion (heat). From Wikipedia. then the work done on the system is same far all adiabatic paths connecting the two states. where vs is the speed of molecules (i. roughly the speed of sound) for the system to be in a reasonable quasi-stationary state. W working rate. the free encyclopedia 1.. o Internal energy. • In general the work is W = p often write dU dα =Q− p . • 2’nd law: Entropy always increases.10 .
such as constant temperature or pressure. The six most common thermodynamic processes are shown below: 1.An isobaric process occurs at constant pressure. it is useful to group these processes into pairs. 4. enthalpy is the internal energy of the system plus the energy related to pressure-volume work. etc. 2. in energetic character. in which each variable held constant is one member of a conjugate pair. Typically. The four most well known potentials are: Internal energy Helmholtz free energy Enthalpy Gibbs free energy Potentials are used to measure energy changes in systems as they evolve from an initial state to a final state. each thermodynamic process is distinguished from other processes. Internal energy is the internal energy of the system. 3.An isenthalpic process occurs at a constant enthalpy. occurs at constant volume.An isothermal process occurs at a constant temperature. 6.An isochoric process. or isometric/isovolumetric process. Thermodynamic potentials As can be derived from the energy balance equation on a thermodynamic system there exist energetic quantities called thermodynamic potentials.Thermodynamic processes A thermodynamic process may be defined as the energetic evolution of a thermodynamic system proceeding from an initial state to a final state. or volume.11 . 1. are held fixed.. Furthermore. The potential used depends on the constraints of the system. respectively. being the quantitative measure of the stored energy in the system. as temperature.An adiabatic process occurs without loss or gain of heat. and Helmholtz and Gibbs free energy are the energies available in a system to do useful work when the temperature and volume or the pressure and temperature are fixed. according to what parameters. 5.An isentropic process occurs at a constant entropy. pressure.
12 . Joules law and has been confirmed to be small in experiments using real gases).1 Constant volume Applying the chain rule simply provides dU ∂U dT ∂U dα = + dt ∂T dt ∂α dt Notably ∂U ∂α has the dimension of pressure and is sometimes called the internal pressure (for an ideal gas ∂U ∂α =0.1. The response may be considered from the response in time or as ordinary differentials. thus 1.4. Cv depends on the total mass of the system and sometimes it is convenient to deal with the specific heat capacity instead.4 Changes due to heating Lets us assume that we heat a certain volume of gas. Q = Cv Notably we also find that ∂C v ∂ ∂U ∂ ∂U = = ≈0 ∂V ∂V ∂T ∂T ∂V This relation holds for an ideal gas where interactions between molecules are negligible. temperature T and volume V. 1. while the third variable p is related to these two by the ideal gas law. dt Its relevance is clear from the following equation appearing for constant volume. heat capacity (at constant volume) Cv = ∂U ∂T dT . V=const. Continuing Q= ∂U ∂T ∂U = ∂T dT ∂U dα dα + +p dt ∂α dt dt dT ∂U dα + + p dt ∂α dt ∂U ∂α = 0 for an ideal gas (pdV=0 for above experiment) The first partial derivative on the right hand side of this equation appears with sufficient frequency that is has acquired a name. Let us write Q= dU dα +p dt dt The internal energy U for a simple closed system such as a gas may be considered s function of the two independent variables. Personally I do think that it is easier to consider changes in time than in differentials.
Fix the piston in place and heat the gas for a certain amount of time.4. We thus find that the heat capacity (or resistance to become warm when heated) is larger under constant pressure than under constant volume.2 Constant pressure To find how the system respond to heating under constant pressure we need to find an expression which has dp/dt.Cv = cv . To show that cp greater than cv makes physical sense. 1. consider an ideal gas confined to a cylinder fitted with the usual frictionless nut tightly fitted piston. This implies that the temperature increase isn’t as great. Stated another way. The temperature of the gas rises in this constant volume process. m 1. which is consistent with what we derived. but in this process the piston rises. Heat the gas for the same amount of time a before. cp is greater than cv. Now let the piston move freely so that gas pressure is constant. Starting as before Q= dU dα +p dt dt dα d T R dT RT dp − 2 =R = dt dt p p dt p dt using that pα = RT we can write Q= R dT RT dp dU dU dT RT dp + p p dt − p 2 dt = dt + R dt − p dt dt dU dT dT RT dp = +R − dT dt dt p dt under constant pressure we find Q = (Cv + R ) C p = Cv + R dT dT = Cp dt dt . thus work is done by the gas and consequently its internal energy doesn’t increase as much as before. Again the temperature increases.13 .
However. This can be shown but I am too lazy ☺ 1.4.3 Constant pressure 2 The derivations for the temperature response to heating under constant volume and constant pressure took different paths. defined as H = U + pα dU dα +p can now be written dt dt The first law Q = Q= dH dp −α dt dt the chain rule gives dH ∂H dT ∂H dp = + . dt ∂T dt ∂p dt We thus have Q= ∂H ∂T ∂H = ∂T dT ∂H dP dP + −α dt ∂P dt dt dT ∂H dp + −α dt ∂V dt 1.For liquids and solid material the compressibility (implying that pdα≈0) is essentially zero and thus C p ≈ Cv . let us redo the calculation in another way. it is convenient to introduce enthalpy.14 .
also called heat content. p=const. no work done and thus the internal energy must remain constant. symbolized by H. to pave the way forward we need to introduce the concept entropy. the free encyclopedia In thermodynamics. p ) = U (T . ∂U ∂α ∂α +p will be considered in later ∂α ∂T ∂T sections. The left part has a certain pressure and the right volume has no pressure.15 . ∂α ∂α C p = Cv + p = Cv + R ∂T C p = Cv + Note that the intermolecular forces are negligible in an ideal law. ideal gas = 0 (Joules law). If the wall is removed gas will go from left to the right side. which is done in section 3. dt Its relevance is clear from the following equation appearing for constant volume.For constant pressure we have that the heat capacity (at constant volume) is Cp = ∂H ∂T dT . the quantity enthalpy. α ) + pα ∂H dT ∂H dp ∂U dT ∂U dα dp dα + = + +α +p ∂T dt ∂P dt ∂T dt ∂α dt dt dt dα ∂α dp ∂α dT + α = α ( p. There is no exchange of heat. Joules law and the expression C p = Cv + From Wikipedia. Q = CP p) H = U + pα H (T . Joules law can be showed in experiments where a chamber is split in two parts. is the sum of the internal energy of a thermodynamic system plus the energy associated 1. T ) ⇒ = dt ∂p dt ∂T dt ∂α dT ∂H ∂U ∂α dα dp ∂H ∂U ∂U ∂α − − −p + ∂P − V ∂α ∂p − p dp dt = 0 ∂T dt ∂T ∂T ∂α ∂T Using the definition of entalphy (and conidering the independent variables to be T and thus ∂U ∂α ∂α +p ∂U ∂α ∂T ∂T . However.
and the total enthalpy of a system cannot be measured directly. meaning to "put into". Enthalpy is a quantifiable state function. for a simple system. we need to do work to push the atmosphere away in order to make room for the system. Enthalpy is a thermodynamic potential. the difference in enthalpy is the maximum amount of thermal energy derivable from a thermodynamic process in which the pressure is held constant. the energy extracted is not just U. Conversely. this mechanical work required is just PV where V is the volume of the system.16 . one can ignore the compression/expansion mechanical work. Therefore. enthalpy is the total amount of energy one needs to provide to create the system and then place it in the atmosphere.with work done by the system on the atmosphere which is the product of the pressure times the volume. then. colloquially. For systems at constant pressure. The term enthalpy is composed of the prefix en-. Assuming the environment is at some constant pressure P. the enthalpy change of a system is measured instead. 1. In other words. when considering change in enthalpy. Therefore. in addition to supplying the internal energy U for the system. if the system is annihilated. A possible interpretation of enthalpy is as follows. Imagine we are to create the system out of nothing. plus the Greek suffix -thalpein. the change in enthalpy is the heat received by the system plus the non-mechanical work that has been done. which is PV. meaning "to heat". with a constant number of particles. and is useful particularly for nearly-constant pressure processes. where any energy input to the system must go into internal energy or the mechanical work of expanding the system. but also the work done by the atmosphere as it collapses to fill the space previously occupied by the system.
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