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Thermodynamics

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published Reflections on the Motive Power of Fire . power. the Carnot cycle. and Motive power.Sadi Carnot. and engine efficiency. This marks the start of thermodynamics as a modern science. Sadi Carnot . a discourse on heat. in 1824. who. The paper outlined the basic energetic relations between the Carnot engine. the "father of thermodynamics".

Its underpinnings. Historically. thermodynamics developed out of need to increase the efficiency of early steam engines. based upon statistical predictions of the collective motion of particles from their microscopic behaviour. is the field of statistical thermodynamics a branch of statistical mechanics. different energy conversions into heat energy. chemical. pressure and volume. Roughly heat means "energy in transit" and dynamics relates to "movement“ • Thus. . mechanical.Histroy of Thermodynamics • In physics. and electrical energy). and its relation to macroscopic variables such as temperature. meaning "heat" and dynamics. thermodynamics (from the Greek therme. meaning "power") is the study of the conversion of heat energy into different forms of energy (in particular. in essence thermodynamics studies the movement of energy and how energy instils movement.

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Thermodynamics:“Thermodynamics is that branch of physics in which we study the interrelationship between the heat energy and mechanical energy”. .

If both energy and material cross the boundary.  If only energy crosses the boundary. separated from its surroundings by some specified boundary – in essence. it is an open system.Definitions  A system is the object or material(s) under study. If neither matter nor energy crosses the boundary. it is an isolated system. some collection of atoms. it is a closed system. .

1 hp lifts 33.g..g.Definitions (2) Work – force applied over a distance against a load (e.000 lbs /ft/min Heat* – the energy that flows from a body at higher temperature to one at lower temperature by virtue of the temperature difference. footpounds. or specific heat capacity heat capacity – the ratio between the heat added (or removed) . and the corresponding rise (or decrease) in the temperature of the material . or Newton-meters = joules) Power – Work per unit time (E. Experiments have shown that every material has a characteristic heat capacity per gram.

pressure. .Definitions (3) Thermodynamic variables can be divided into two categories: Extensive variables – variables that are proportional to the size of the system. volume and mole number (mass) Intensive variables .. g. E. and are independent of he size of the system..g. e.variables that specify local properties. temperature.

heat. The possible exchanges of work. A system is separated from the remainder of the universe by a boundary which may be imaginary or not. but which by convention delimits a finite volume. Everything in the universe except the system is known as surroundings.Thermodynamic systems An important concept in thermodynamics is the “system”. or matter between the system and the surroundings take place across this boundary . A system is the region of the universe under study.

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However. Fowler[citation needed]. the law is more fundamental than any of the others. long after the first three laws were already . the need to state it explicitly as a law was not perceived until the first third of the 20th century.(1889-1944) The term zeroth law was coined by Ralph H. In many ways.

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0th Law of Thermodynamics Thermal Equilibrium is the condition where there is no net heat flow between two bodies that have been placed in thermal contact. If A is in thermal equilibrium with B and C is in thermal equilibrium with B then A is in thermal equilibrium with C .

lift weight. • Work done by the gas = Area under the .Work done BY a gas • Work is Energy. • Heat is Energy • (½ mv2av) = (3/2)kBT • W = F∆y = PA ∆y =P ∆V • Raise piston. • Now the gas has less Energy in it.

For a repeatable process. . must return to initial state.Path Does Matter Work is Area under the Curve.

23-5 Work done on or by an ideal gas 1. Work done on an ideal gas p ideal gas x (a) Fx W v1 v1 v ∆W = − P ⋅ ∆V { (b) dW = − P(V) ⋅ dV W = − ∫ P(V) ⋅ dV vi vf .

P B A D C Two paths: A B D A C D vi vf V . the work done on the gas is equal to the area under the curve representing the process. (b) The pressure force is not a conservative force.Work done on gas in a more general form: W = − ∫ PdV (a) If PV relationship is known.

) vi v vi = v f v W = − ∫ P(V)dV = −(23-17) P ∫ dV = − P(v f − vi ) = − P ⋅ ΔV (c).W = − ∫ PdV 2. Work done at constant pressure (P is const.) p p vf W ≠0 W = 1 (23-16) W=0 (b). Work done at constant volume (V is const. Several typical thermal processes (a). Work done at constant temperature (T is const.) namely “isothermal process”. p vi vf v PV = constant .

and the initial pv = const.(d). we have γ PV γ = PiVi = constant vi vf V Fig 23-16 .1 .Vi . γ Pi Pf Pi . (23-19) P ( γ = 1 ~ 1） .1 If we know . T can be changed. Q=0. pv γ = const. γ PV = const. Work done in thermal isolation Thermal isolation is also called “adiabatic” process.

We can now find the adiabatic work: PiVi P= γ V γ W = .∫ PdV PV γ dV = − ∫ i γi dV = − PiVi ∫ γ Vi V V γ PiVi PV V 1γ − 1γ − =− (Vi − V f ) = i i [( i ) γ −1− 1 ] γ −1 γ − 1 Vf Vf γ By further using 1 W= ( Pf V f − PiVi ) γ −1 PiVi = Pf V f γ γ (23-22) .

What is Heat? Heat is Thermal Energy
Energy transferred between two objects because of

temperature difference. 1 calorie is the heat required to raise the temperature of one gram of water by one degree Celcius.
 (1 Btu is heat required to raise one pound of water by one degree

Fahrenheit)

1 cal = 4.186 Joules Work is Energy. Heat is generated in mechanical

processes. Known as MECHANICAL EQUIVALENCE OF HEAT

Thermal Energy Transfer
Specific Heat Q=mc∆T or Latent Heat

Q=mL Heat transfers between different objects based on temperature difference. The greater the ∆T, the greater the rate. Does not matter which has more energy (ice berg vs. coffee cup), only ∆T

Three Ways to Burn Yourself
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What is Temperature Temperature is a measure of the kinetic energy of matter. KE = (½mv2)av = 3/2 kBT . Collision between molecules causes energy transfer Motion of molecules causes pressure (collisions with container).

Zero Degrees Absolute Zero (Kelvin Scale) (-273. .15 oC) No motion of molecules Pressure is Zero.

No motion =No Energy =No Temperature •0 Celcius is pretty HOT = 273 Kelvin •Can’t really get to zero Kelvin.•T related to energy. •milliKelvin is easy. any more is hard (Noble Prize awarded for laser cooling) •Deep Space is about 3K .

So is the entire store of internal energy. No rotational kinetic energy. The total internal energy of n moles of an ideal monatomic gas is 1 KT 1 Eint = (nN A ) K trans 1 1 = nN A KT = nRT 1 1 . Internal energy of ideal monatomic gas Translational kinetic energy is 1 K trans = KT 1 No potential energy.The internal energy of an ideal gases 1.

2. Internal energy of molecule consisting of twoO N . such as y d Fig 23-18 z X The total kinetic energy of a diatomic molecule is 1 1 1 1 1 1 1 1 1 1 K = mv x + mv y + mv z + I x ω x + I y ω y 1 1 1 1 1 U=0 Etot=K . CO particles 1 1 .

1 1 Eint = N ( KT ) = nRT 1 1 E Notes: 1* int here dependents only on T and degree of freedom.5. . also oscillating degrees of freedom. The internal energy for different kinds of ideal gases: (a) Monatomic ideal gas (b) Diatomic gas 1 1 Eint = N ( KT ) = nRT 1 1 (c) A polyatomic gas generally has six degrees int = N ( 1 ) = 1 E of KT nRT 1 (d) If the molecule is not a rigid one. there are freedom. 2* Equipartition of energy theorem only apply in classical physics.

FIRST LAW OF THERMODYNAMICS Q = Heat transferred TO a system W = Work done BY a system U = Internal Energy of a system ∆U = Uf – Ui = Q – W .

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First Law PRINCIPLE of CONSERVATION of ENERGY In a cyclic system (where the system is the same at the end as at the beginning) ∆U =0 Q =W .

but exists forever .First Law • PRINCIPLE of CONSERVATION of ENERGY • In a cyclic system (where the system is the same at the end as at the beginning) • ∆U = 0 • Q =W • Energy is conserved It can neither be created nor destroyed.

For a thermodynamic system. The law of conservation of energy of the system can be expressed as (First law of thermodynamics) Q + W = ∆Eint (i) Q is the energy transferred (as heat) between the system and its environment because of . internal energy is the only type of energy the system may have.The first law of thermodynamics 1.

f − Eint.(ii) W is the work done on ( or by) the system by forces that act through the system boundary (a) (b) (c) W initial state Boundary Environment Eint.f final state ∆Eint = Eint.i process Q Eint.i = Q + W .

Specific heat ： The heat capacity per unit mass of a body C Q c= = m m∆T The heat capacity (C) is characteristic of a particular object. Q C= ∆T .Heat capacity and specific heat 1. Heat capacity C ： 2. but the specific heat (c) characterizes a kind of substance.

(23-10) Q = ∫ m ⋅ c(T ) ⋅ dT = m ∫ c(T )dT 3. Q Q n--. we obtain the “molar heat capacity”. Molar heat capacity If we multiply the specific heat by the molar mass M.the molar number cmol = M = m∆T n∆T .Usually both C and c depend on the temperature and condition under which the heat Q is added to the material.

the temperature of the sample does not rise. In this case. *4. Heats of Transformation (Latent heat) When heat enters a sample. the sample may change from one phase or state to another. Vice versa. Larger 3R .*Measured at room temperature and atmospheric pressure.

(23-28). ∆Eint Cv = = n∆T n∆T (23-31) Using Eqs(23-27).23-7 Heat capacities of an ideal gas 1. we have . Molar heat capacity at constant volume W =1 Constant = ∆Eint Q volume (23-30) Cv If represents the molar heat capacity at Q constant volume.(23-29).

1 C v = R = 1. Molar heat capacity at constant pressure P B Fig 23-19 shows two isotherms ∆T differing in the process.1 R 1 J Mol ⋅ K ( monatomic gas) ( diatomic gas ) ( polyatomic gas) } D V Rigid model 2. .1 1 J Mol ⋅ K 1 C v = 1 = 1.1 1 J Mol ⋅ K 1 1 C v = R = 1. C n is fixed in temperature by A Fig 23-19 .

P B Path AB is the constant-volume process. AC Along AB: Along AC: A V ∆Eint. AB = ∆Eint. AC = Q + W { W = − P∆V Q = nC P ∆T . Path AC is a constant pressure process. C The change in internal energy is the same for path AB and AC. AB = nCV ∆T ∆E int. ∆Eint.

Using the ideal gas law W = − P∆V = − nR∆T ∆Eint.1 1 J Mol ⋅ K 1 1 gas) R = 1. AC = nC P ∆T − nR∆T = nCV ∆T or C P = CV + R 1 C P = R = 1.1 R 1 J gas ) Mol ⋅ K .1 CP = 1J Mol ⋅ K 1 ( monatomic ( diatomic ( polyatomic C P = 1 = 1.

(W = 1 ) d ( PV ) = d (nRT ) PdV + VdP = nRdT (23-49) . Adiabatic process Q ( ) =1 Let’s derive: PV γ = const.23-8 Applications of the first law of thermodynamics (for ideal gases) 1. ∆Eint = ∆W dEint = dW = − PdV Q = 1  dEint can always be expressed as: PdV = −nCv dT PV = nRT dEint = nCv dT .

Take the ratio between Eqs(23-49) and PdV + nRdT R (23-48)VdP PdV = − nC v dT =− Cv CV + R CP VdP =− =− = −γ PdV Cv Cv ∫ Pf Pi V f dV dP = −γ ∫ Vi V P PiVi = Pf Vf γ γ dP dV = −γ P V Pf Vf ln = −γ ln Pi Vi Pf V f −γ ln = ln( ) Pi Vi (23-51) CP γ= Cv .

The container is insulated. In this process. so the process is adiabatic. and when the stopcock is opened. no work is done. . Free expansion insulating Stopcock The gas in Fig(23-22) is ( 隔离阀 ) initially in one side of the container. the gas expands into the previously Fig 23-22 evacuated half.5. gas vacu.

T and P do not have unique value. But the intermediate process during intial and final state is nonequilibrium. and we can not plot this process on a PV diagram. ) ∆Eint = 1 (∆T = 1 . as is the final state.W Hence = 1 Q = 1 (23-58) The initial state ( all gas on one side ) is an equilibrium state.

in. in.Heat engines and Reversible Work Piston stop Piston area = 10 sq.) . Gas (pressure = 100 lbs/sq.

Gas (pressure = 100 lbs/sq. in.Heat engines and Reversible Work Weight (1010 lbs) Piston stop Piston area = 10 sq. in.) .

any conditions sufficient for reversibility are also sufficient for equilibrium.Summary on reversible work  In a heat engine. maximum efficiency (maximum work) is achieved when the engine works reversibly. . thus the reversible work is equal to the maximum work.  It is accepted in thermodynamics that because there is no detectable difference between a system at equilibrium and one changing reversibly at an infinitesimal rate.  An engine (or process) doing reversible work stays close to equilibrium (a state so balanced that the smallest increment of change in the controlling variables (here gas pressure or load) will reverse the process. All physical changes that occur reversibly in a thermodynamic system do so in a nearequilibrium state.

Things that make processes irreversible: • friction • heat transfer • mass transfer • mixing. or frying an egg. is an example of a reversible process. . slowly enough that its temperature doesn't change. There aren't a lot of truly reversible processes around. Letting a gas expand v e r y s l o w l y in a chamber. blowing up a stick of dynamite. An irreversible process would be burning a piece of paper.Physicists classify processes as reversible and irreversible.

in this case by a series of pistons. .Thermodynam ic system Typical thermodynamic system. showing input from a heat source (boiler) on the left and output to a heat sink (condenser) on the right. Work is extracted.

and discards the rest. Thanks to Dr.Thermodynamics: Heat Engines An engine is a device which converts energy into mechanical force or motion. converts some of it to useful work. . Bieniek for the picture. A heat engine takes energy in the form of heat.

.The first law of thermodynamics says. (We will see later that the second law puts even lower limits on maximum machine efficiency. that you can't make a machine which creates more work than the energy you input into it. Sorry. You can’t get more work out than you put energy in. It says that no machine can be more than 100% efficient. for example. You really can't get something for nothing.) Another name for a machine which creates energy is a perpetual motion machine of the first kind.

Heat Engine Generalized Thermodynamic Engine Must be ∆T to get work done There is always loss of Heat to environment .

Qc W Qh − Qc E= = =1 − Q Qh Qh .

Work is transport of heat from put in to extract heat from hot to cold cold HOT WOut HOT WIn COLD COLD . Heat Pump Heat Engine extracts • Heat Pump is a Heat Engine work from the running backwards.Heat Engine vs.

A-B Isothermal expansion B-C Adiabatic (free) expansion C-D Isothermal Compression D-A Adiabatic Compression .Carnot Cycle Idealized repeatable cycle.

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Thermal Efficiency for an ideal Carnot Cycle Th − Tc Tc Efficiency = =1 − carnot Th Th .

Power Plant as Heat Engine .

any real engine will have other places where energy is lost (e. friction) so real engines have efficiencies lower than the theoretical best. or if the heat source (the steam) is at an infinite temperature.Notice that you can have an efficiency of 1 (100% efficient) only if the temperature of the heat sink (the river. Neither of these ideal cases is even remotely practical. Worse yet.g. TH e=1 TC heat in (TH) work done “waste” heat (TC) . in the case of the power plant) is at absolute zero.

. ..” The Laws of Thermodynamics: Entropy The second law of thermodynamics deals with entropy.” Next we will learn how the second law of thermodynamics says you can't even get equal amounts of “something” for “something.We have seen how the first law of thermodynamics says you can't get “something” for “nothing. Has anybody heard of entropy? Who can tell me what it is. so I had better talk about it for a minute.

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energy must be expended. entropy increases. at the cost of other regions of the universe in which order is decreased. If an event occurs spontaneously. If entropy is to be decreased. “What we did: worked …” Life is interesting in that it creates small regions of the universe in which order is increased. The greater the entropy of a system. .Entropy is the physicist's measure of disorder. the greater the disorder.

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RUDOLF_CLAUSIUS .

flows from Hot to Cold Heat Energy does NOT spontaneously flow from cold to hot .2nd Law of Thermodynamics Heat Energy. on its own.

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The Second Law essentially says that it is impossible to obtain a process where the unique effect is the subtraction of a positive heat from a reservoir and the production of a positive work. In this sense. and the ratio of heat to work will never equal 100% due to energy expanding away from its source. It moves away form its source. . In machine terms. energy or heat cannot flow form a colder body to a hotter body. Energy exhibits entropy. You cannot keep a continual flow of heat to work to heat to work without adding energy to the system. you have to add energy to get more work.

” .Statement of kelvin  “It is impossible to obtain a continious supply of work from a body by cooling it to a tempreture below the coldest of its surroundings.

g. Nonequilibrium conditions E. E.  Truly ideal behavior is rare. Nonideal behavior Classical thermodynamics Relies on simplifying assumptions that are sometimes violated. vapor pressure) that are directly proportional to their concentration.:  Compounds in solution have properties (e. but not how fast.  No impurities or surface films.g.Limitations of Thermodynamics Classical thermodynamics does not cope with: Dynamics (rates) Can tell you whether a process or reaction will occur.g.: A chemical reaction may proceed despite having a positive free energy if driven by the continual removal of the products .

This is important in applications such as the design of engines. .The Ideal Gas Law Thermodynamics is useful in understanding the behavior of gasses.

conclusion With these tools. materials science. chemical engineering. thermodynamics describes how systems respond to changes in their surroundings. aerospace engineering. mechanical engineering. cell biology. phase transitions. biomedical engineering. such as engines.  The results of thermodynamics are essential for other fields of physics and for chemistry. chemical reactions. . transport phenomena. This can be applied to a wide variety of topics in science and engineering. and even black holes.