Thermodynamics

The First Law of Thermodynamics Thermodynamic Thermodynamic Processes (isobaric, isochoric, isothermal, adiabatic) Reversible and Irreversible Processes Heat Engines Refrigerators and Heat Pumps The Carnot Cycle Entropy (The Second Law of Thermodynamics) The Third Law of Thermodynamics

The Zeroth Law of Thermodynamics

If A is in thermal equilibrium with C and B in th thermal l equilibrium ilib i with ith C then A and B have to be in thermal equilibrium. q No heat flows!

Internal Energy
From http://en.wikipedia.org/wiki/Internal_energy.........

In thermodynamics, thermodynamics the internal energy of a thermodynamic system, or a body with well-defined boundaries, denoted by U, or sometimes E, is the total of the kinetic energy due to the motion of molecules (translational, rotational, vibrational) and the potential energy associated with the vibrational and electric energy of atoms within molecules or crystals. It includes the energy in all the chemical bonds, and the energy of the free conduction electrons in metals. free, metals

TheFirstLawofThermodynamics
The first law of thermodynamics says the change in internal energy of a system is equal to the heat flow into the system plus the work done on the system.

U = Q W

First Law of Thermodynamics The change in a systems internal energy is related to the heat and the work work. U=Uf Ui =Q W
Where: Uf =internalenergyofsystem@end Ui =internal i lenergyof fsystem@start Q=netthermalenergyflowinginto y during gp process system Positivewhensystemgainsheat Negativewhensystemlosesheat W=networkdoneby thesystem Positive whenworkdonebythesystem Negativewhenworkdoneon thesystem

ThermodynamicProcesses
A state variable describes the state of a system at time t, but it does not reveal how the system was put into that state. Examples of state variables: pressure, temperature, volume, number of moles, and internal energy. Thermal processes can change the state of a system. We assume that thermal processes have no friction or other dissipative forces. In other words: All processes are reversible (Reversible means that it is possible to return system and surroundings to the initial states) REALITY: irreversible
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Humpty Dumpty sat on a wall wall. Humpty Dumpty had a great fall All the kings horses and all the kings men Couldnt Couldn t put Humpty Dumpty together again again
* Martin Schullinger-Krause (PH202 Winter 2008) 7

A PV diagram g can be used to represent p the state changes g of a system, provided the system is always near equilibrium.

The area under a PV curve gives the magnitude of the work done on a system. W<0 for compression p and W>0 for expansion.

To go from the state (Vi, Pi) by the path (a) to the state (Vf, Pf) requires a different amount of work then by path (b). To return to the initial point (1) requires the work to be nonzero.

The work done on a system depends on the path taken in the PV diagram. The work done on a system during a closed cycle can be nonzero nonzero.
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An isothermal process implies p that both P and V of the gas change (PVT).

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Specific Heats under constant pressure and constant volume Specific heat Q = m c T For a gas we use Molar specific heat Q = n C T Constant Volume: CV Constant Pressure : CP

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ThermodynamicProcessesforanIdealGas
No work is done on a system when its volume remains constant (isochoric process). For an ideal gas (provided the number of moles remains U constant), = Q W = Q 0 the change in internal Q = U = n C T energy is
V

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For o a co constant sa p pressure essu e ( (isobaric) soba c) p process, ocess, the ec change a ge in internal energy is

U = Q W
where

W = PV = nRT

and Q = nC P T .

CP is the molar specific heat at constant pressure. For an ideal gas CP = CV+R.

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For a constant temperature (isothermal) process, U = 0 and the work done on an ideal gas is

Vf Vf W = NkT ln = nRT ln V V . i i U = 0 Q = W

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We have found for a monoatomic gas U = 3/2 n R T Constant volume: 3/2 n R T = n CV T Constant pressure: U= Q CV= 3/2 R Q = U + W

n CP T = 3/2 n R T + n R T CP= 5/2 R CV CP = R (always valid for any ideal gas)

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Adiabatic (not passable) processes

(no heat is gained or lost by the system Q Q=0 0, i i.e. e system perfectly isolated )

Q=0 and so U= -W

P V = constant (isothermal) P V = constant (adiabatic) = CP/CV For a monoatomic gas therefore = 5/3

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Example: An ideal gas is in contact with a heat reservoir so that it remains at constant temperature of 300 300.0 0K K. The gas is compressed from a volume of 24.0 L to a volume of 14.0 L. During the process, the mechanical device pushing the piston i t t to compress the th gas is i f found dt to expend d5 5.00 00 kJ of f energy. How many moles of the ideal gas are in the system? How much heat flows between the heat reservoir and the gas, and in what direction does the heat flow occur?
Vf W = nRT RT ln( ) n = Vi W Vf RT ln( ) Vi = 5000 J = 3.7 mol l 8.31 ln(14 / 24)

This is an isothermal process, so U = Q - W = 0 (for an ideal gas) and W = Q = - 5.00 5 00 kJ kJ. Heat flows from the gas to the reservoir.
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An ice cube placed on a countertop in a warm room will melt The reverse process cannot occur: an ice cube will melt. not form out of the puddle of water on the countertop in a warm room.

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Any process that involves dissipation of energy is not reversible. Any process that involves heat transfer from a hotter object to a colder object is not reversible.

The second law of thermodynamics (Clausius Statement): Heat never flows spontaneously from a colder body to a hotter body.
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HeatEngines
A heat engine is a device designed to convert disordered energy into i ordered d d energy. The net work y an engine g done by during one cycle is equal to the net heat flow into the engine during the cycle (U= 0).

W net = Qnet
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The efficiency of an engine is defined as

net work done by the engine Wnet e= = heat input QH

(e.g. a efficiency of e=0.8 means 80% of the heat is converted to mechanical work)

Note: Qnet = Qin - Qout

Wnet net e work wo ou output pu e= = QH heat input QH QC QC = = 1 . QH QH

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RefrigeratorsandHeatPumps
Here, heat flows from cold to hot but with work as the input. Pump

Refrigerator

K = Coefficient of performance
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ReversibleEnginesandHeatPumps
A reversible engine can be used as an engine g ( (heat input from a hot reservoir and exhausted to a cold reservoir) or as a heat pump (heat is taken from cold reservoir and exhausted h t dt to a h hot t reservoir).

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From the second law of thermodynamics, no engine can have an efficiency yg greater than that of an ideal reversible engine Carnot engine that uses the same two reservoirs. The efficiency of this ideal reversible engine is

TC er = 1 . TH

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DetailsoftheCarnotCycle
The ideal engine of the previous section is known as a Carnot engine. engine The Carnot cycle has four steps: 1. Isothermal expansion: takes in heat from hot reservoir; keeping the gas temperature at TH. 2. Adiabatic expansion: the gas does work without heat flow into the gas; gas temperature decreases to TC. 3 Isothermal 3. I h l compression: i H Heat QC is i exhausted; h d gas temperature remains at TC. 4 Adiabatic compression: raises the temperature back to 4. TH.

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The Carnot engine model was graphically expanded upon by Benoit Paul mile Clapeyron p y in 1834 and mathematically elaborated upon by Rudolf Clausius in the 18 0 and 1850s d 60s 60 from which the concept p of entropy emerged

The Carnot cycle illustrated

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The Otto cycle

Its power cycle consists of adiabatic compression heat addition at constant compression, volume, adiabatic expansion and rejection of heat at constant volume and characterized by four strokes, or reciprocating movements of a piston in a cylinder: intake/induction stroke compression stroke power stroke exhaust stroke

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Entropy
Heat flows from objects of high temperature to objects at low temperature because this process increases the disorder of f the system. Entropy is a measure of f a systems disorder. Entropy is a state variable.

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If an amount of heat Q flows into a system at constant temperature, then the change in entropy is

Q S = . T
Every irreversible E i ibl process i increases th the t total t l entropy t of f th the universe. Reversible processes do not increase the total entropy of the universe.

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The second Th d law l of f thermodynamics th d i (Entropy Statement): The entropy of the universe never decreases.

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Example: An ice cube at 0.0 C is slowly melting. What is the change in the ice cubes entropy for each 1.00 g of ice that melts? To melt ice requires Q = mLf joules of heat. To melt one gram of ice requires 333 333.7 7 J of energy energy. The entropy change is

Q 333.7 J S = = = 1.22 J/K. T 273 K

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300K Q 5K

Q 300 J S hot = = 1 J/K. h t = T 300 K Q + 300 J S cold = = = 60 J/K. T 5K

htt // http://www.youtube.com/watch?v=Xa6Pctf23tQ t b / t h? X 6P tf23tQ

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StatisticalInterpretationofEntropy

A microstate specifies the state of each constituent particle in a thermodynamic y system. y A macrostate is determined by the values of the thermodynamic state variables.

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probability of a macrostate =

number of microstates corresponding to the macrostate total number of microstates for all possible macrostates

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The number of microstates for a g given macrostate is related to the entropy.

S = k ln

where is the number of microstates.

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TheThirdLawofThermodynamics

It is impossible to cool a system to absolute zero.

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