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Thermodynamics

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

Sadi Carnot

Histroy of Thermodynamics
In physics, thermodynamics (from the Greek therme,

meaning "heat" and dynamics, meaning "power") is the study of the conversion of heat energy into different forms of energy (in particular, mechanical, chemical, and electrical energy); different energy conversions into heat energy; and its relation to macroscopic variables such as temperature, pressure and volume. Its underpinnings, 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. Roughly heat means "energy in transit" and dynamics relates to "movement Thus, in essence thermodynamics studies the movement of energy and how energy instils movement. Historically, thermodynamics developed out of need to increase the efficiency of early steam engines.

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

Definitions
A system is the object or material(s)

under study, separated from its surroundings by some specified boundary in essence, some collection of atoms. If neither matter nor energy crosses the boundary, it is an isolated system. If only energy crosses the boundary, it is a closed system. If both energy and material cross the boundary, it is an open system.

Definitions (2)
Work force applied over a distance against a load (e.g. footpounds, or Newton-meters = joules) Power Work per unit time (E.g., 1 hp lifts 33,000 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. Experiments have shown that every material has a characteristic heat capacity per gram, 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

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

Thermodynamic systems

An important concept in thermodynamics is the system. Everything in the universe except the system is known as surroundings. A system is the region of the universe under study. 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. The possible exchanges of work, heat, or matter between the system and the surroundings take place across this boundary

(1889-1944)

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

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

Work done BY a gas


Work is Energy. Heat is Energy

( mv2av) = (3/2)kBT W = Fy = PA y =P V Raise piston, lift weight. Now the gas has less Energy in it. Work done by the gas = Area under the

Path Does Matter

Work is Area under the Curve. For a repeatable process, must return to

initial state.

23-5 Work done on or by an ideal gas


1. Work done on an ideal gas

p ideal gas x (a)

Fx

v1

v1

W = P V

(b)

dW = P(V) dV W = P(V) dV
vi vf

Work done on gas in a more general form:

W = PdV
(a) If PV relationship is known, 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.

P B A D C
Two paths: A B D A C D

vi

vf V

W = PdV
2. Several typical thermal processes

(a). Work done at constant volume (V is const.) p p vf W 0 W = 1 (23-16) W=0


(b). Work done at constant pressure (P is const.)

vi v

vi = v f v

W = P(V)dV = (23-17) P dV = P(v f vi ) = P V


(c). Work done at constant temperature (T is const.) namely isothermal process,

p
vi
vf v

PV = constant

(d). Work done in thermal isolation Thermal isolation is also called adiabatic process. Q=0. T can be changed. PV = const. (23-19) P

( = 1 ~ 1 .1 .1
If we know , and the initial

pv = const.
pv = const.

Pi
Pf

Pi ,Vi

, we have

PV = PiVi = constant

vi

vf

Fig 23-16

We can now find the adiabatic work:

PiVi P= V

W = - PdV PV dV = i i dV = PiVi Vi V V PiVi PV V 1 1 = (Vi V f ) = i i [( i ) 1 1 ] 1 1 Vf


Vf

By further using

1 W= ( Pf V f PiVi ) 1

PiVi = Pf V f

(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=mcT 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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au e se par rgy (Hea d b tic i t R y d les s car Ris en (air rie es. en adi d s erg at ma ion ity ch, wate by ter y an an r ial d c (ph ge , etc ) oll s) . ide oton wit s ca h o rry the r

What is Temperature
Temperature is a

measure of the kinetic energy of matter. Collision between molecules causes energy transfer Motion of molecules causes pressure (collisions with container). KE = (mv2)av = 3/2 kBT

Zero Degrees
Absolute Zero (Kelvin Scale)

(-273.15 oC) No motion of molecules Pressure is Zero.

T related to energy.

No motion =No Energy =No Temperature


0 Celcius is pretty HOT = 273 Kelvin

Cant really get to zero Kelvin. milliKelvin is easy, any more is hard (Noble Prize awarded for laser cooling) Deep Space is about 3K

The internal energy of an ideal gases


1. Internal energy of ideal monatomic gas Translational kinetic energy is 1

K trans =

KT 1

No potential energy. No rotational kinetic energy. So is the entire store of internal 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

2. Internal energy of molecule consisting of twoO N , CO particles 1 1 , such as

y
d

Fig 23-18

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 x + I y y 1 1 1 1 1
U=0 Etot=K

5. 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,
also oscillating degrees of freedom.

1 1 Eint = N ( KT ) = nRT 1 1

E Notes: 1* int here dependents only on T and degree of 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

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

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, but exists forever

The first law of thermodynamics

1.For a thermodynamic system, internal energy is the only type of energy the system may have. 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

(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,i

process

Q
Eint,f

final state

Eint = Eint, f Eint,i = Q + W

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

Q C= T

Usually both C and c depend on the temperature and condition under which the heat Q is added to the material. (23-10) Q = m c(T ) dT = m c(T )dT

3. Molar heat capacity


If we multiply the specific heat by the molar mass M, we obtain the molar heat capacity. Q Q n--- the molar number cmol = M = mT nT

*Measured at room temperature and atmospheric pressure.


*4. Heats of Transformation (Latent heat)

When heat enters a sample, the sample may change from one phase or state to another. In this case, the temperature of the sample does not rise. Vice versa.

Larger 3R

23-7 Heat capacities of an ideal gas


1. 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, Eint Cv = = nT nT (23-31) Using Eqs(23-27),(23-28),(23-29), we have

1 C v = R = 1.1 1 J Mol K 1 1 C v = R = 1.1 1 J Mol K 1 C v = 1 = 1.1 R 1 J Mol K

( monatomic gas)

( diatomic gas ) ( polyatomic gas)

}
D
V

Rigid model

2. Molar heat capacity at constant pressure P B Fig 23-19 shows two isotherms T differing in the process. . C n is fixed in temperature by
A Fig 23-19

P B Path AB is the constant-volume process; Path AC is a constant pressure process. C

The change in internal energy is the same for path AB and AC. Eint, AB = Eint, AC
Along AB: Along AC:

Eint, AB = nCV T

E int, AC = Q + W

{ W = PV
Q = nC P T

Using the ideal gas law


W = PV = nRT
Eint, AC = nC P T nRT = nCV T

or

C P = CV + R

1 C P = R = 1.1 1 J Mol K 1 1 gas) R = 1.1 CP = 1J Mol K 1

( monatomic ( diatomic ( polyatomic

C P = 1 = 1.1 R 1 J

gas )

Mol K

23-8 Applications of the first law of thermodynamics


(for ideal gases) 1. Adiabatic process Q ( ) =1

Lets derive:

PV = const.
Eint = W dEint = dW = PdV

Q = 1

dEint can always be expressed as:

PdV = nCv dT
PV = nRT

dEint = nCv dT , (W = 1 )

d ( PV ) = d (nRT ) PdV + VdP = nRdT

(23-49)

Take the ratio between Eqs(23-49) and PdV + nRdT R (23-48)VdP


PdV = nC v dT = Cv
CV + R CP VdP = = = PdV Cv Cv

Pf

Pi

V f dV dP = Vi V P

PiVi = Pf Vf

dP dV = P V Pf Vf ln = ln Pi Vi Pf V f ln = ln( ) Pi Vi (23-51) CP = Cv

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

W Hence = 1 Q = 1

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

) Eint = 1 (T = 1

Heat engines and Reversible Work

Piston stop

Piston
area = 10 sq. in.

Gas
(pressure = 100 lbs/sq. in.)

Heat engines and Reversible Work


Weight
(1010 lbs)

Piston stop

Piston
area = 10 sq. in.

Gas
(pressure = 100 lbs/sq. in.)

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. 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. 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, any conditions sufficient for reversibility are also sufficient for equilibrium.

Physicists classify processes as reversible and irreversible. Things that make processes irreversible: friction heat transfer mass transfer mixing.

An irreversible process would be burning a piece of paper, blowing up a stick of dynamite, or frying an egg. 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, slowly enough that its temperature doesn't change, is an example of a reversible process.

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, in this case by a series of pistons.

Thermodynamics: Heat Engines


An engine is a device which converts energy into mechanical force or motion.

A heat engine takes energy in the form of heat, converts some of it to useful work, and discards the rest.

Thanks to Dr. Bieniek for the picture.

The first law of thermodynamics says, for example, that you can't make a machine which creates more work than the energy you input into it.

It says that no machine can be more than 100% efficient. (We will see later that the second law puts even lower limits on maximum machine efficiency.)

Another name for a machine which creates energy is a perpetual motion machine of the first kind.

You cant get more work out than you put energy in. You really can't get something for nothing. Sorry.

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

Heat Engine vs. Heat Pump


Heat Engine extracts

Heat Pump is a Heat Engine work from the running backwards. Work is transport of heat from put in to extract heat from hot to cold cold

HOT
WOut

HOT
WIn

COLD

COLD

Carnot Cycle

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

Thermal Efficiency for an ideal Carnot Cycle


Th Tc Tc Efficiency = =1 carnot Th Th

Power Plant as Heat Engine

Notice that you can have an efficiency of 1 (100% efficient) only if the temperature of the heat sink (the river, in the case of the power plant) is at absolute zero, or if the heat source (the steam) is at an infinite temperature. Neither of these ideal cases is even remotely practical.

Worse yet, any real engine will have other places where energy is lost (e.g. friction) so real engines have efficiencies lower than the theoretical best.

TH e=1 TC
heat in (TH)

work done waste heat (TC)

We have seen how the first law of thermodynamics says you can't get something for nothing. Next we will learn how the second law of thermodynamics says you can't even get equal amounts of something for something.

The Laws of Thermodynamics: Entropy


The second law of thermodynamics deals with entropy, so I had better talk about it for a minute. Has anybody heard of entropy? Who can tell me what it is...

Entropy is the physicist's measure of disorder. The greater the entropy of a system, the greater the disorder. If an event occurs spontaneously, entropy increases. If entropy is to be decreased, energy must be expended.

What we did: worked

Life is interesting in that it creates small regions of the universe in which order is increased, at the cost of other regions of the universe in which order is decreased.

RUDOLF_CLAUSIUS

2nd Law of Thermodynamics


Heat Energy, on its own, flows from Hot to

Cold
Heat Energy does NOT spontaneously flow

from cold to hot

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. Energy exhibits entropy. It moves away form its source. In this sense, energy or heat cannot flow form a colder body to a hotter body. You cannot keep a continual flow of heat to work to heat to work without adding energy to the system. In machine terms, you have to add energy to get more work, and the ratio of heat to work will never equal 100% due to energy expanding away from its source.

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.

Limitations of Thermodynamics
Classical thermodynamics does not cope with: Dynamics (rates)
Can tell you whether a process or reaction will occur, but not how fast.

Nonideal behavior
Classical thermodynamics Relies on simplifying assumptions that are sometimes violated. E.g.: Compounds in solution have properties (e.g. vapor pressure) that are directly proportional to their concentration. No impurities or surface films.

Truly ideal behavior is rare.

Nonequilibrium conditions
E.g.: A chemical reaction may proceed despite having a positive free energy if driven by the continual removal of the products

The Ideal Gas Law


Thermodynamics is useful in understanding the

behavior of gasses. This is important in applications such as the design of engines.

conclusion
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, aerospace engineering, mechanical engineering, cell biology, biomedical engineering, materials science,

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