## Are you sure?

This action might not be possible to undo. Are you sure you want to continue?

Laws of Thermodynamics

Classical thermodynamics is the branch of physics concerned with heat and

related thermal phenomena. It was well established by the middle of the nine-

teenth century. Statistical mechanics is a theoretical branch of physics that

provides an interpretation of thermodynamics in terms of a combination of mi-

croscopic physics and statistical concepts; it was ﬁrst being developed in the

middle of the nineteenth, with the major advances early in the twentieth cen-

tury.

1.1 Classical thermodynamics

Thermodynamics is a phenomenological branch of physics: it is a summary

of the properties that real physical systems exhibit. The early history of the

ﬁeld revolved around the nature of heat, and the relation between heat and

temperature. Following the experimental work of Joule it became accepted that

heat is a form of energy, and this is the starting point for our discussion in the

form of the ﬁrst law of thermodynamics.

Another ingredient in early ideas on thermodynamics concerned perpetual

motion machines. Nobody was ever able to make a perpetual motion machine

operate on its own, but why? It was realized that one class of suggested per-

petual motion machines violated the ﬁrst law of thermodynamics, that is, they

involved creating energy out of nothing. Hence, this class could be dismissed

as impossible by postulating that heat is a form of energy and that energy is

conserved. However, there was a second class of suggested perpetual motion ma-

chines which didn’t work but which were consistent with energy conservation.

Another law of thermodynamics was introduced to summarize the fact that this

class of perpetual motion machines also does not work. This is the second law of

thermodynamics, which expresses the observational fact that certain processes

that are allowed by the ﬁrst law of thermodynamics never happen. The second

1

law can be expressed in terms of a new thermodynamic variable called entropy.

One statement of the second law is that in any physical process the total entropy

never decreases.

For example, if we drop a red hot cannon ball into a bucket of cold water,

we end up with a bucket of warm water and a warm cannon ball. However, if

we start from a bucket of warm water and a warm cannon ball we never observe

the cannon ball jumping out red hot leaving a bucket of cold water. Such

processes always go in one direction: heat ﬂows from hotter to colder bodies.

The explanation based on the second law is that the entropy of the bucket of

warm water and the warm cannon ball is higher than the entropy of the bucket

of cold water and the red hot cannon ball, and the second law requires that no

process lead to a net decrease in entropy.

There are certain processes that are reversible, and for these the entropy

does not change. That is, reversible processes occur at constant entropy.

The concept of entropy is a subtle one in classical thermodynamics. It has

a relatively simple interpretation in statistical mechanics: entropy is a measure

of randomness, and the Universe evloves from a more ordered to a less ordered

state.

There are certain systems that superﬁcially appear to violate the second

law of thermodynamics. One class involves self gravitating systems: interstellar

gas clouds collapse to form stars; also the galaxies must have formed from a

much more uniform distribution of matter in the early epoch of the Universe.

In these systems, highly structured systems develop from essentially uniformly

distributed matter. Biological systems also evolve from simpler to more complex

structures. However, a more careful examination shows that in both cases the

total entropy increases as these systems evolve.

Physical quantities

The laws of thermodynamics force us to deﬁne certain physical variables and to

quantify them. The basic thermodynamic variables are heat, temperature and

entropy. There are other variable that we can use to describe a system. Suppose

for example that the system is the air in this room. We can do measurements

to determine the volume of the system, the pressure that the air exerts, the

density of the air, the chemical composition of the air, and so on. We are

familiar with the concept of the temperature of the air, which we measure with

a thermometer. However, the heat in the air and the entropy of the air are

not familiar. Nevertheless, all these are examples of physical quantities that

describe our system.

A formal deﬁnition of a physical quantity is:

A physical quantity is deﬁned by the sequence of operations used to determine

its value.

This sequence of operations will often include calculations as well as measure-

ments.

2

A physical law can now be deﬁned:

A physical law is a relation involving physical quantities that is found to be

satisﬁed by physical systems under speciﬁed conditions.

Some physical laws are very simple. For example, measuring a mass using a scale

deﬁnes a physical quantity, and measuring mass using a spring balance deﬁnes

another physical quantity. A simple physical law is that these two types of mass

are the same thing: this law implies that these are two diﬀerent but equivalent

ways of measuring the same physical quantity (mass). A related physical law,

with more profound consequences, is that inertial mass and gravitational mass

are equal.

In thermodynamics we are concerned with thermodynamic systems, with the

air in this room being one illustrative example of a thermodynamic system. A

somewhat better example is the air inside a balloon. This system is characterized

by its volume, pressure, temperature and density. Another feature concerns the

transport of heat across the surface of the balloon. If no heat is allowed to cross

the surface (the balloon is made of thermally insulating material that allows no

heat conduction), we say that the system is (thermally) isolated and the changes

are then said to be adiabatic.

1.2 The laws of thermodynamics

After the ﬁrst and second laws of thermodynamics had been recognized and

thermodynamics was becoming a more formal subject, it was realized that there

was no consistent deﬁnition of temperature. A zeroth law of thermodynamics

was added to rectify this. Later still, a third law of thermodynamics was added

to summarize the observed properties of matter at extremely low temperatures.

Zeroth Law: If two systems are in thermal equilibrium with a third system,

then they are in equilibrium with each other.

The zeroth law allows one to order systems according to the direction heat ﬂows

when two systems are put into thermal contact. One system is said to be hotter

than another if heat ﬂows from the former to the latter when they are put into

thermal contact. This allows one to introduce a parameter, called an empirical

temperature, which is the same for all bodies that are in thermal equilibrium

with each other. This is done by constructing one system, called a thermometer,

that allows one to ascribe a number to the temperature, e.g., the height of a

colored liquid in a glass tube.

First Law: Heat is a form of energy, and energy is conserved.

The idea behind the ﬁrst law is familiar to any thinking person in the modern

world. We pay for energy, in the form of electricity, gas, oil, etc., which we use for

heating, and we know that the amount of heat that we get is proportional to the

amount of energy that we pay for. Heat is said to be generated by doing work on

the system. The simplest example is the work done by a mechanical force: the

3

work is then the force times the displacement. In simple thermodynamic systems

this appears with the force being identiﬁed as the pressure (= force per unit area)

and the displacement being identiﬁed as the change in volume (= displacement

of a surface area times that area). Another example of work iinvolves electricity:

the force is then identiﬁed as the EMF (= electrical potential diﬀerence) and

displacement as the charge transferred (= electrical current × time). Other

force-displacement pairs that will appear in this course include surface tension

and surface ares, and the chemical potential and chemical concentration.

Second Law: There are several diﬀerent ways of expressing the second law of

thermodynamics, and the following are three examples.

Clausius’ principle: No cyclic process exists which has as its sole eﬀect the trans-

ference of heat from a colder body to a hotter body.

Kelvin’s principle: No cyclic process exists which produces no other eﬀect than

the extraction of heat from a body and its conversion into an equivalent amount

of work.

Carath´eodory’s principle: There are states of a system, diﬀering inﬁnitesimally

from a given state, which are unattainable from that state by any quasi-static

adiabatic process.

The second law (especially in the Carath´eodory form) allows one to order the

states according to the direction that the system is allowed to evolve. A pa-

rameter, called an empirical entropy, is ascribed to each state, such that this

parameter never decreases spontaneously. In the absence of external agents do-

ing work on the system, any change in the system is either reversible, which

involves no change in entropy, or irreversible, which involves an increase in en-

tropy.

The bucket of warm water with the warm cannon ball has a higher entropy

than the bucket of cold water and the red hot cannon ball, so that the evolution

is irreversible and can go in only one direction. To reverse the change we need

to do work on the system: mechanical work to lift the cannon ball, and ther-

modynamic work, using some form of refrigerator to decrease the temperature

of the bucket of water, and some other process to heat the cannon ball.

Third Law:

The entropy of a system approaches a constant value as the temperature ap-

proaches absolute zero.

The third law is relatively easy to understand from a statistical point of view

in which entropy is associated with disorder. As absolute zero is approached,

all thermal motions cease, and any system must approach an ordered state in

which the particles do not move. Hence, the entropy of a system is deﬁned

only to within an arbitrary constant, and only changes in entropy have physical

signiﬁcance. The changes in entropy become negligibly small as absolute zero

is approached.

4

1.3 Thermodynamic variables

To describe these ideas quantitatively we need to introduce thermodynamic

variables and state functions. For the present let the pressure, P, be the only

force that we consider. Then an inﬁnitesimal change in the volume, dV , implies

an inﬁnitesimal amount of work done on the system, dW = −PdV . Note the

sign: a positive change dV implies that the system expands a little, and hence

that the system does work against the external pressure force (P is always

positive), so that with dW deﬁned as the work done on the system, we need

a minus sign. Let dQ be the amount of heat added to the system. Let U be

the internal energy of the system. Then the ﬁrst law requires conservation of

energy, which is expressed through the relation dU = dQ +dW = dQ−PdV .

The absolute temperature and the metrical entropy

The ﬁrst law enables one to deﬁne an empirical temperature and the second

law allows one to deﬁne an empirical entropy. What this means is that the

laws allow us to order states with parameters t and s. Consider two states of

a system labeled 1 and 2, with parameters t

1

, s

1

and t

2

, s

2

, respectively. For

t

1

> t

2

we say that state 1 is hotter than state 2. The observational fact is that

if the system is brought into thermal contact with some other system so that

heat can be added or taken away from our system, then heat is required to ﬂow

out the system to get from state 1 to state 2, and heat is required to ﬂow into

the system to get from state 2 to state 1. For s

1

> s

2

it is possible for state

2 to evolve into state 1 without any work being done on the system, but it is

impossible for state 1 to evolve into state 2.

The temperature that we are familiar with is the Celsius scale, which diﬀers

from the absolute temperature (Kelvin) scale, by 273.15 K. That is, absolute

zero is −273.15

◦

C. The unit of the absolute temperature scale is the kelvin,

denoted K. The existence of the absolute temperature scale involves a rather

subtle argument, which can be summarized as follows.

Consider the heat, Q, transferred to the system in some irreversible change

(this is, found by integrating the elements dQ over a range of inﬁnitesimal

changes). The zeroth and second laws imply that Q = Q(t, s) is some function

of t and s. For a reversible change we know that s does not change, and a

reversible change corresponds to no transfer of heat. Hence for a reversible

change we have dQ = 0 and ds = 0. Now consider an irreversible change,

ds = 0. In an irreversible change we have dQ = λds, where λ = λ(t, s) is some

function of the empirical temperature and the empirical entropy. The subtle

argument implies λ(t, s) is of the form λ(t, s) = T(t)φ(s), that is, that λ(t, s)

depends on t and s only in the form of a product of a function, T(t), of t and

a function, φ(s), of s. The argument involves imagining splitting the system

into two parts, labeled A and B say. (Imagine splitting the system consisting

of the air in the room into two parts corresponding to the air in two halves of

5

the room.) Each of these parts is a thermodynamic system in itself, and hence

we have dQ

A

= λ

A

ds

A

, dQ

B

= λ

B

ds

B

, with Q

A

, λ

A

functions of t

A

, s

A

and

Q

B

, λ

B

functions t

B

, s

B

. The amount of heat is additive, so that we have

dQ = dQ

A

+dQ

B

. The empirical temperature of the two halves is the same, so

that we have t

A

= t

B

= t. The total empirical entropy s depends on s

A

, s

B

and

t. One can satisfy these diﬀerential relations only if the dependences of λ, λ

A

and

λ

B

on t are all of the same functional form, a function T(t) say. It then follows

that if one writes λ(t, s) = T(t)φ(s), λ

A

(t, s) = T(t)φ

A

(s), λ

B

(t, s) = T(t)φ

B

(s)

and S(s) =

_

ds φ(s), S

A

(s

A

) =

_

ds

A

φ

A

(s

A

), S

B

(s

B

) =

_

ds

B

φ

B

(s

B

), one

has dS = dS

A

+ dS

B

. The function T(t) is the absolute temperature, and the

function S(s) is the metrical entropy.

From now on by temperature and entropy we mean the speciﬁc functions T

and S, respectively. One then has dQ = TdS. The combined ﬁrst and second

laws of thermodynamics now imply that in an inﬁnitesimal change, the internal

energy, U, of a system changes according to

dU = TdS −PdV. (1.1)

Dependent and independent variables

The variables in our thermodynamic relations appear in pairs: P, V and T, S

in the case considered so far. One of each pair is chosen as the independent

variable. According to (1.1) the variables we are allowing to change are V and

S, which are therefore identiﬁed as the independent variables. The other two

variables, P and T, are then the dependent variables, in the sense that they

should be regarded as functions of S, V in (1.1). Speciﬁcally, the relation (1.1)

determines the change in the internal energy when the independent variables S

and T are changed. By implication, U = U(S, V ), is a function of these two

variables.

The internal energy is an example of a state function. If we know U(S, V )

as a function of S and V , then we know everything there is to know about the

system from a thermodynamic viewpoint. Noting that we have

dU =

_

∂U

∂S

_

V

dS +

_

∂U

∂V

_

S

dV, (1.2)

comparison of (1.1) and (1.2) implies

T =

_

∂U

∂S

_

V

, P = −

_

∂U

∂V

_

S

. (1.3)

That is, given the state function U(S, V ) we may ﬁnd the dependent variables

T and P as functions of the independent variables S and V using (1.3).

Also we can classify variables as intrinsic, which do not depend on the

amount of the system, or extrinsic, which are proportional to the amount of

the system. The variables P, T are intrinsic and V , S are extrinsic.

6

1.4 Speciﬁc heats and expansion coeﬃcients

The way a system responds to changes in variables is described in terms of

various coeﬃcients that are derived by partial diﬀerentiation of the appropriate

state function.

Consider how the energy of a system changes as heat is added to it. An

element of heat is dQ = TdS. The eﬀect of adding heat is diﬀerent if one does

so at constant volume or at constant pressure. At constant volume no work is

done, but this is not so at constant pressure. The speciﬁc heats at constant

volume and at constant pressure are deﬁned by

c

V

= T

_

∂S

∂T

_

V

, c

P

= T

_

∂S

∂T

_

P

, (1.4)

respectively.

The coeﬃcient of thermal expansion is deﬁned by

β =

1

V

_

∂V

∂T

_

P

. (1.5)

Another coeﬃcient is that of isothermal compressibility:

κ = −

1

V

_

∂V

∂P

_

T

. (1.6)

1.5 The equation of state

Any speciﬁc thermodynamic system may be described by an equation of state,

which is some functional relation between the P, V and T. We may write the

equation of state in the form

f(P, V, T) = 0, (1.7)

where the function f depends on the particular system.

The simplest system is an ideal gas. In this case the equation of state is

PV = NkT, (1.8)

where N is the number of particles and k is Boltzmann’s constant. Another

example of an equation of state is for a van der Waal’s gas:

_

P +

a

v

2

_

(v −b) = RT, (1.9)

where a and b are constants, v = V N

0

/N is the molar speciﬁc volume, R = N

0

k

is the gas constant, and N

0

is Avagadro’s number. The equation of state (1.9)

reduces to (1.8) for a = 0, b = 0.

7

Appendix A: Rules of Partial Diﬀerentiation

1). Let f(x, y, z) be any diﬀerentiable function. Then one has

df =

_

∂f

∂x

_

y,z

dx +

_

∂f

∂y

_

x,z

dy +

_

∂f

∂z

_

x,y

dz. (A.1)

The order of diﬀerentiation is reversible:

_

∂

∂y

_

∂f

∂x

_

y,z

_

x,z

=

_

∂

∂x

_

∂f

∂y

_

x,z

_

y,z

. (A.2)

2). Let there be a relation f(x, y, z) = 0 that can be solved for x = x(y, z),

y = y(x, z) or z = z(x, y). Then the partial derivative of the ﬁrst of these

functions with respect to y at ﬁxed z is related to the partial derivative of the

second with respect to x at ﬁxed z by

_

∂x

∂y

_

z

_

∂y

∂x

_

z

= 1. (A.3)

The partial derivatives also satisfy the chain rule

_

∂x

∂y

_

z

_

∂y

∂z

_

x

_

∂z

∂x

_

y

= −1. (A.4)

3). Let f(x, y) be a function of x and y with y = y(x, z) a function of x and a

third variable, z. Then f = f

_

x, y(x, z)

_

may also be regarded as a function of

x and z. One has

df =

_

∂f

∂x

_

y

dx +

_

∂f

∂y

_

x

dy, (A.5)

df =

_

∂f

∂x

_

z

dx +

_

∂f

∂z

_

x

dz, (A.6)

dy =

_

∂y

∂x

_

z

dx +

_

∂y

∂z

_

x

dz. (A.7)

On inserting (A.7) into (A.5) and comparing the result with (A.6), one ﬁnds

_

∂f

∂x

_

z

=

_

∂f

∂x

_

y

+

_

∂f

∂y

_

x

_

∂y

∂x

_

z

, (A.8)

_

∂f

∂z

_

x

=

_

∂f

∂y

_

x

_

∂y

∂z

_

x

. (A.9)

8

Exercise Set 1

1.1). The coeﬃcient of isothermal compressibility is

κ = −

1

V

_

∂V

∂P

_

T

, (E1.1)

and the coeﬃcient of thermal expansion is

β =

1

V

_

∂V

∂T

_

P

. (E1.2)

Show that for an ideal gas one has κ = 1/P, β = 1/T.

1.2). Repeat the calculations in the previous problem, but for a van der Waal’s

gas. Show that one has

κ =

v

2

(v −b)

2

RTv

3

−2a(v −b)

2

, β =

Rv

2

(v −b)

RTv

3

−2a(v −b)

2

. (E1.3)

9

- L8 Entropydaniceuy
- T D AssignmentVineet K. Mishra
- Thermodynamics dnotesatcrooks
- Entropy and the Second Lawkumar
- Mixture 04Rita E. Appiah
- B T D notesvikramviv
- chap1Dennis Alvaro Garcia Gutierrez
- 13.107 Engineering Thermodynamics (MPNSU)depakb016
- Assignment 12sruthis_8
- Carnot Cycle 2011 10 13Mazen Diab
- Basic Thermo 2sklux
- Chapter 3-Thermodynamics FinalSwapnil Rahane
- Thermocarlo manabat
- Chapter 3-thermodynamics final.docgsudhanta1604
- Basics of ThermodynamicsKaviArasu
- TERMODİNAMİK NOTLAR---notesAli Sener
- Chapter- 1 - Introduction _EME_A J Modiashishjmodi
- Lecture 03Rahul Bhatt
- 9A03302 Thermodynamicssivabharathamurthy
- Heat & Thermodynamicsdso
- A Thermodynamics History (1)Jaster Monloise Baña Sanico
- ThermodinamikaNella Sri Pujirahayu
- Thermo-Review_PENT.pdfDzuhri Ferianto
- 6kkprasannan
- Che 212 Lecture NoteSeun Akinsanya
- Module 1-1Parekh Deep
- ThermodynamicsShyam Sunder
- Hukum Termodinamikalele12
- Tong - Lectures on Statistical PhysicsNarmel
- Thermodynamics NotesShankara Subramanian

- A Review on LI-BR Water Absorption Systems Analysis Using Artificial Neural NetworkInternational Journal for Scientific Research and Development
- Tmp 1804Frontiers
- tmp9649.tmpFrontiers
- tmp8EE8.tmpFrontiers
- tmp2B1C.tmpFrontiers
- tmp6FE1Frontiers
- Tmp 6201Frontiers
- Entropy – Why the World as Wezerohedge
- tmpD7C3Frontiers
- tmp2B9Frontiers
- tmp182F.tmpFrontiers
- Tmp 6500Frontiers
- tmpAE76.tmpFrontiers
- tmp8718.tmpFrontiers
- Tmp 2069Frontiers
- tmp8E92Frontiers
- tmp6CE5Frontiers
- tmp2FCA.tmpFrontiers
- Tmp 9969Frontiers
- tmp5B63.tmpFrontiers
- Von Baeyer - Maxwell's Demon (1998) - SynopsisMark K. Jensen
- Development and theoretical analysis of mathematical expressions for change of entropy for exothermic reactions in different reacting environments and conditions for minimization of energy losses in the processInternational Journal for Scientific Research and Development
- tmp18CFrontiers
- tmp6213.tmpFrontiers
- tmp44E3.tmpFrontiers
- tmpDD23.tmpFrontiers
- Vixs Systems v. Entropic Communications et. al.PriorSmart
- Tmp 3015Frontiers
- tmpC763.tmpFrontiers
- tmpD60FFrontiers

- Foul Condensate6Arun Yoga
- Foul CondensateArun Yoga
- Foul Condensate5Arun Yoga
- Foul Condensate7Arun Yoga
- Boiler Classification and ApplicationArun Yoga
- Foul CBoiler ClassificationArun Yoga
- Foul Condensate8Arun Yoga
- 087 Soot BlowersArun Yoga
- ClydeBergemannSootblowers_PrinceGeorge06Arun Yoga
- Foul Condensate2Arun Yoga
- Foul Condensate4Arun Yoga
- Automated Recovery Boiler Soot Blowing Control SystemArun Yoga
- RevolutionArun Yoga
- Foul Condensate2Arun Yoga
- Heat TransferArun Yoga
- Cladding TechnologyArun Yoga
- GreenArun Yoga
- Intro Propulsion Lect 3Arun Yoga
- By DonatingArun Yoga
- RevolutionArun Yoga
- Intro Propulsion Lect 6Arun Yoga
- Condensate System PipingArun Yoga
- CategoryArun Yoga
- M5l23Arun Yoga
- M4l22Arun Yoga
- M5l24Arun Yoga
- Air Pollution in IndiaArun Yoga
- Soot BlowerArun Yoga
- Soot BlowersArun Yoga
- Intro Propulsion Lect 7Arun Yoga

Sign up to vote on this title

UsefulNot usefulClose Dialog## Are you sure?

This action might not be possible to undo. Are you sure you want to continue?

Loading