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Thermodynamic variables

Path Function

State Function
I

II

III

WI WII WIII
(Path Function)
(VB-VA)I = (VB-VA)II = (VB-VA)III
(state Function)

Between two states the change in a state variable is


always the same regardless of which path the
system travels.
b

dV V

Va

Differential of a state function is called


EXACT DIFFERENTIAL
b

dW W
a

Wa

Differential of a path function is called


inexact differential.

yb

II
ya

xa
b

dz

xb

ydx area I

Path dependent hence inexact differential

dz

ydx xdy

d ( xy ) xb yb xa y a

area I area II

Does not depend on path hence exact differential

Simple test to see whether a differential is


exact
(Eulers Criterion for exactness)
p f (T , V ) is a state function
then
p
p
dp
dT
dV

T V
V T
With the condition that


V T


T V

Molar volume of an ideal gas


RT
Vm
P
Vm
dVm

Vm
dP

dT
p

RT
R
dVm
dP
dT
2
P

P
RT
R
R

2
2
T
P
P
P P
P

State variables are also called state properties.


The state of a system is defined as the complete set
of all its properties which can change during
various specified processes.
When a system is at equilibrium, its state is defined
entirely by the state variables, and not by the
history of the system.
The properties of the system can be described by an
equation of state which specifies the relationship
between these variables.

State Variables
P,T,V
Cut into half
P,T,V/2

P,T,V/2

P and T are intensive variables, V is an extensive variable


The variables often form pairs such that their product has
the dimensions of energy (e.g. pressure & volume in a
gas). The intensive member plays the role of force and
the extensive the role of displacement.

We can influence a system either by doing work


(e.g. compression), or thermally (e.g. heat with a
flame).
Work is done when an object is moved
against an opposing force.
The energy of the system is its capacity to
do work.
Heat is energy in transit due to
temperature difference.

Work is transfer of energy that make use of


organized motion.

When a system does work, it stimulates orderly


motion in the surroundings.

Heat is the transfer of energy that makes use of


unorganized molecular motion.

When energy is transferred to the


surroundings as heat, the transfer stimulates
disordered motion of the atoms in the
surroundings.

Joules experiment
Joule heated water by performing work on it, in this
case by rotating a paddle wheel.

adiabatic

He found that the temperature rise was dependent


only on the amount of work but independent of
how the work was performed (e.g. quickly or
slowly, large or small paddle wheel).

Temperature rise means there is change in state.

The property of the system whose change is


calculated in this way is called internal energy.

U wadiabatic

Same change in state (temperature rise) can be


achieved by allowing heat to flow in.
System in
state 1

Heat
reservoir
Heat conducting Wall

system

System in
state 2

U q

Heat
reservoir
Heat
reservoir

(no work done)

Energy can be converted from one form to another,


but it cannot be created or destroyed.

U q w
Change in internal energy of a closed system is
equal to the energy that passes through its
boundary as heat or work.
For a infinitesimal changes of state
dU dq dw

The first law contains three essential features :

It is a statement of the principal of conservation of energy.

It requires the existence of the internal energy function.


It leads to the definition of heat as energy in transit.

U is a function of the state variables and can be written

as
U f (V , T )

But Q and W are not functions of the state so we


cannot determine quantities like
Q
W
or
P
V

For an adiabatic system,


dq 0
dU

dw

This means that work needed to change an


adiabatic system from one specified state
to another specified state is a state
function.
wad is a state function.

wad U

Ui

General expression for work


dw Fdz

dw pex Adz
dw pex dV
V

Vi

pex dV

(a) Free expansion


pex=0, w=0
(b) Expansion against constant pressure
(Expansion of gas formed in a chemical reaction)

h
P2,V2,T

P1,V1,T

P1
P2
V1

V2

V1

V2

P1
P2
P1
P2
V1

V2

P1
P2
V1

V2

For infinite number of step


P1
P2
V1

V2

Infinite state expansion is called reversible


process.

These infinite-step processes at constant


temperature are reversible because the energy
accumulated in the surroundings in the
expansion is exactly the amount required to
compress the gas back to the initial state.
P1
P2
V1

V2

h
P2,V2,T

P1,V1,T

P1
P2
V1

V2
h

P1,V1,T

P2,V2,T

P2
P1
V2

V1

Important points about reversible processes


They can be reversed at any point in the process by making
an infinitesimal change.
A reversible expansion or compression requires
A balancing of internal and external pressure.
Time to reestablish equilibrium after each
infinitesimal step.
Absence of friction.
For the processes in the chemical industry, the greater
the irreversiblity, the greater is the loss in capacity to do
work. Every irreversibility has its cost.

Ways to approach reversibility

Heat may be transferred nearly reversibly if the


temperature gradient across which it is transferred is
made very small.
Electrical charge may be transferred nearly
reversibly from a battery if a potentiometer is used
so that the difference in electric potential is very
small.
A liquid may be vaporized nearly reversibly if the
pressure of vapor is made only very slightly less
than the equilibrium vapor pressure.

h
P2,V2,T

P1,V1,T

P1

=P2(V2-V1)

P2
V1

V2
h

P2,V2,T

P1,V1,T

P1
=-(P1(V2-V1))

P2
V1

V2

h
P2,V2,T

P1,V1,T

P1
=nRTln(P1/P2)

P2

V2

V1
h
P2,V2,T

P1,V1,T

P1

=-nRTln(P1/P2)

P2
V1

V2

The variables often form pairs such that their


product has the dimensions of energy). The
intensive member plays the role of force and the
extensive the role of displacement.
Type of Work Intensive
variable

Extensive
Variable

Differential
work

Expansion

-PdV

Surface

(surface
tension)
F

dA

FdL

(potential
diff.)

dQ

Elongation
Electrical

dU dq dwexp (PV kind) dwe

Heat
Heat is energy in transit due to
temperature difference.

Mechanical definition= wad-w

If a quantity of heat is required to increase the temperature


of a body by dT , the heat capacity C is defined to be

dQ
q
C

C
TdT

Since heat is an inexact differential, depending upon the


way in which energy changes occur, then it is clear that
there cannot be a unique heat capacity for a system either.

So the quantity of heat which


flows in will depend upon the
path of the transformation
and there will be an infinite
number of heat capacities.

Of the infinite possible number, it is customary to define


two heat capacities. Heat capacity at constant volume CV
and heat capacity at constant pressure Cp

dqV CV dT
CV is called heat capacity at constant volume.
CV can be determined by burning a known
mass of substance that has known heat output.
With CV known, it is simple to interpret an
observed temperature rise as a release of heat
Specific heat is essentially a measure of how
thermally insensitive a substance is to the
addition of energy.

Most processes that occur in the laboratory, on the


surface of the earth, and in organisms do so under a
constant pressure of one atmosphere

Some of the energy supplied as heat to the


system is returned to the surrounding as
expansion work.

Specific heat is essentially a measure of how thermally


insensitive a substance is to the addition of energy.
For solids and liquids cV and cp are very similar.
Aluminium

900 J Kg-1 C-1

Wood

1700 J Kg-1 C-1

Water
4186 J Kg-1 C-1
The high specific heat of water is the reason that
coastal regions have milder climates than inland regions
at the same latitude.

Important point about Internal energy


Internal energy is the total of the
kinetic energy of the constituent atoms or molecules due to their
motion (translational, rotational, vibrational) and
the potential energy associated with intermolecular forces. It
includes the energy in all of the chemical bonds, and the energy
of the free, conduction electrons in metals.

Important point about Internal energy


Internal energy does not include the translational or
rotational kinetic energy of a body as a whole.

It also does not include the relativistic mass-energy


equivalent E = mc2.

It excludes any potential energy a body may have


because of its location in external gravitational or
electrostatic field, although the potential energy it has in
a field due to an induced electric or magnetic dipole
moment does count.

dU dq dw
U q p PV

(at constant P)

U 2 U 1 q p P (V2 V1 )
q p (U 2 PV2 ) (U 1 PV1 )
H 2 H1

Enthalpy is a state function.


Enthalpy is an extensive quantity.
The change in enthalpy is equal to the heat
absorbed in a process at constant pressure if the
only work done is reversible pressure-volume
work.

H f ( P, T )
H
H
dT

At constant pressure,

dH

dH

dT

dH dq P

C p dT

dT
P

dP
T