P0

0
0 V0 2V0

Figure 2 .2 For the change in state of a mole of gas from (2P0 ,V0 ) to (P0 ,2V0 ), the work
Lecture 4-5
done on the gas depends on the path. By the upper path, w ! !2P0 V0 . By the lower path,
w ! !P0 V0 . For a clockwise cyclic process, w ! !2P0 V0 " P0 V0 ! !P0 V0 . In the cyclic
process, the gas is returned to its initial state, and so "U ! 0 ! q ! P0 V0 . Thus, q ! P0 V0
and heat is absorbed by the system in the cyclic process.
Work is a path function: In the example to the
Isobaric step
right, the first path amounts to 2P0V0, while Initial
(heat flows in)
state
giventhe second
change one
in state of is -P
the water V .calorimeter
in the
0 0
In an adiabatic
can be accomplished in differ-
2P0
ent ways involving the same amount of work, or by different sequences of steps,
process
the change (isolated
in state is independentsystem), where
of the path there is
and is dependent no
only on the total Isochoric step

exchange ofmakes
energy is allowed,
to express thethe total
(heat flows out)
amount of work. This it possible change in state of a system
in anchange
adiabatic process
of statein terms
can of the
bework required, without
represented bystating
onlythe thetype of P0

work or the sequence of steps used. The property of the system whose change is
work.
calculated in this way is called the internal energy U. Since the internal energy U
of a system may be increased by doing work on it, we may calculate the increase 0
in internal energy from the work w done on a system to change it from one state 0 V0 2V0
= (in an adiabatic
to another in an adiabatic process:
process) Figure 2 .2 For the change in state of a mole of gas from (2P0 ,V0 ) to (P0 ,2V0 ), the
done on the gas depends on the path. By the upper path, w ! !2P V . By the lower 0 0
w ! !P0 V0 . For a clockwise cyclic process, w ! !2P0 V0 " P0 V0 ! !P0 V0 . In the
"Uand! w work (in anare
adiabatic process) Joule had process, the
(2gas
.6)is returned to its initial state, and so "U ! 0 ! q ! P0 V0 . Thus, q !
But the heat related. and heat is absorbed by the system in the cyclic process.

shown
In words, that.
the work done on a closed system in an adiabatic process is equal to
mgh in
the increase > internal
KE energy of the system. The symbol " indicates given changeof
the value in state of the water in the calorimeter can be accomplished in d
ent ways involving the same amount of work, or by different sequences of
the mgh
quantity=inKE
the final
+ heatstate minus the value of the quantity in the initial state;
the change in state is independent of the path and is dependent only on the
"U ! U2 ! U1 , where U1 is the internal energy in the initial state and is work.
U2 of
amount the This makes it possible to express the change in state of a sy
in an adiabatic
internal energy in the final state. If the system does work on its surroundings, w isprocess in terms of the work required, without stating the ty
work or the sequence of steps used. The property of the system whose chan
1 cal
negative and,=furthermore,
4.198 J. "U is negative (i.e., the internal energy ofcalculated
the systemin this way is called the internal energy U. Since the internal ener
decreases) if the process is adiabatic. of a system may be increased by doing work on it, we may calculate the inc
1 cal is the heat required to increase the internal
Although equation 2 .6 provides a way to determine the changeinin energy from the work w done on a system to m
internal change it from one
temperature
energy of a system, it doesofnot1provide
gm water by 1 degree.
a way to determine
to another in an adiabatic process:
the absolute magnitude
of the internal energy of the system. However, the internal energy can be fixed Figure "U !2w.3 Joule (in an heated
adiabaticwater
process)
by
arbitrarily for some given equilibrium state of the system, and equation 2 .6 can performing work on it, in this case
Therefore,
be used to determineinternal energy
the internal energy can also
with respect to that be changed by done
state.the work
In words,
reference using heat
on a closed system in an adiabatic process is equ
by rotating
the increase in internal energy of athepaddle
system.wheel, and " indicates the va
The symbol
into the system
When equation without
2 .6 is applied doing
to a system anysize,
of arbitrary work.
the internal energy
the quantity in the found that
final state the the
minus temperature
value of therise de- in the initial
quantity
is an extensive quantity, but in working problems we will often deal"with U !U molar pends
2 ! U1 , where U1 only
is the on the amount
internal energy inof
thework
initial state and U2
!1 energy in the final state. If the system does work on its surroundings
internal
quantities and express the change in molar internal energy "U in J mol . done on the system.
= (when no work is done) negative and, furthermore, "U is negative (i.e., the internal energy of the sy
decreases) if the process is adiabatic.
Although equation 2 .6 provides a way to determine the change in int
energy of a system, it does not provide a way to determine the absolute magn
So the first law of thermodynamics states that,
of the internal energy of the system. However, the internal energy can be
arbitrarily for some given equilibrium state of the system, and equation 2 .
be used to determine the internal energy with respect to that reference stat
When equation 2 .6 is applied to a system of arbitrary size, the internal e
= + is an extensive quantity, but in working problems we will often deal with m
quantities and express the change in molar internal energy "U in J mol!1 .

For an infinitesimal change in state,

= + (First Law of Thermodynamics)

Here, since is path depedent, is path dependent, but is not

path dependent. This is taken to be a postulate. The change in the
internal energy is thus either by changing the heat or by doing
work on the system.

The fist law is also called as the law of conservation of energy

 For a cyclic process, the change in the internal energy is zero. This
is represented mathematically as, = 0.

Microscopic definition of heat and temperature and work:

energy can be changed by moving particles in different
energy levels
energy can be changed by doing work

4U 4U
4U 4U
3U 3U 3U
2U 2U
2U 2U
1U 1U 1U
0
0 0 0

U =1 U=3 U =1 U=2
Adding heat, q = 2 applying work, w = 1

[In the right figure above, energy of the level 1 changes as high as the energy
of the level 2. Energy of the level 2 changes to as high as energy of level 4. Level
themselves do not change]

!! !!
From the expression of particle in a box, ! = !!!! . So, by changing
, we can change the separation. Therefore, by changing the
volume (! ) of the box we can change the energy. This is the
energy that is obtained by doing work on the system. You will see
later how this expression gives the energy of an ideal gas at finite
temperature.

Work at constant temperature: Quasi-static process, reversible,

and irreversible process.
Chapter 2 First Law of Thermodynamics

m
P2

h
m
P1, V1, T
P1
P2, V2, T

V2 V1
(a) (b) (c)

Figure 2 .6 Compression of a gas from P1 , V1 , T to P2 , V2 , T in a single step.

piston. The cylinder is immersed in a thermostat at temperature T, and the space

above the cylinder is evacuated so that the final pressure P2 is due only to the
mass m . The gas is initially confined to volume V1 because the piston is held up by
stops. When the stops are pulled out, the piston falls to the equilibrium position,
and the gas is compressed to volume V2 . The pressure of the gas at the end of the
process is given by

mg
P2 ! (2 .30)
A

where g is the acceleration due to gravity, and A is the area of the piston. The
 area A, and acceleration of gravity g .
However, we can carry out the compression with less work if we do it in two
or more steps, as shown in Fig. 2 .7. We can compress the gas in two steps by first
using a mass m ! just large enough to compress the gas to volume (V1 " V2 )/2 in

P2 P2 P2

P1 P1 P1

V2 V1 V2 V1 V2 V1
(a) (b) (c)

Compression of Compression
Figure 2 .7 a gas in of one, two,P1three,
a gas from and
, V1 , T to P 2 , V2 , Tinfinite steps.
in two, three, and an infinite
number of steps.

Work done for compression is shown above by the shaded area.

Work done for expansion will be different for non-infinite step.
Notice that, only for the infinite steps, we need to do the smallest
amount of work on the system to compress the gas from V1 to V2.
Therefore, minimum work is done on the system in a reversible
process between two state points.

(Why temperature needs to be constant? Why do we need to heat the

system? Cant the system do some work using its internal energy here?)
Yes. It is called adiabatic expansion. If we allow heat to flow then the
temperature will become equal. Thus, for an infinitesimal process,
temperature will remain constant.

!"
! = !

!"#$%&'(% = = ! (! ! ) (one-step work)

This is irreversible because same work cannot be obtained by

reversing the situation in which case,
!"#$%&''(") = ! ! ! = ! ! ! .
[Since, ! < ! , !"#$%&''(") > |!"#$%&'(% | ]

[Note that, the signs of !"#$%&'(% and !"#$%&''(") are different. This is
because, both are considered to be work done on the system. Therefore,
the signs will be same if we consider negative work done on the system is
the same as positive work done by the system. During expansion, work
done by the system = !"#$%&'(% = ! (! ! ). Due to this change in sign, a
maximum work done by the system is the minimum work done on the
system.]
! !
!"#$%&'(% = !
=
! !"#
(infinite-step work)

This is reversible because same magnitude of work is obtained by

reversing the situation in which case,
 ! !
!"#$%&''(") =
! !"#
=
! !"#
.

In the above, work done on the system during compression = work

done by the system during expansion.

So, maximum work is done by the system if the expansion from V2

to V1 is done by infinite step, i.e., reversibly. Since reversibility
cannot be achieved in real life, these kinds of infinitely slow
processes are termed as quasi-static process. Values obtained from
quasi-static and reversible process are taken to be same.

We do many such irreversible processes every day, every minute.

This means that we can no longer get back to the previous state
ever. This is precisely the arrow of time. We will come back to it
later during second law of thermodynamics.

Constant temperature reversible work done for ideal gas is thus:

!! !! !"# !!
=
!! !"#
= !! !
= ln !!
.

Heat is a path function.

Heat = specific heat X temperature change.

For gases, there is no single value of specific heat; it depends on

whether the process happens at a constant volume or at a
constant pressure.
We will first see the constant volume change. Taking (, )

!" !"
= !" !
+ !" !

[Note that, is function of any of the two variables that define the
system. For convenience we take and ]

Using the first law, = = + !"#

!" !"
= !" !
+ !"# + !" !

!"
Since is constant, ! = !" !

 T2
#UV ! "T1
CV dT ! qV (2 .48)

This is illustrated in Fig. 2 .11. Over a small temperature range CV may be nearly
constant so that
#UV ! CV (T2 ! T1 ) ! CV #T (2 .49)
Define the specific heat at constant volume as ! . ! is a state
In principle,
function as the
quantity ("U /"V )T may be measured in an experiment de-
! is also a state function (path is defined here).
vised by!!Joule. Imagine
!" two gas bottles connected with a valve and enclosed in a
! = !"!isolated
thermally [Definition]
= !"container, as shown in Fig. 2 .12. The two bottles constitute the
!
system under consideration. The first bottle is filled with a gas under pressure, and
the second is evacuated. When the valve is opened, gas rushes from the first bottle
Above
into equation
the second. can
Joule found thatbe used
there was noto find out
discernible the
change in the temper-
ature once thermal equilibrium had been established, and so dq ! 0. No work is C
change in the internal energy for finite change T2
done in this expansion since Pext ! 0, and so dw ! 0 and dU ! dq " dw ! 0. q= C dT
in temperature
Since at constant
the temperature is constant, equation 2volume.
.44 becomes T1

#"V $
"U T1 T2
!! dU ! dV ! 0 (2 .50)
! = !! !
= ! T
T
Figure 2 .11 The heat q absorbed
Since dV ! 0, by a substance when it is heated
Over a small change in "U temperature CV may be considered is equal to the integral of C dT

constant (see figure above) # $

"V T
!0
and thus the above equation
(2 .51) from the initial temperature T1
can
to the final be T2 . If an
temperature
written as, amount n is heated at constant vol-
Thus , Joule concluded (incorrectly) that the internal energy of the gas is inde- ume, C ! nCV , and if an amount
pendent of the volume. However, this method is not very sensitive because of the n is heated at constant pressure,
large
heat
! = capacity
! of the
! != gas
bottles relative to the gas. Equation 2 .51 actually C ! nCP .
!

! = ! (for all systems)

Change of state at constant pressure: Similar to change in

internal energy, enthalpy changes for heating at constant
pressure.

! = ! [! denotes change in heat]

! ! = ! ! !
! + ! ! ! = ! -- (1)

The heat change is now the difference of two specific quantities.

Lets define these quantities as enthalpy,

= + (Definition of enthalpy)
= + [ = 0 at constant pressure]

Then,
! ! = ! [From Eq. (1) above]
! =
! =

Heat absorbed in a process at constant pressure is equal to the

change in enthalpy.

is an exact differential because ! is exact (path is fixed here).

Pressure and temperature are natural variable of enthalpy.
 !" !"
= !" !
+ !" !

Since = 0 and ! =

!"
! = !" !

Note, the specific heat at constant pressure now can be defined as,

!!! !"
! = !"
= !" !

Taking specific heat to be constant within a specific interval of

temperature, we can write,

!!
! = !! !
= !

For gases, it can be shown that

CP > CV. For ideal gas, CP - CV = R. [Show the proof]. Specific heats
are defined for a mole of gas.

! = = +
! ! !
Now,
!" !"
= !" !
+ !" !

!" !" !" !" !"

So, !" !
= !" ! !" !
+ !" ! !" !

!" !" !" !"

Or, !" !
= !" !
+ !" ! !" !
----(2)

!" !"
So, ! = !" !
+ !" !
!" !" !" !" !"
= !" !
+ !" ! !" !
+ !" !
[Substituting !" !
from Eq. (2)]
!" !"
= ! + !" !
-----------(3) [Since, !" !
= 0 for ideal gas]

!"
But, = !" !
=

So, from (3) we get, ! = ! + , where everything is defined for n

mole of gases. In constant pressure, some extra heat is required to
5.60 Spring 2008 Lecture #3 page 4
do the work in addition to increasing the temperature. So, ! is
larger than ! .
U
Joule Free Expansion of a Gas (to get )
V T
Joule Free Expansion indirectly measures

Adiabatic
Adiabatic process, = 0q = 0
gas vac Expansion into vacuum, = 0
(!"#Expansion
= 0) into Vac. w = 0
So, =
(pext
+ =0)= 0
gas (p1!"
, T1, V1) !"
= gas (p2, T2, V2)
= !" !
+ !" !

Since q = w =!"0 dU or U = 0 Constant U

= ! + !" !
= 0 -----(4)
U
Recall dU = CV dT + dV = 0
V T
!"
For ideal gas, we knowtheoretically that !" = 0 [Since U=3/2 RT ].
!
U
So, = ! for ideal gas. [Note the difference from earlier result
! = ! , which dV = C
is Utrue fordT
V T
V all U sytesm]

U T Tgases.

= 0 for all = CV expansion
isothermal or compression
measure of ideal
in Joule exp't!
Again, = 0Vimplies
T V
that U = 0. V U

The physical origin of

this
T effect
Tcomes
from the fact that in ideal
Joule
gas, only energy lim
did this. = energy
kinetic
is the because dU
the = CV dT Care
particles dV
V J so
V U V U
V 0 J
far away that there is no attraction between them and therefore,
Joule coefficient
it does not matter if the volume increases.

For Ideal
In general, gas
however, we can =0 exactly
J continue Eq. (4) as,

!"
dU = CV dT Always for ideal gas
So, ! = ! !
!"
!" !
!"
U(T) only depends on T
!" !
= ! !" !
= ! ! , where ! is measured in Joules
experiment
The internaland it isof
energy called Joules
an ideal coefficient.
gas depends onlyIton
measures the
temperature
change in temperature for free expansion ( = 0) at isolated
condition (dU=0), achieved by free expansion ( = 0) at
Consequences
adiabatic condition U == 00). For all isothermal expansions or
(
compressions of ideal gases
!" !"
So, = !" !
+ !" !

=
!" U = C dT
! ! = !V ! !
For any
!" ideal gas change in state
=
!" ! !" ! ! !
Since ! can be measured experimentally, we can get the value of
!"
!" !
experimentally for all real gases. For real gases, increase in
volume will reduce the potential energy and therefore, U will
decrease, decreasing the temperature.

It can be shown mathematically that for van der Waals gases,

!" !
!" !
= / ! . So, ! = ! ! ! ! . So, T will decrease for increase in
!
volume at the isolated condition for van der Waals gases.

Adiabatic Work (Work at constant heat): = 0, So, =

56 Chapter 2 First Law of Thermodynamics

For reversible adiabatic process,
!! !! 1.0

!!
=
!! !"#
A

or, = ! ! = 0.8

Isothermal
!! !
But, !!
= ! ! ! = ! (! ! ) 0.6
!

P/bar
B
Adiabatic
So, = ! (! ! ) 0.4

!"
Now, ! = = !
0.2

!! !" ! 0.0
Or, !
= ! 20 25 30 35
V/(L mol1)
40 45 50

Figure 2 .15 Isothermal and reversible adiabatic expansions of one mole of an

monatomic gas.
!! !! !" !! !"
!! !
= !! !
2.11 THERMOCHEMISTRY

!! !! !! The quantity of heat evolved or absorbed in a chemical reaction or a phase ch

! ln !!
= ln !!
= ln !! can be determined by measuring the temperature change in an adiabatic pro
Since very small temperature changes can be measured, this provides a s
tive method for studying the thermodynamics of chemical reactions and p
changes. If the temperature rises when a reaction occurs in an isolated sy
!! !! !/!! !! !!!
!!
= !!
= !!
, where = ! /! = 1 + / then in order to restore that system to its initial temperature, heat must b
lowed to flow! to the surroundings. Such a reaction is said to be exothermic
the heat q is negative. If the temperature falls when a reaction occurs in an
!! !! !! !!! ! ! ! the surroundings to the system to restor
!! !!
= !!
Or, ! ! = ! ! = ! or = !!
, where =
lated system, heat must flow from
! ! Such a reaction is said to be endothermic
system to its initial temperature.
the heat q is positive.
Since the enthalpy is an extensive property that is a function of the sta
!! !! !!
the system,
!!! ! (at constant T and P ) can be written in terms o
its differential

! ! of the
partial molar enthalpies !!!
species in!!!
the system (see equation 1.37 in Se
!"#!$!%#& = = !! = 1.10): = ! !
!! !! 1 !!
1
Ns
dH ! ! Hi d ni (
i !1

Since no energy is supplied from outside, the

where Nwork done in an
s is the number of species and Hi is the molar enthalpy of species i . W

adiabatic process is less than that of isothermal [See the figure

the temperature and the pressure are constant, equation 2.57 yields
N

above]. Therefore, pressure drops more in adiabatic expansion dH ! dqP ! ! Hi d ni (

i !1

than in a corresponding isothermal process.