JOULE EXPERIMENT

A schematic diagram of the apparatus used by Joule in an attempt

to measure the change in internal energy when a gas expands
isothermally (gas expands into a vacuum).
The heat absorbed by the gas is proportional to the change in
temperature of the bath.
lim p1 → 0, ∆Tbath = 0
p1is the pressure of the gas &
it expands into the bulb at p 2 = 0
∆U = q + w
w = 0 & q = CV ∆T
when a low pressure gas (ideal gas)
is expanded it does so without a change in internal energy, U.
 ∂U   ∂U 
dU =   dT +   dV
 ∂T V  ∂V T
From Joule' s experiment,
dU = 0 & dT = 0
 ∂U  Conclusion:
hence   = 0 for an ideal gas. The internal energy of the gas is independent of the volume.
 ∂V T
i.e., U = f(T) only for an ideal gas.
1
 Joule Thomson Experimentt
A diagram of the apparatus used for
measuring the Joule-Thomson effect
is shown here. The gas expands
through the porous barrier, which
acts as a valve, and the whole
apparatus is thermally insulated. This
arrangement corresponds to an
isenthalpic expansion (expansion at
constant enthalpy). Whether the
expansion results in a heating or a
cooling of the gas depends on the
conditions.

2
Joule Thomson expansion.
A gas at initial temperature and pressure Ti , pi
is expanded at constant pressure through a
small valve or what is called a porous plug
under adiabatic condition [system insulated so
that no heat can go in or out]. For this process
we can show that the enthalpy remains
constant.
INITIAL: Push piston in and the gas volume goes from Vi to 0 but the pressure stays
constant as the gas escapes through the small porous plug or throttling valve. Thus
the work done on the gas is:
Wi = -pi ( 0 – Vi ) = pi Vi
FINAL: The RHS piston is pushed out by the gas at a lower constant pressure and the gas
volume goes from 0 to Vf. Thus the work done by the gas is:
Wf = - pf (Vf – 0 ) = - pf Vf

3
The overall physical result of the gas expansion through the valve is that when
the pressure changes from pi to pf there is a temperature change in the gas from
Ti to Tf. The temperature and pressure changes are easy to measure and the
ratio

H (T , p)
For ideal gas, H = f(T) only
 ∂H   ∂H 
dH =   dT +   dp
 ∂T p  ∂p T  ∂H 
  = 0
for.isenthalpic
 ∂p T
 ∂H 
0 = C p dT +   dp for real gas
 ∂p T
 ∂T  1  ∂H   ∂H 
  = −     ≠ 0
 ∂p  H Cp  ∂p T  ∂p T
 ∂T 
  = µ JT
 ∂p H

In almost all cases the JT coefficient is positive in value. This means that when a
gas expands and pressure drops δp < 0 via a JT process, δT <0 and the gas cools.
This is the principle behind the cooling and liquefaction of gases that is used
in refrigeration.
4
Properties of the Joule Thompson coefficient
μJT = fn(T,p) of each gas and so its value changes
with temperature and pressure at which the
expansion occurs.
μJT > 0 for most T and p conditions but under
certain conditions it can be negative. Then the
gas will heat up instead of cooling when the
expansion occurs. The temperature at which μJT =
0 is called the inversion temperature.

•The inversion temperatures for three real

gases, nitrogen, hydrogen, and helium.

5
Gas Liquefaction:
The diagram shows how a gas can be liquefied by
repeated circulation of a gas undergoing JT cooling.
First, the gas is compressed. This heats up the
gas but it is cooled down partially through a heat
exchanger (cooling vanes) to the ambient
temperature.
The gas passes expands through a valve
and undergoes JT cooling. It is then made
to re-circulate and cool the incoming gas.

Repeating this cycle eventually gets the temperature of the gas

exiting the valve below the boiling point and the gas condenses.
This was the method used to first liquefy nitrogen and oxygen gas.
Hydrogen and helium have low inversion temperatures and thus
must be pre-cooled before undergoing JT cooling.

6
Refrigeration:
Principle of Operation: The freon is compressed by the
motor (bottom, back of the fridge). This heats the freon
but it is cooled back to near ambient temperature by the
heat exchanger (metal grid at back of fridge which feel
warm). The compressed freon enters the expansion coils
in the freezer compartment where it cools down. Then it
undergoes JT expansion and condenses. The fan
circulates the air between the main compartment and
the freezer. The warmer air from the main compartment
provides the heat of vaporization used to evaporate the
freon which returns as a gas to the compressor. Thus the
fridge air cools. This is the cold air which re-circulates to
cool the freezer and the main compartment.
For freon μJT = 1.2 K atm-1. Thus for a pressure drop of 40 atm
in the fridge the temperature drop of the freon is δT = μJT δp
= -48 K which is more than enough to get the freezer
compartment to about -15 °C required to keep ice cream
quite solid. 7
 Carnot Heat engine
Heat engine is defined as a device that converts heat energy into mechanical
energy through a cyclic process OR more exactly a system which operates
continuously and only heat and work may pass across its boundaries.

Surrounding

HTER= High Temperature Energy Reservoir

LTER= Low Temperature Energy Reservoir

The engine consists of an idealized cylinder with a piston that can slide without
friction and can do work on the surroundings or have the surrounding do work on
the gas.

You wants to see the engine:

http://galileoandeinstein.physics.virginia.edu/more_stuff/flashlets/carnot.htm 8
Description of the Carnot Cycle: The cycle is performed through a sequence of four stages that
system return to its initial state at the end.

Stage 1: Reversible isothermal expansion from A to B

In the first stage, the piston moves downward while the engine ∆U1 = q1 + W1
absorbs heat from a source and gas begins to expand. Isothermal
expansion, because the temperature of the gas does not change.

Stage 2: Reversible adiabatic expansion from B to C

In the second stage, the heat source is removed; the piston
continues to move downward and the gas is still expanding while ∆U2 = W2
cooling (lowering in temperature). Adiabatic expansion because
energy stays.
Stage 3: Reversible isothermal compression from C to D
The piston begins to move upward (the surrounding do work on ∆U3 = q2 + W3
the system), which evolve heat q2 and which goes to sink. The
engine gives energy to the environment.

Stage 4: Reversible adiabatic compression from D to A

In the final stage, the piston to move upward and the cool gas is
∆U4 = W4
isolated and compressed. Its temperature rises to its original
state. Point C to point D illustrate this behavior; a continuing
increase in pressure and decrease in volume to their initial
position. Energy stays, so it's an adiabatic compression. 9
10
11
12
13
The change in U of the system for the cycle ∆Ucy is:

∆Ucy = ∆U1 + ∆U2 + ∆U3 + ∆U4 = zero

∆Ucy = 0 = ( q1 + q2 )+(W1+W2+W3+W4)

∆Ucy = 0 = qcy + Wcy

-Wcy = qcy = ( q1 + q2 )

For Carnot heat engine, it is consider that:

∴ Wcy = q1 − q2

Thus, the work Wcy done by the engine in a cycle is equal to the
difference between the heat in q1 and the heat out q .
2

14
In practice, the low-temperature reservoir of a heat engine is often
the atmosphere so that the economic cost of producing work in
the surroundings is mainly that of supplying q1.
Efficiency ε of a heat engine:
It is the ratio of the work done on the surrounding to the heat input at the
higher temperature.

− Wcy Wcy q2
ε= = = 1−
q1 q1 q1
0 <ε < 1

It is clear that to increase the value of ε of a Carnot heat engine, one would
like to reduce heat rejected to the cold reservoir q2, which is impossible to be
zero.

15
 Application in engines

The Carnot Cycle forms the perfect process of a heat

engine. Many engineers tried to reach this kind of cycle.
Rudolf Diesel had the most success and his engine is
nearly as perfect as the Carnot engine. There are also
other cycles, e.g. the Stirling Cycle you see on the right
side.

16
Description of the Carnot Cycle: The cycle is performed through a sequence of four stages that
system return to its initial state at the end.

Stage 1: Reversible isothermal expansion from V1 to V2 at T1 ∆U1 = q1 + W1

 V2 
W 1 = − nRT 1 ln  
 V1 
Stage 2: Reversible adiabatic expansion from V2T1 to V3 T2
T2
∆U2 = W2
W2 = ∫C
T1
V dT

Stage 3: Reversible isothermal compression from V3 to V4 at T2

∆U3 = q2 + W3
 V4 
W 3 = − nRT 2 ln  
 V3 
Stage 4: Reversible adiabatic compression from V4T2 to V1 T1
T1 ∆U4 = W4
W4 = ∫C
T2
V dT

17
 ∴ W cy = W 1 + W 2 + W 3 + W 4
 V2   V3 
T2 T1

W cy = − nRT 1 ln 
 V1
 +

∫C
T1
V dT − nRT 1 ln 
 V4
 +

∫C
T2
V dT

 V2   V4 
Wcy = −nRT1 ln  − nRT2 ln 
 V1   V3 
 V2   V3 
Wcy = −nRT1 ln  + nRT2 ln 
 
 V1   V4 
From the adiabatic process: from V2 to V3 and from T1to T2
α −1
 T2   V2  C 
  =   α =  p  ∴T1 ( V2 )α −1 = T2 ( V1 )α −1
 T1   V3   CV 
α −1
 T1   V4 
  =  
 T2   V1  ∴T1 ( V1 )α −1 = T2 ( V4 )α −1

 V2   V3 
∴   =   18
 V1   V4 
  V2   V3 
∴   =  
 V1   V4 
Substitute in Wcy equation
 V2 
Wcy = − nR( T1 − T2 ) ln 
 V1 
V 
and q1 = −Wcy = nRT1 ln 2 
 V1 
Substitute in in the efficiency equation
Wcy T1 − T2  T2 
ε= = = 1 −  
q1 T1  T1 
Thus, high efficiencies are obtained if the ratio T2/T1 is small.

In practice, T2 is close to room temperature and T1 is made as

high as possible.

19
 Second Law of thermodynamics
Kelvin’s statement “It is impossible to produce work in the surrounding
using a cyclic process connected to a single heat engine reservoir”

Clausius’ statement “It is impossible to carry out a cyclic process using an engine
connected to two heat reservoirs that will have as its only effect the transfer of a
quantity of heat from the low-temperature reservoir to the high-temperature reservoir”

WcyT1 − T2  T2 
ε= = = 1 −   For any fluid
q1 T1  T1 

20
Types of possible processes:
(a) SPONTANEOUS(irreversible):
these occur naturally without any effort on our part:
mixing of two gases
heat flow from a hot to cold body
forgetting the second law
spending money
today becomes tomorrow
things never are as they were
(b) UNNATURAL:
these only occur with energy or work input on our part separating
gases in a mixture:
heat flow from a cold to hot body
learning the second law
earning money
(c) EQUILIBRIUM(reversible):
these show no overall change and are easily reversed
balanced budget
knowledge of thermodynamics two minutes after the final exam
evaporation « condensation of water in a closed bottle.
21
Second Law of Thermodynamics

• It is very important law in chemistry, because it

tell us whether a reaction will occur or not and in
which direction.
• A new state function (entropy) will appear,
which will tell us whether a chemical reaction or
physical process can occur spontaneously or not.

22
 ENTROPY

Matter tends to become Energy tends to become

disordered disordered

23
 Entropy
From the efficiency of a reversible Carnot engine

q2  T2  q2 T2
ε = 1 + = 1 −   ∴ + =0
q1  T1  q1 T1
 q1  q2 q1
X   ∴ + =0
 T2  T2 T1
where dq
dS =
T
This is the change in entropy and it is a state function.

The change in a state function around any cycle is zero

∴ ∆ S cy = ∆ S 1 + ∆ S 2 + ∆ S 3 + ∆ S 4
24
 q1 q2
∴ ∆ S cy = +0 + +0
T1 T2
Where for adiabatic steps: ∆S 2 = ∆S 4 = zero
Because there is no change in entropy

dqrev
∫ T =0
∴ ∫ dS = 0

25
 Chemical thermodynamics Second
Law
•The thermodynamic temperature scale is defined so that during a reversible
cycle among states that returns to the original state, the integral of dq/T is zero.
Hence there exists another variable of state S, the entropy, whose change is
given by:

dq
dS =
T
•If at any time our closed cycle deviates from reversibility and undergoes a
spontaneous change, we find that the integral of dq/T is always positive.

26
 The Clausius Theorem
According to Carnot theory “ No engine operating between two heat reservoirs
can be more efficient than a reversible Carnot engine operating between the
same two reservoirs”

i.e. ε ≤ ε rev
For any arbitrary engine Carnot reversible engine

q2 q 2 ( rev ) − q2 − q 2 ( rev T2
∴1+ ≤ 1+ ∴ ≥
)
=
q1 q 1 ( rev ) q1 q 1 ( rev ) T1
Where q2 and q2(rev) have negative sign

− q2 T2 − q2 q1 q2 q
∴ ≥ OR ∴ ≥ OR 0 ≥ + 1
q1 T1 T2 T1 T2 T1
This equation were derived before in the case of reversible Carnot engine, and for the four
steps of the cycle:
qi
∑ Ti
≤ 0 27
This apply for any engine operating in a cyclic with many heat reservoirs.
As in general:

dq
∫ T
≤ 0
It concluded that:
• If any part of the cyclic process is irreversible (natural), the inequality (<) applies
and the cyclic integral is negative.

• If a cyclic process is reversible, the equality applies exactly as Carnot cycle.

• It is impossible for the cyclic integral to be greater than zero.

Note that the temp. that appears in the cyclic integral in the above equation is that of the
heat reservoir or surr. When the process is reversible, Tsurr =Tsys.

28
 The second Law in Practical Applications

By applying the Clausius theorem to an irreversible cycle:

State 1 irreversib
  le
→ State 2 reversible
 → State 1

According to the above equation:

2 1 2 2
dq dq rev dq
∫1 T + ∫2 T < 0
irrev
∫
1
irrev

T
− ∫ dS
1
< 0
2 2
• Thus dq irrev
∴ ∆ S = ∫ dS > ∫
1 1
T
• OR dq irrev
dS > ∫
T

• This for an infinitesimal irreversible process in an isolated system and represent a

second definition of the entropy.

29
 The full definition of entropy

By applying the Clausius theorem to an irreversible: cycle:

dq
dS ≥ ∫ irrev

This represent the second Law in the useful form.

• The equation describes three types of processes:

dq
dS > Spontaneous and irreversible process
T
dq
dS = Reversible process
T
dq Impossible process
dS <
T
30
 For closed system dq = zero for finite change

∆S > 0 Spontaneous and irreversible process

∆S = 0 Reversible process

∆S < 0 Impossible process

Changes in entropy of an isolated system with time

S
S increases spontaneously until equilibrium is
reached.

The thermodynamic does not give the time

required to reach equilibrium, but it gives the
direction.
t

31
 Entropy changes in reversible processes
Relation between entropy change and enthalpy

The transfer of heat from a body to another at infinitesimally change of

temperature is reversible.
Example: vaporization of a pure liquid into its vapor at the equilibrium vapor
pressure and constant T. Liquid ( T , p )  →Vapor( T , p )
S2 2
dqrev qrev
∫S 1ds =∫1 T = S2 −S1 = ∆S = T
Where qrev is the heat absorbed in the reversible ∆H
change at constant p and is equal to ∆H. ∴ ∆S =
T
This equation can be used to calculate ∆S of sublimation, melting, …etc.

Ex: n-hexane boils at 58.7 oC at 1 atm and its ∆Hvap,m is 28.85 kJ mol-1at
this temperature. What is ∆Svap of n-hexane when it vaporized at the
boiling point?
∆H vap ,m 28850J / mole
∆Svap ,m = = = 84.41J /( K .mole )
T ( 278.1 + 58.7 )K 32
 ∆S( liquid ) > ∆S( solid ) At equilibrium

This means that entropy is a measure of the disorder of the system.

Note: the molecules of gas are more disorder than those of liquid and the
molecules of liquid are more disorder than those of solid .

liquid

solid

33
The general equation for change in entropy for reversible processes:

(a) Adiabatic dqrev = 0

(b) Isothermal T = constant

(c) Isobaric p = constant

(d) Isothermal, Isobaric

34
 (e) Isochoric V = constant

(e) Isothermal and Ideal Gas where Vi → Vf

For isothermal conditions
For isothermal, ideal gas, reversible conditions

(g) Ideal Gas:

Any Process going from state Ti, pi, Vi → Tf, pf, Vf

35
This equation for an ideal gas is extremely useful because it applies to any process and
only requires a knowledge of the initial and final state i.e. any two of temperature,
pressure and volume. It can be used instead of some of those equations derived earlier
since it reduces to those previously derived.

For example, if the process is isobaric then pi= pf and

Substituting in the above general equation for an ideal gas

If the process is adiabatic we recall that:

36
 ∆S for Irreversible Processes:

Consider a system going from an initial to a final state by a reversible path and an
irreversible path.

How can we get ∆Ssys for the irreversible path?

Note that (qsys)irrev ≠ (qsys)rev since Path A and Path B are different. On the other
hand entropy is a state function and the final state is the same for both paths and
so ∆Ssys for the two paths must be the same. Thus the way to get (∆Ssys)irrev is to
devise a reversible path from the initial to the final state and use the equations
developed for the reversible case.

37
Find the value of ∆S of the system, surroundings and universe when 2 mol of
N2 at 300 K doubles in volume from 4 to 8 L for various processes. Assume
that the gas is ideal and that Cv,m = 20.8 J K-1 mol-1.

1. Reversible, isothermal:

Analysis:
Isothermal expansion so entropy of system should increase ∆Ssys > 0
Process is reversible so by the second law ∆Suniv = 0
Since ∆Suniv = ∆Ssys + ∆ssurr ∆Ssurr = - ∆ssys
Since gas is ideal gas we only need to know the initial and final states to find the
change in the system entropy via the general equation.

Calculation:
General equation for ideal gas

Since Ti = Tf the equation reduces to

38
2. Irreversible, isothermal expansion against constant external pressure of 1 atm (until
volume reaches 8 L). The initial and final states are as before.

Calculation
To get ∆Ssurr need to get the heat transferred to the system to keep the gas temperature
constant when the gas expands. For ideal gas, isothermal process

39
 3. Reversible, Adiabatic Expansion to final volume of 8 L

Calculation:
All entropy changes already calculated by simple analysis but we should calculate Tf and pf.
40
4. Irreversible Adiabatic Expansion to 8 L against a constant external pressure of 1 atm.

41
42
43
 ABSOLUTE ENTROPIES AND THE THIRD LAW

The experimental observation showed that changes in entropy approach

zero as the temperature approaches zero.

The statement:
The entropy of a perfect crystal is zero at 0 K

This is because a perfect crystal one in which all the atoms are
perfectly ordered in their lattice positions.

The equation:

44
In going from 0 K to some temperature T we need to account for the
possibility that the compound passes through all its physical states of
solid, liquid and gas. At each temperature where a phase transition
occurs there will be an entropy jump given by

Thus the most general change in the compound is

45
There are two types of randomness in crystals at absolute zero are
ignored in calculating entropies for chemical purpose only:

1. Most crystals are made up of a mixture of isotopes species. Because

the reactants and products I a rxn contain the same mixture of
isotopes, their entropies are ignored.
2. There is a nuclear spin at 0K that is ignored because it exists in both
reactants and products.

Entropy Change s for chemical reactions:

Recall that θ stands for the standard pressure of 1 atm (or 1 barr). As before
the temperature is taken as 298 K and Sθ(298) values are given in
Tables of thermodynamic data.
46
 α-D glucose] to give alcohol
Example: Fermentation of sugar [α

Value is > 0 since there are more products than reactants and
especially because of the gaseous product

47
How to calculate Sθ values at any temperature?

Example: Calculate Sθm for silver at 500 K given that Cp,m = 3R and
available Sθ(298) = 42.68 J K-1 mol-1

48