Laws of Thermodynamics

CHEH 240 Lecture 3

Introduction
 Built on 4 Laws and “simple” mathematics
 0th Law ⇒ Defines Temperature (T)
 1st Law ⇒ Defines Energy (U)
 2nd Law ⇒ Defines Entropy (S)
 3rd Law ⇒ Gives Numerical Value to Entropy

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Thermal equilibrium

 If two closed system with fixed volumes are brought

together (thermal contact), what will happened?

 Changes may take place in the properties of both

and finally a state is reached in which there is no
further change, i.e. reach equilibrium and both
system will have the same final temperature.
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The Zero’th Law of Thermodynamic
 It is concerned with thermal equilibrium between three bodies, A, B
and C.

Consequences of the Zero’th law:

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First Law of Thermodynamics
 The 1st Law of Thermodynamics is “the law of
conservation of Energy”, which is a book keeping
equation to account for the interchange and
relationship among energy, work and heat.
 Leads to the definition of new thermodynamic state
function called internal energy (u) and also the
enthalpy (H) which can be defined in terms of p,V, and
U.
 First Law also deals with thermochemistry (heat
produced or absorbed during chemical reaction and
solution process).

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DEFINITION OF TERMS
1. Universe = System + Surroundings
2. Types of Systems (open, closed, and isolated)
3. Properties of the System (Extensive and Intensive)
4. State of the System (condition or state of the thing of
interest)
5. Path: This refers to how the initial state is changed to
the final state and specifies how the variables like
temperature, pressure and volume are changed to
bring about the change in state. (how you will go from
Jeddah to Madinah)
REVERSIBLE PATH: one in which the changes are done infinitely slowly
so that the system is always in a state of “equilibrium”. (moving
piston slowly)
IRREVERSIBLE PATH: this refers to a change which is done quickly and
with large finite changes in the variables – this is what happens in
real life. (drop weight on the piston suddenly).

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7. PATH FUNCTION: (work, heat) this is a quantity whose
value depends on how the system goes from the initial to
final state – it only appears when a system is undergoing a
change. For example, work is only done when an object is
moved against a force.
 STATE FUNCTION: (energy, entropy, enthalpy, Gibbs energy)
this is a quantity whose value depends on the state of the
system and not how it got there.

 8. INTERNAL ENERGY U is the total energy of all the

molecules in the system
 U =∑ kinetic energy (translation, vibration, rotation) +
potential energy (due to the interaction of the molecules)

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 Work, w
 Work : transfer of energy that can cause motion against an opposing force.
 In mechanics: work is defined in terms of the distance x that a force F moves an object.
Work = Force (F)x Length(L)

 In thermodynamics: work is usually expressed in terms of a pressure changing a volume rather than a force
moving through a distance. But these are equivalent.

where pext is the external pressures due to the weight;

dVgas is the volume change of the gas.

Note that:
pressure = force/area so force = pressure x area
w = force x distance = (pressure x area) x distance
= pressure x volume
Work unit is Joule = kg m2 s-2

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 Conventions for Work
Work is DONE ON the system [weight drops, gas is compressed,
gas energy increases] by the surroundings OR is DONE BY the
system [weight rises and gas expands] on the surroundings.
Doing work on the system [compressing a gas to a higher
pressure] increases the system energy since the gas has now a
greater potential to push back and do work back on the
surroundings - like compressing a spring.

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 How many paths do we have?
PATH 1: irreversible expansion
by knocking off two of the weights to get
to Vf .
PATH 2: irreversible expansion
by knocking off one weight and then
knocking off a second weight soon after
i.e. get to Vf by two successive step
changes in pressure.
PATH 3: reversible expansion
in which the weight is reduced in
infinitesimal steps so that as pext
changes it differs from pgas by an
infinitesimal amount, dp, and VI changes
to Vf in a smooth even fashion.
Since the gas is ideal we know how p
changes with V in this case.
i.e. p = nRT/V and a plot of p vs V
is hyperbolic.
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Work for an irreversible isothermal process

w   pext dV
f

wirrev   pext  dV
i

irreversible & const. pressure

f f

 w   p  dV
i
ext
i

wirrev   pext (V f  Vi )
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Work for an reversible isothermal process

w   pext dV
wrev   psystemdV (reversible)
pV  nRT (ideal gas )
dV
wrev   nRT
V
f f
dV
 w
i
rev   nRT 
i
V
Vf
wrev   nRT ln
Vi
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One mole of an ideal gas at 300 K in 1.0 L is expanded to 2.0 L
isothermally via two different paths. Calculate the work.
Path A: an irreversible expansion against a constant external pressure
of 12.3 atm –gas will expand until its pressure matches 12.3 atm.
Path B: a reversible, isothermal expansion until the final pressure is
12.3 atm.
•So, before doing any calculation you should do a simple analysis to predict
something about your answers and what equations to use.
•(i) Both paths are expansions so the work should be negative in value.
•(ii) Both paths lead to the same final state (p=12.3 atm, V= 2 L) but we know that
the irreversible work done BY the system is less in magnitude so the magnitude of
the work for path A should be less
•(iii) Irreversible work, constant external pressure w = -pextDV
Reversible work, constant pressure w = - pDV

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 Joule’s experiments

Adiabatic process: is one in which the system

is thermally isolated so that there is no
exchange of heat with the surroundings.

It was well known that heat and work both change the energy of a system.
Joule conducted a series of experiments under adiabatic condition which
showed the relationship between heat and work in a thermodynamic cycle for a
system.
He used a paddle to stir an insulated vessel filled with fluid.
The amount of work done on the paddle was noted (the work was done by
lowering a weight, so that work done = mgz).
The property of the system whose change calculated in this way is called the
internal energy (U).
∆U =w (in an adiabatic process)
Later, this vessel was placed in a bath and cooled. The energy involved in
increasing the temperature of the bath was shown to be equal to that
supplied by the lowered weight.

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 Heat, q
Heat: Transfer of energy as a result of Temp difference between
System & Surrounding
Or a change in the state of system (change in U) by allowing heat
to flow in and out.

•Heat change (q): that which is transferred from hot bodies to

cold ones during equilibration.
•Convention:
heat transfer into the system from hot surroundings is positive
heat transfer by the system to cold surroundings is negative. 17
 First Law of Thermodynamics
The increase in internal energy as a result of heat absorbed is diminished
by the amount of work done on the surroundings
The internal energy of a given system can
be changed from adding both heat and work

∆U = q + W
dU = q +  w =  q - pdV

By convention, heat added to the system,

 Q is positive
and work done by the system on its surroundings,
 w is negative.

This is also called the Law of Conservation of Energy

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For a closed system from an initial state
(p1, V1, T1) to a new state (P2, V2, T2),
and back to (P1, V1, T1) that the sum
of ‘q’ and ‘w’ transferred across the
boundaries of the system is zero.

Neither ‘q’ nor ‘w’ is a variable of state; the quantities exchanged around
closed paths of both heat and work can be non-zero; only the sum is
conserved.
We can, however, define a variable of state U, the internal energy, whose
change for a closed system is given by
dU = q + w = q – pdV

This is the First Law of Thermodynamics. Note: absolute values of U are

arbitrary; only its changes dU are significant

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 A gas was compressed by 300 J as work from the
surrounding, and 70 J heat was transferred from the gas to
the surrounding. Calculate the internal energy of the gas.

What is given:
The gas accept work from the surrounding
W is positive = +300 J
But, it lost heat to the surrounding
q is negative = -70 J

∆U = q + W = (-70 J) + 300 J = 230 J

For the Surrounding

∆U = - 230 J

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 If a gas is compressed from 400 ml to 200 ml under external
pressure with 3 atm and the gas evolved 13 J as heat, calculate
the change in the internal energy (∆U) and work for the gas and
change in the internal energy (∆U) for the surrounding.

What is given:
V1 = 400 ml = 0.4 L
V2 = 200 ml = 0.2 L
∆V = V2 –V1 = 0.2 – 0.4 = -0.2 L
q = -13 J and pext = 3 atm

W = - pext x ∆V = -3 atm x (-0.2 L) = 0.6 atm L

1 atm L = 101.3 J
W = 0.6 x 101.3 = 60.78 J
q = -13 J
∆U = q + W = (-13 J) + 60.78 J = 47.78 J

For the Surrounding

∆U = - 47.78 J

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 Two moles of gas at 1 bar and 298 K are compressed at
constant T by use of 5 bar pressure. How much work is
done on gas? If the compression is driven by 100 kg mass,
how far will it fall in the earth’s gravitational filed?

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 Work for an irreversible isothermal process
According to VDW equation
 
   nRT
2
 p  an V  nb
 V 2 
 
 2 
 p  an   nRT

 V2 

V  nb 
nRT an 2
p 

V  nb  V 2

The equation for the max work of isotherm expansion of a VDW gas:
dWrev = - pdV
V2
 nRT an 2 
 dV
W rev   dW rev    
 V  nb
V1 

V2  

V2
 nRT an 2 
 dV
W rev   dW rev    
 V  nb
V1 

V2  


V 2  nb 2 1 1 
W rev   nRT ln  an   
V1  nb  V1 V 2 
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