Heat &

Thermodynamics
Phy 107 course
Zaid Bin Mahbub (ZBM)
DMP, SEPS, NSU
One of the principal branches of physics and engineering is thermodynamics, which is the study and
application of the thermal energy (often called the internal energy) of systems. One of the central
concepts of thermodynamics is temperature.

Temperature is one of the seven SI base quantities. Physicists measure temperature on the Kelvin scale,
which is marked in units called kelvins. Although the temperature of a body apparently has no upper
limit, it does have a lower limit; this limiting low temperature is taken as the zero of the Kelvin
temperature scale.
The Zeroth Law of Thermodynamics

If bodies A and B are each in thermal equilibrium with a third body T, then A and B are in thermal
equilibrium with each other.

(a) Body T (a thermoscope) and body A are in thermal equilibrium. (Body S is a thermally insulating
screen.) (b) Body T and body B are also in thermal equilibrium, at the same reading of the
thermoscope. (c) If (a) and (b) are true, the zeroth law of thermodynamics states that body A and
body B are also in thermal equilibrium.
Heat Transfer

Heat is the energy transferred between a system

and its environment because of a temperature
difference that exists between them.

The SI unit for heat should be the one we use for

energy—namely, the Joule.

The calorie is now defined to be 4.1868 J (exactly),

with no reference to the heating of water.

The “calorie” used in nutrition, sometimes called

the Calorie (Cal), is really a kilocalorie.
 Thermodynamic Process

The walls of the cylinder are made of insulating material that does not
allow any transfer of energy as heat. The bottom of the cylinder rests on a
reservoir for thermal energy, a thermal reservoir (perhaps a hot plate)
whose temperature T you can control by turning a knob.

The system (the gas) starts from an initial state i, described by a pressure
Pi, a volume Vi, and a temperature Ti.

You want to change the system to a final state f, described by a pressure Pf,
a volume Vf , and a temperature Tf .

The procedure by which you change the system from its initial state to its
final state is called a thermodynamic process.
 Thermodynamic Process

Suppose that you remove a few lead shot from the piston of Fig, allowing the gas to push the piston
Ԧ
and remaining shot upward through a differential displacement 𝑑 𝑠Ԧ with an upward force 𝐹.

Since the displacement is tiny, we can assume that 𝐹Ԧ is constant during the displacement. Then 𝐹Ԧ has a
magnitude that is equal to pA, where p is the pressure of the gas and A is the face area of the piston.
The differential work dW done by the gas during the displacement is,

𝑑𝑊 = 𝐹. 𝑑𝑠 = 𝑝𝐴. 𝑑𝑠 = 𝑝 𝐴. 𝑑𝑠 = 𝑝𝑑𝑉

𝑉
Thus total work done, 𝑊 = ‫𝑉𝑑𝑝 𝑓 𝑉׬ = 𝑊𝑑 ׬‬
𝑖

F P

x V
(a) The shaded
area represents the work W
done by a system as it goes
from an initial state i to a final
state f. Work W is positive
because the system’s
volume increases. (b)W is
still positive, but now
greater. (c)W is still positive,
but now smaller. (d)W
can be even smaller (path
icdf ) or larger (path ighf).
(e) Here the system goes
from state f to state i as the
gas is compressed to less
volume by an external
force. The work W done by
the system is now negative.
( f ) The net work Wnet done
by the system during
a complete cycle is represented
by the shaded area.
Path dependent work done! Non conservative case!!
First law of thermodynamics

You have just seen that when a system changes from a given initial state to a given final state, both the work W and
the heat Q depend on the nature of the process.

Experimentally, however, we find a surprising thing. The quantity 𝑄 − 𝑊 is the same for all processes.

It depends only on the initial and final states and does not depend at all on how the system gets from one to the
other. All other combinations of Q and W, including Q alone, W alone, Q + W, and Q - 2W, are path dependent;

only the quantity 𝑄 − 𝑊 is path independent.

First law of thermodynamics
The quantity 𝑄 − 𝑊 must represent a change in some intrinsic property of the system.
We call this property the internal energy Eint and we write

∆𝑬𝒊𝒏𝒕 = 𝑬𝒊𝒏𝒕,𝒇 − 𝑬𝒊𝒏𝒕,𝒊 = 𝑸 − 𝑾

𝒅𝑬𝒊𝒏𝒕 = 𝒅𝑸 − 𝒅𝑾

The internal energy Eint of a system tends to increase if energy is added as heat Q and tends to decrease if
energy is lost as work W done by the system.

The first law of thermodynamics states that whenever heat is added to a system, it transforms
to an equal amount of some other form of energy.

𝑸 = ∆𝑬𝒊𝒏𝒕 + 𝑾

This added energy does one or both of two things: (1) increases the internal energy of the system if it remains
in the system and (2) does external work if it leaves the system.

For an ideal gas, the internal energy Eint depends only on temperature, not on pressure or volume
The translational kinetic energy K of the molecules in an ideal gas is related to the absolute temperature by:
3
𝐾 = 𝑛𝑅𝑇
2

Where n is the number of moles of gas and R is the universal gas constant.

If the internal energy of a gas is just this translational kinetic energy, then
3
𝐸𝑖𝑛𝑡 = 𝑛𝑅𝑇
2

Then, the internal energy will depend only on the temperature of the gas, and not on its volume or pressure.

If the molecules have other types of energy in addition to translational kinetic energy, such as rotational energy, the
internal energy will be greater than that given by the equation.

1
But according to the equipartition theorem, the average energy associated with any degree of freedom will be 𝑅𝑇
2
per mole, so again, the internal energy will depend only on the temperature and not on the volume or pressure.
The 1st law, however, does not necessarily tell us which direction a spontaneous change will occur. While
in many cases systems will tend towards energy minima, this isn't always the case. An ice cube at a
temperature above freezing will spontaneously melt, this melting requires energy to be added to the
system.

A reversible process is defined as a process that can be reversed without leaving any trace on the
surroundings. It means both system and surroundings are returned to their initial states at the end of the
reverse process. Reversible processes do not occur and they are only idealizations of actual processes.

Some factors that cause a process to become irreversible:

• Friction • Unrestrained expansion and compression • Mixing • Heat transfer (finite ΔT) • Inelastic
deformation • Chemical reactions
Entropy and the Second Law of Thermodynamics

The second law of thermodynamics tells

us that heat naturally flows from a hot
body (such as molten lava, shown here
flowing into the ocean in Hawaii) to a
cold one (such as ocean water, which is
heated to make steam). Is it ever possible
for heat to flow from a cold body to a hot
one?
A process whose only net result is to absorb heat from a cold reservoir and release the same amount of heat to a hot
reservoir is impossible.
CLAUSIUS STATEMENT

No system can absorb heat from a single reservoir and convert it entirely into work without additional net changes in
the system or its surroundings.
KELVIN STATEMENT

It is impossible for a heat engine working in a cycle to produce only the effect of absorbing heat from a single
reservoir and performing an equivalent amount of work.
HEAT-ENGINE STATEMENT

If an irreversible process occurs in a closed system, the entropy S of the system always increases; it never decreases.
ENTROPY STATEMENT
Change in entropy:
𝒇
𝒅𝑸
∆𝑺 = 𝑺𝒇 − 𝑺𝒊 = න
𝒊 𝑻
Here Q is the energy transferred as heat to or from the system during the process, and T is the temperature of the system
in kelvins.

Thus, an entropy change depends not only on the energy transferred as heat but also on the temperature at which the
transfer takes place.

Because T is always positive, the sign of S is the same as that of Q.

The SI unit for entropy and entropy change is the joule per kelvin (J/K).

The Second Law of Thermodynamics

If a process occurs in a closed system, the entropy of the system increases for irreversible processes and remains constant
for reversible processes. It never decreases.

In equation form, ∆𝑆 ≥ 0
A Statistical View of Entropy

The macroscopic properties of gases can be explained in terms of their microscopic, or molecular, behavior.
Such explanations are part of a study called statistical mechanics.

The number of microstates that correspond to a given configuration 1 or 2, the multiplicity W of that
configuration.
𝑁!
𝑊=
𝑛1 ! 𝑛2 !
All microstates are equally probable.
2
𝑆 = 𝑘𝐵 ln 𝑊 (Boltzmann’s entropy equation).

During an irreversible process, the entropy of the universe increases.

For any process, the entropy of the universe never decreases.

1
When firecrackers explode, disorder
increases:
The neatly packaged chemicals
within each firecracker are dispersed
in all directions, and the stored
chemical energy is converted to
random kinetic energy of the fragments.

The mixing of colored ink and

water starts from a state of relative order
(low entropy) in which each fluid is separate
and distinct from the other. The final
state after mixing is more disordered (has
greater entropy). Spontaneous unmixing of
the ink and water, a process in which there
would be a net decrease in entropy, is
never observed.
A System is in Equilibrium if its Properties or Variables do not change with time.

– Thermal Equilibrium
No Temperature or Pressure Gradients in the System.

– Mechanical Equilibrium
No Unbalanced Forces or Torques in the System.

– Chemical Equilibrium
No tendency of the System to undergo Chemical Reaction or Diffusion.

– Electrical Equilibrium
No Electrical Potential Gradients in the System.
A state variable is a property of a system that depends only on the current, equilibrium state of the system and thus do
not depend on the path by which the system arrived at its present state.

Internal Energy Eint:

Internal energy is a state variable that can be thought of as the energy of the system (sensible, latent, chemical bond,
nuclear etc.).

Enthalpy H:
Enthalpy is a state variable that is most easily thought of as heat energy, although strictly speaking it's only heat energy
in a system that is at constant pressure and which experiences no other work (other than constant pressure expansion).

Entropy S:
Entropy has many definitions, many of which are applicable under specific circumstances. We'll think of S as a measure
of disorder, i.e. higher values of S are systems with greater disorder. A similar but slightly different view is that S
represents the number of possible states for a system.
Variables that do depend on path are known as (not surprisingly) path variables.

Heat energy Q:
The heat exchanged between a system and its environment for some change in state is a path variable.

Work W:
The work exchanged between a system and its environment for some change in state is a path variable.