THERMODYNAMICS

WORK, ENERGY AND HEAT

• Thermo=energy and dynamics=transformations
• Thermodynamics tries to establish relationships between different properties
of matter and the way they change after undergoing processes
• To describe and make predictions about the behaviour of the system in terms
of its energy as well
• We are going to look at changes in the state of matter before and after a
process
• Thermodynamics is a universal law
 Thermodynamics
• Thermodynamics is conducted under a system-centered view of
the universe.
• The Universe is divided into two parts: System and its
Surroundings
• Thermodynamic system, ( working substance), is defined as
that part of the universe that is under consideration.
• A hypothetical boundary separates the system from the rest of
the universe, which is referred to as the environment,
surroundings, or reservoir.
• Thermodynamics is basically concerned with the flow and
balance of energy and matter in a thermodynamic system.
Three types of thermodynamic systems are distinguished based on the possible
transfer of mass and energy upon the system boundaries:
• (1) Open systems: exchanging energy (heat and work) and matter with their
environment.
• A boundary allowing matter exchange is called permeable. The ocean would be
an example of an open system????.

• (2) Closed systems :

• * Able to exchange energy (heat and work) with their environment.
• * No transfer of mass with its surroundings
• Whether a system exchanges heat, work or both is usually thought of as a
property of its boundary. e.g closed flask
(3) Isolated systems : completely isolated in every way from their
environment. Is not influenced in any way by the surroundings.
* No energy in the form of heat or work may cross the boundaries
* No mass may cross the boundaries of the system
Example, insulated rigid container, such as an insulated gas cylinder
Energy: a property of matter that makes things happen, or in case of
stored or potential energy, has the potential to make things happen.
Changing a property of a system, like pressure, temperature, volume
etc is due to energy.
Nature of Energy

• The internal energy(U) of a system is the total kinetic and potential

energy of the molecules in the system𝑈 = σ 𝐾𝐸 + σ 𝑃𝐸
• It is denoted by ΔU the change in internal energy when a system
changes from an initial state i with internal energy 𝑈𝑖 to a final
state f of internal energy 𝑈𝑓 : Δ𝑈 = 𝑈𝑓 − 𝑈𝑖
• The internal energy is a state function its value depends only on
the current state of the system and is independent of how that
state has been prepared.
 Measuring Internal Energy
Internal energy, heat, and work are all measured in the same units, the joule (J).
1 J = 1 kg m2 s −2
Heat and work are equivalent ways of changing a system’s internal energy.
We are interested in ∆ 𝑈
If the System loses Energy via heat or work, ∆ 𝑈 < 0
The Surroundings , ∆ 𝑈 > 0 ∴ ∆𝑈 𝑠𝑦𝑠 = −∆𝑈𝑠𝑢𝑟𝑟
First law of thermodynamics

The Surroundings , ∆ 𝑈 > 0 ∴ ∆𝑈 𝑠𝑦𝑠 =

− ∆𝑈𝑠𝑢𝑟𝑟
 Work, heat and energy

• The fundamental physical property in thermodynamics is work.

• Work: is the motion against an opposing force, e.g. raising a weight
somewhere in the surroundings or expansion of a gas that pushes out
a piston and raises weight.
• When work is done on an otherwise isolated system (for instance, by
compressing a gas), the energy of the system is increased.
• When the system does work (when the piston moves out or the spring
unwinds), the energy of the system is reduced and it can do less work
than before.
• Energy can be neither Created nor destroyed, merely be transformed
from one form to another.
 Work, heat and energy
• When the energy of a system changes as a result of a
temperature difference between the system and its surroundings
this means that energy has been transferred as heat.
• An exothermic process is a process that releases energy as heat
into its surroundings.
• An endothermic process is a process in which energy is acquired
from its surroundings as heat. An example of an endothermic
process is the vaporization of water.
• If a system is isolated from its surroundings, then no change in
internal energy takes place.
• A diathermic system (Diabatic) is one in
which heat can go in or
out of the system. Adiabatic: An adiabatic
system is one in which heat cannot go in
or out of the system.
• (a) When an endothermic process occurs
in an adiabatic system, the temperature
falls;
• (b) if the process is exothermic, then the
temperature rises.
• (c) When an endothermic process occurs
in a diathermic container, energy enters as
heat from the surroundings.
• (d) If the process is exothermic, then
energy leaves as heat, and the process is
isothermal.
• In molecular terms, heating is the
transfer of energy that makes use of
disorderly molecular motion. The
disorderly motion of molecules is called
thermal motion.

• In contrast, work is the transfer of

energy that makes use of organized
motion. When a weight is raised or
lowered, its atoms move in an organized
way (up or down).
 Measuring changes in internal energy
• Lets consider infinitesimally small changes, 𝑑𝑈 = 𝑑𝑞 + 𝑑𝑤 (dw
and dq inexact differential and difficult define initial and final
state)
𝑈𝑓
• ‫ 𝑞𝑑 ׬ = 𝑈𝑑 𝑖𝑈׬‬+ 𝑑𝑤 = 𝑈𝑓𝑖𝑛𝑎𝑙 − 𝑈𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = 𝑞 + 𝑤
• ∆𝑈 = 𝑞 + 𝑤
• U is a state function (capital letter), path-independent (it depends
only on final and initial states, q+w are non-state functions and
are path-dependent.
• This equation is the mathematical statement of the First Law, also
shows the fact that the internal energy is constant in an isolated
system (for which q = 0 and w = 0).
Example
WORK
A typical physics example d𝑤 = 𝐹 𝑑𝑥

Displacement is necessary for work to occur

• Pressure-volume work-work involving a gaseous system
expanding or contracting against an external pressure.

• Expansion and Contraction of a

gas (increase in volume and
decrease in volume respectively)
Expansion work
• Expansion work=Pressure-volume
work (system expands against an
opposing pressure)
• P1 and Pext are both pushing dx
against the frictionless piston
• For expansion P1>Pext
• The gas expands until there is a
mechanical equilibrium Pint=Pext
• 𝑑𝑤 = 𝐹 𝑑𝑥 𝐹 = 𝑃𝐴
𝐹 = −𝑃𝑒𝑥𝑡. 𝐴
𝑑𝑤 = −𝑃𝑒𝑥𝑡. 𝐴. 𝑑𝑥
𝑑𝑤 = −𝑃𝑒𝑥𝑡. 𝑑𝑉
Work done by a gas as it expands (dV) and drives back the atmosphere.
This means that the gas is doing work on the surrounding, volume (𝑑𝑣
+) increases and 𝑑𝑤 is negative and decreases internal energy.
 Example: Ideal gas expansion at constant T
• Pext is constant throughout
the process
• Integrate (Vi to Vf) to get total
work done
• ‫ ׬ = 𝑤𝑑 ׬‬−𝑃𝑒𝑥𝑡𝑑𝑉
𝑤 = −𝑃𝑒𝑥𝑡∆𝑉
• The shaded area is the work
done by the gas
P2
• The work done is minimum
during irreversible expansion
• ∆𝑉 +∴ 𝑤 −
Contraction work
• Contraction work=Pressure-
volume work (system contracts
against an opposing pressure)
• The gas contracts until there is a dx
mechanical equilibrium Pint=Pext
(P1=Pext)
• 𝑑𝑤 = −𝑃𝑒𝑥𝑡. 𝑑𝑉 (volume is
decreasing)
• ∆𝑉 −∴ 𝑤 +
• Work is done by the surrounding
on the system, internal energy of
the system will increase.
•
Example of compression work of an ideal gas
at constant temperature
• Pext >Pint
• Compression work is larger than
expansion, however work is
positive for the system because
the surroundings does the work
• This process is still irreversible
• The shaded area represents
work done during compression
NOTE
• This equation was derived for a cylinder and a piston, but its applicable to
systems of any shape.
• Although the equation was derived for a gas, it is applicable to any state
of matter.
• The pressure appearing in this expression in the external pressure not
internal.
• This is because work is observed and evaluated in terms of changes
brought about in the surroundings not changes taking place in the system.
• This equation applies to a system undergoing an infinitesimal change or
process.
• If we are interested in calculating the work done during a finite process
we must imagine that the finite process has been divided into an infinite
number of infinitesimal step, and the results obtained for every step are
summed up to give the work done for the entire finite process
• Mathematically this summation corresponds to the process of integration
Expansion at constant P and T:multiple steps
process (Reversible)
• Infinite number of steps, the entire region under the curve gets
more and more shaded
• Amount of work done will be equivalent to the area under the curve
and the Pext comes closer and closer to the Pgas (gas does maximum
work)
• Each step is accompanied by a mechanical equilibrium
• Each step is reversible, this is reversible work