THE FIRST LAW OF THERMODYNAMICS

• The FIRST LAW OF THERMODYNAMICS is a special case of

the LAW OF CONSERVATION OF ENERGY
• The amount of work transferred is
equal to the heat transferred.

𝑸𝒏𝒆𝒕 = 𝑾𝒏𝒆𝒕

• A cycle means the initial and final

states are the same.
• This process would not be isolated
• On PV diagram, a cyclic process is
represented as closed curve.
• Thus the internal energy must be zero.
• The change of internal energy of
the system is the difference
between the heat entering the
system from surrounding, and
work energy leaving the system.

Δ𝐸 = 𝑄 − 𝑊

• Energy stored by a system, and it

is neither heat nor work, is called
internal energy.
• Consider a system which changes
its state from state 1 to 2 by
following path A and return from
state 2 by following path B.
• Change in energy between two
states of the system will be the
same even if the system retuned
from state 2 to state 1 by
following the path C instead of B.
• Therefore, energy has definite
value for every state of the
system.
• Hence, it is a point function and a
property of the system.
Energy is the capacity to do work.

In thermodynamics, energy can be stored in two

forms:
• Energy in transit
• Work and heat interactions are the forms of energy transit,
observed at the boundaries of a system.
• They are not properties of a system.
• They are path functions, their magnitudes depend upon the
path system follows during a change of state.
• Energy in storage
• Energy in storage is internal energy.
• Is a point or state function.
• Thus it is a property of a system.
 Two modes in which energy
may be stored in a system
Macroscopic energy
mode
Microscopic energy
• Macroscopic kinetic energy
• Macroscopic potential
mode
energy
• Macroscopic kinetic
energy
• Consider a fluid
element of mass m
having the mass
velocity V (as shown in
figure).
• The macroscopic
kinetic energy EK of the
fluid element by virtue
of its motion is given
by:
• Macroscopic potential
energy
• If the elevation of the
fluid element from an
arbitrary datum is z,
then the macroscopic
potential energy EP by
virtue of its position is
given by:

Where g is the
acceleration due to
gravity
• Refers to the energy stored in the molecular and atomic
structure of the system, which is called the molecular
internal energy or simply internal energy, customarily
denoted by the symbol U.
• For example, gas, is composed of molecules. Molecules are in
random thermal motion with an average velocity v, constantly
colliding with one another and with the walls. Due to a collision,
the molecules may be subjected to a rotation as well as
vibration, and can have different kind of internal energy.
• If ℰ represent the energy of one molecule, then,
ℰ = ℰ𝑡𝑟𝑎𝑛𝑠 + ℰ𝑟𝑜𝑡 + ℰ𝑐ℎ𝑒𝑚 + ℰ𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑖𝑐 + ℰ𝑛𝑢𝑐𝑙𝑒𝑎𝑟 + ⋯

• If N is the total number of molecules in the system,

then total internal energy is
𝑈 = 𝑁ℰ
• Defined as the rate of change of specific energy with respect
to temperature when the volume is held constant.
𝛿𝑢
𝑐𝑣 =
𝛿𝑇 𝑣
• For constant volume process
𝑇2

Δ𝑢 𝑣 = න 𝑐𝑣 𝑑𝑇
𝑇1
• When volume is held constant
𝑇2

𝑄 𝑣 = න 𝑐𝑣 𝑑𝑇
𝑇1
• The enthalpy of a substance, h, is defined as:
ℎ = 𝑢 + 𝑝𝑣
Where,
u is the specific internal energy, kJ/kg
P is pressure, kPa
v is specific volume, m3/kg

• Enthalpy of an ideal gas depend only on temperature as

the internal energy of an ideal gas depends only on the
temperature:
ℎ = 𝑢 + 𝑅𝑇
• 𝑐𝑝 is defined as the rate of change of enthalpy with
respect to temperature when the pressure is held
constant:
𝛿ℎ
𝑐𝑝 =
𝛿𝑇 𝑝
• Since h, T and P are properties, so 𝑐𝑝 is the property of
the system. Like 𝑐𝑣 , 𝑐𝑝 should not be defined in terms of
heat transfer of constant pressure, although 𝛿𝑄 𝑝 = 𝛿ℎ.
• For a constant pressure process:
𝑇2

Δh p = න 𝑐𝑝 ⋅ 𝑑𝑇
𝑇1
• For a closed stationary system of unit mass:
𝑇2

𝑄 𝑝 = න 𝑐𝑝 𝑑𝑇
𝑇1
• 𝑐𝑝 is a property of the system just like 𝑐𝑣 . The heat
capacity at constant pressure 𝑐𝑝 is equal to 𝑚𝑐𝑝 (J/K).
• An isolated system is one in which is no interaction of
the system with the surroundings.
• For isolated system:
• 𝛿𝑄 = 0
• 𝛿𝑊 = 0
• The first law of isolated system given as:
• 𝛿𝐸 = 0
• 𝐸 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

Energy of an isolated system is always constant

 Positive interaction Negative interaction

Q SYSTEM W W SYSTEM Q
• A stationary mass of gas is compressed without friction
from an initial state of 0.3m3 and 0.105MPa to a final
state of 0.15m3 and 0.105MPa, the pressure remaining
constant during the process. There is a transfer of
37.6kJ of heat from the gas during the process. How
much does the internal energy of the gas change?
• A piston and cylinder machine contains a fluid system
which passes through a complete cycle of four processes.
During a cycle, the sum of all heat transfers is -170kJ. The
system completes 100 cycles per min. Complete the
following table showing the method for each item, and
compute the net rate of work output in kW.
Process Q (kJ/min) W (kJ/min) 𝚫𝐄 (kJ/min)
ab 0 2170
bc 21000 0
cd -2100 -36600
da