Microscopic Energy

P M V Subbarao
Professor
Mechanical Engineering Department

A Thermodynamic Property of Substances…..

Hydro Electric Plant : The Work Done by A Falling Water
psur = patm Ligament patm

H
 Microscopic Energy

• This energy is defined as the energy associated with the

random, disordered motion of molecules and due to
intermolecular forces.
• It is separated in scale from the macroscopic ordered
energy associated with moving or stationary objects;
• It refers to the invisible form of energy at atomic and
molecular scales.
• Popularly known as Internal Energy, U.
 Internal (Microscopic) Energy : Ideal Gas
• Internal energy involves energy at the microscopic scale.
• Potential and Kinetic energies of individual molecules/atoms.
• But the potential energy is associated with intermolecular forces
which are presumed to be zero in an ideal gas.
• Therefore the internal energy of an ideal gas is entirely kinetic
energy.
Internal (Microscopic) Energy : Monatomic Ideal Gas
• For an ideal monatomic gas, this is just the translational
kinetic energy of the linear motion of the "hard sphere" type
atoms.
For a monatomic ideal gas this change
in internal energy is given by :
~ 3 ~
U  nR T
2

3
U  mRT
2
 Internal (Microscopic) Energy : Diatomic Ideal Gas
• For polyatomic gases there is rotational
and vibrational kinetic energy as well.
Internal (Microscopic) Energy : Polyatomic Ideal Gas
 Internal (Microscopic) Energy : Other Substances
• Then in real gases, liquids and solids there is potential energy
associated with the intermolecular attractive forces.
 Increase of Internal Energy

Supply enough heat to each of these systems till the there is 1C
increase in temperature.
Internal Energy and Temperature
 Internal Energy of an Ideal Gas
• Internal energy in general includes both kinetic energy and
potential energy associated with the molecular motion.
• But the potential energy is associated with intermolecular
forces which are presumed to be zero in an ideal gas.
• Therefore the internal energy of an ideal gas is entirely
kinetic energy.
• For a monoatomic ideal gas this change in internal energy is
given by
3
U  nRT
2

•If rotation and vibrational kinetic energies are involved

(polyatomic molecules) then
f f : Number of degrees of freedom of
U  nRT
2 a molecule
 Means to Measure Energy

• Macroscopic Energy: Easy to measure.

• Microscopic Energy: Needs a detailed experiment.
• Identify methods to measure economically.
 Measurement of Change in Internal Energy
• First law for A control mass:

Q  dU  pdV
1Q2 = U2 – U1 Constant Volume Heating

• Consider a homogeneous phase of

a substance with constant
composition.
• Define Specific Heat: The amount
of heat required per unit
mass/mole to raise the temperature
by one degree.
• No change in other forms of
energy, except internal energy.
 Constant Volume Specific Heat

• The molar specific heat at constant volume is defined by

• For a monatomic ideal gas,

U 2  U1  nRT2  T1 
3
2

f
U  nRT
2
CV Specific Heats of Ideal Gases

Experimental
results
 Constant Volume Heat Capacity
Gas
CV(J/mol K) CV/R
Ar 12.5 1.50
He 12.5 1.50
CO 20.7 2.49
H2 20.4 2.45
HCl 21.4 2.57
N2 20.6 2.49
NO 20.9 2.51
O2 21.1 2.54
Cl2 24.8 2.98
CO2 28.2 3.40
CS2 40.9 4.92
H2S 25.4 3.06
N2O 28.5 3.42
SO2 31.3 3.76
 Polytropic Process of A Control Mass
• Polytropic process of a control mass:

q  du  pdv

u 2  u1 R
Cn  
T2  T1 1  n 
 Measurement of Changes during Constant Pressure
Process

• Constant pressure heating of a

control mass:

1 Q2  U 1W2 Constant Pressure Heating

1 Q2  U  pV2  V1 
 Changes during Constant Pressure Process
• Infinitesimal constant pressure heating process by a control mass:
Q  dU  W Q  dU  pdV
Q  dU  pdV  Vdp  Vdp
Q  dU  d  pV 
The quantity pV is also having a
behaviour of property !
This is called flow energy, flow work or
internal work. Constant Pressure Heating
However, the significance of this
property is not felt in a Control Mass.
Q  d U  pV 
Another way of representing this
effect is to combine U and PV.
Let this be H.
The issue of Increasing unit Temperature of A Pure
Substance
 Flow Work or Flow Energy
• Unlike control mass, control volumes involve mass flow across
their boundaries.
• The substance inside a control volume will be at some pressure,
temperature…..
• The fluid entering the control volume is pushing itself against
the pressure of the control volume.
• Some work transfer is involved in pushing this mass into the
control volume.
• This is an internal work.
• This is called flow work or flow energy.
 Visualization of Flow Work

F p

• F= pA will be a driving force responsible for the pushing

of the fluid into the CV.
• This force will perform a work transfer of F.L to push the
fluid.
• Therefore, the flow work = F ×L = p × A × L = p × V
• This can exists even when there is a fluid pushed out of the
CV.
 Flow work

• It is interesting to note that unlike other work quantities, the

flow work is expressed in terms of state variables.
• This is also a state variable, point function and hence a
thermodynamic property.
• This is also called flow energy, convected energy or transport
energy.
• The total energy of non flowing fluid: E = m(u + ½V2 + gz)
• The total energy of flowing fluid: Q =m(u + pv + ½V2 + gz).
• This total energy is also called as Methalpy.
• The term u + pv is called as specific Enthalpy, h.
 Energy transport by Moving fluid
• Amount of energy transport by a moving fluid of mass m:
Q = mθ = m ( h + ½V2 + gz )
• Rate of Energy Transport:

  V 2

Q  m   h   gz 
 2 
 Internal Energy & Enthalpy of Wet Mixtures
• x is the dryness fraction.
• U = (1-x) Uf + x Ug
• Specific Internal energy: Internal energy per unit mass ; u
• u = (1-x) uf + x ug
• Specific enthalpy
• h = (1-x) hf+ x hg

T
ufg

uf u ug