Thermodynamics :

 ‘William Thomson’ coined the term.

 Thermodynamics is the science of macroscopic systems, i.e. of systems composed of N particles
(atoms, molecules, ions, etc.),
 Thermodynamics deals with stability of systems which involves the study of temperature, heat
and their relation to energy, radiation, work, and properties of matter.

• The energy can be of any forms such as electrical, mechanical, or chemical energy.

System: Collection of objects we are examining.

Surrounding : The environment surrounding the system. Technically, it includes the rest of the universe.

 Some diathermal systems allow heat to travel in and out due to the diathermal walls. While,
some systems donot allow heat to flow in and out due to the adiabetic walls. No real system can
be truly adiabetic.

Internal Energy:

“the sum of all the molecular kinetic energies & the sum of all the molecular potential energies
exhibited by the particles of a substance.”

• It is represented by ‘U’.
• It is associated with the atomic motion.
• It is directly proportional to Temperature of a Sample.

Note :

 Substance doesn’t contain HEAT , it contains INTERNAL ENERGY.

Internal Energy can be increased due to :

1. Heat Transfer
2. Friction
3. Structural Deformation ( Bending a piece of metal or stretching a rubber band )
  Internal Energy can also be used to do work through “Heat Transfer”, “Pressure-Volume Work”
by an expanding gas or some other process. Thus, we can say that ;

‘the internal energy is a state function and it depends only on the state of the system &
NOT on how it got to that state.’
State function:
“ A measureable quantity that has a unique value for each given state of a system.”
Or
“Quantities which describes the state of a system.”

All state functions are path-independent and they can inter-related with oneanother.
Examples:

 Mass ( No. of moles ) , Volume , Temperature , Pressure, Entropy, Internal Energy etc.

Note :

• “ Work and Heat ” are not state functions or state variables.

Zeroth Law of thermodynamics:

It was proposed by R.H.Fowler.

“ If two systems are in thermal equilibrium with a third system then, those two are in thermal
equilibrium with eachother.”

If two objects are at the same temperature there will be no heat flow between them. This marks that
the temperature is therefore the indicator of thermal equilibrium.

First Law of thermodynamics:

First Law of thermodynamics is also known as the “law of conservation of energy” which states as;

“ Energy can neither be created nor be destroyed rather it can be converted into one form to another.”

It basically outlines the relationship between the internal energy (U) , work (W) & heat (Q).

ΔU=Q−W
Where ;
ΔU = Change in the internal energy

Q = Energy transferred to or from the system as heat.

W = Workdone on or by the system.
All these quantities will be measured in joules (J).
Metabolism in Human Body:
If we apply the first law of thermodynamics to the human body:

we know that the body can do work. If the internal energy is not to drop, there must be energy
coming in. It isn’t in the form of heat; the body loses heat rather than absorbing it. Rather, it is
the chemical potential energy stored in foods.
• The metabolic rate is the rate at which internal energy is transformed in the body.

Limitations of First Law of Thermodynamics:

• The limitation of the first law of thermodynamics is that it does not say anything about
the direction of flow of heat.
• It does not explains whether the process is a spontaneous process or not.
• The reverse process is not possible. In actual practice, the heat doesn’t convert
completely into work.
• If it would have been possible to convert the whole heat into work, then we could drive
ships across the ocean by extracting heat from the water of the ocean.
2nd Law of thermodynamics:
“ No cyclic process can convert heat into work with 100% efficiency”.
Or
“ Heat spontaneously flows from a region of high temperature to a region of low temperature,
and not the other way round.”

Entropy:
“ It represents the inevitable partial loss of an engine’s ability to convert the heat energy into
work.” .
 The amount of entropy is also a measure of the molecular disorder or randomness, of a
system.
 Entropy is a state function measured in J/K.
 It will be represented by the letter ‘S’.
S= Q/ T

S = 0 for a Carnot Engine.

Enthalpy:
“It represents the measure of heat in the system.”
The formula H = U + PV. H is the enthalpy value, U is the amount of internal energy, and P and
V are pressure and volume of the system.
Types of Exchange:
Two types of exchange can occur between system and surroundings:
(1) Energy exchange (heat, work, friction, radiation, etc.)
(2) Matter exchange (movement of molecules across the boundary of the system and
surroundings).
Types of Systems:
1. Open System. ( Matter and Heat Exchange )
2. Closed System ( Only Heat Exchange ; No Matter Exchange )
3. Isolated System ( No interaction of Heat & Matter )
 Isothermal Isobaric Iso-volumetric/ Isochoric Adiabetic
Constant temperature = Δ T = 0 Constant pressure = Δ P = 0 Constant volume = Δ V = 0 No heat transfer
ΔQ=0
ΔU =0 W = P ΔV ΔU = Q-0 =Q
Q-W Q =W W= P (V2 –V1 ) ΔU = -W
ΔQ= ΔU + P (V2 –V1 ) or
W = - ΔU
P = the actual pressure not
changing

This means that the heat Some heat is used to raise Heat given is used for rise in Internal energy of the system
energy given to the system is the temperature and part of it temperature. However, changes as a result of doing
then used by the system to used to do the work. No work is done on or by the work on its surroundings or
do work rather than system. surroundings doing work on
increasing the internal the system.
energy of the system.
EXAMPLES
Suppose we take a container
with water. Now, we heat it.
An ideal work of a car engine There is a pressure on it, i.e; the Bomb Calorimeter Processes occurring in Earth’s
atmospheric pressure. After Atmosphere.
sometime we find that these
molecule are converting into
vapours and the vapours takes a
larger volume. So, converting
into steam is actually the
change in the volume ; the work
is being done and due to the
heat the gas expands , but the
pressure remains constant as it
is an open system not a closed
system.
 Type of boundary Examples Interactions

Open A water in a container. All interactions possible

(Mass, Work, Heat)

Closed Cooling a water bottle in a fridge. Matter cannot enter or leave

Semi-permeable --- Only certain species can enter or leave

Insulated (Adiabetic) --- Heat cannot enter or leave

Rigid --- Mechanical work cannot be done*

Isolated Thermos flask No interactions are possible**

Quasi-Static Process

“ A process in which system remains close to an equilibrium state at each time, such process will be termed as
the quasi-static process or quasi-equilibrium process.”

For example, if a person is coming down from roof to ground floor with the help of ladder steps then it is a
quasi-static process. But if he jumps from roof to ground floor then it will not be a quasi-static process.

• An ideal process can be defined in which the deviation from thermodynamic equilibrium is infinitesimal.

Thermo-dynamic Equilibrium

If a system is in thermal, chemical and mechanical equilibrium, then we can say that this system is in thermo-
dynamic equilibrium.