Concept of Thermodynamics

Thermodynamics
Thermodynamics describes how thermal energy is converted to and from other
forms of energy and how it affects matter. It helps us to predict whether any
chemical reaction can occur under the given set of conditions and to predict the
extent of the reaction before the equilibrium is attained
Some important terms used in this concept are as follows-
System
The part of the universe chosen for thermodynamic consideration is called a system.
Surroundings
The remaining portion of the universe excluding the system is called surroundings.
Universe system surroundin gs

Open system
A system is said to be an open system if it can exchange both matter and energy with
the surroundings.
Closed system
If a system can exchange only energy with the surroundings but not matter, it is
called a closed system.
Isolated system
If a system can neither exchange matter nor energy with the surroundings, it is called
an isolated system.
Extensive properties
These are the properties which depend upon the quantity of matter contained in the
system. e.g., mass, volume and heat capacity.
Intensive properties
Unlike extensive properties these properties depends only on nature of the
substance. e.g., temperature, pressure, density.

State of a System
The state of a system means the condition of the system which is described in terms
of certain observable properties as temperature, pressure volume etc. of a system.
Path functions
Path functions are properties or quantities whose values depend on the transition of
a system from the initial state to the final state. E.g., Heat and work.
State functions or variables
A physical quantity is said to be state function if its value depends only upon the
state of the system and does not depend upon the path by which this state has been
attained. E.g., pressure, volume, temperature.

Thermodynamic equilibrium
A system is said to be thermodynamic equilibrium if its macroscopic properties like
temperature, pressure do not change with time. For thermodynamic equilibrium to
occur these three equilibrium must occurs simultaneously in the system
1. Chemical Equilibrium : A system in which the composition of the system remains
fixed and definite.
2. Mechanical Equilibrium : No chemical work is done between different parts of the
system or between the system and surrounding.
3. Thermal Equilibrium : Temperature remains constant.

Thermodynamic process : When the thermodynamic system changes from one state
to another, the operation is called a process.
The various types of the processes are
Isothermal process : Temperature is constant throughout the process.
Adiabatic process : In this process there is no heat flow between system and
surrounding.
Isochoric process : In this process volume of the system is kept constant.
Isobaric process : In this process pressure of the system is kept constant.

Reversible process
It is a process which is carried out infinitesimally slowly so that all changes occurring
in the direct process can be exactly reversed and the system remains almost in a
state of equilibrium with the surroundings at every stage of the process.
Irreversible process
A process which is not carried out infinitesimally slowly so that the successive steps
of the direct process cannot be reversed and any change in the external conditions
disturbs the equilibrium.
Cyclic processes
A cyclic process is a sequence of processes that leaves the system in the same state
in which it started.

Internal energy of a system, E

The sum of the kinetic and potential energies of all the particles making up a
substance is referred to as the internal energy.
Total energy, ET of a quantity of substance is the sum of its kinetic and potential
energies as a whole (EK + EP) plus its internal energy.

ET = EK + EP + U

Total internal energy of a gas

Gas molecules have energy due to various motions, such as translational, vibrational
and rotational motions and according KTG gas molecules dot have potential energy.
All the different modes that contribute to the total internal energy of a gas molecule
are called degrees of freedom.
A monoatomic gas molecule has three degrees of freedom; a diatomic molecule has
five degrees of freedom while each triatomic molecule and subsequent polyatomic
molecules are considered to have six degrees of freedom.

ILLUSTRATIONS

Example 1. Explain why thermos flask is an isolated system .

Solution:
As no exchange of energy or matter take place through its walls, so thermos flask is
an isolated system.

Example 2. Show that refractive index is an intensive property.

Solution:
Refractive index is an intensive property because it does not depend on amount of
matter but on its nature.

Example 3. Work is not a state function . Justify

Solution:
Work is not a state function as during a process its value depends on the path
followed. The value of enthalpy, internal energy and entropy depends on the state
and not on the path followed to get that state, hence these are state functions.

Example 4. The total internal energy change for a reversible isothermal cycles is?
Solution:

Since E 0 for isothermal reversible cycle.

As When a system is carried through a cyclic process its initial and final internal
energies are equal.

Example 5. Internal Energy is a state function or a path function? What do you

actually interpret form this statement?
Solution:
Internal Energy is a state function; it means that whatever path we take the change
in internal energy is independent of the path taken. For instance if we consider that
we move from A to B and then B to C which have UA, UB and UC internal energies
respectively. Then total or net change in internal energy would be UC UA.

EXERCISE
Q 1. Identify the intensive quantity from the following
(a) Enthalpy and temperature
(b) Volume and temperature
(c) Enthalpy and volume
(d) Temperature and refractive index
Ans. d)
Because they do not depend on amount of matter but on its nature.

Q 2. Reaction occuring in a closed vessel is an example of

(a) Closed system
(b) Open system
(c) Isolated system
(d) Non-thermodynamic system
Ans. a)
As energy can be exchanged but mass cannot be.

Q 3. Whic of the following is/are basic state variables of a given thermodynamic

system ?
(a) volume
(b) pressure
(c) temperature
(d) all the above
Ans. d)
As their value depends only upon the state of the system and does not depend upon
the path by which this state has been attained.

Q 4. Heat absorbed by a system is

(a) state function
(b) path function
(c) both a and b.
(d) none
Ans. b)
As it depends on path followed by the system.

Q 5. The process, in which no heat enters or leaves the system, is termed as

(a) Isochoric
(b) Isobaric
(c) Isothermal
(d) Adiabatic
Ans. d)
For adiabatic process there is no heat flow between system and surrounding
i.e., q = 0.

Q 6. Let us consider a system in which we have points A, B, C and D. UA, UB, UC and
UD are the internal energies at the points respectively. What will be the net change
in internal energy if we move from A to B then B to C then C to D and then back D to
A.
(a) UA UD
(b) UB - UC
(c) UD - UA
(d) ZERO
Ans. d)
Since, internal energy is a state dependent function and the state does not change at
the end. It starts at A and ends at A (a cyclic process). Therefore, net change in
internal energy is zero.

Q 7. What is the change in internal energy of a system if no work is being performed

and it is an adiabatic process?
(a) Q
(b) W
(c) ZERO
(d) None Of These
Ans. c)
Since, no work performed therefore dW=0 and adiabatic process hence, dQ=0.
Therefore, dU=0.