Thermodynamic terms

 System and its surroundings:

A system in thermodynamics refers to that part of universe in
which observations are made and remaining universe constitutes
the surroundings. The surroundings include everything other than
the system. System and the surroundings together constitute the
universe .
The universe = The system + The surroundings
 For example, if we are studying the reaction between two
substances A and B kept in a beaker, the beaker containing the
reaction mixture is the system and the room where the beaker is
kept is the surroundings.
 Note that the system may be defined by physical boundaries, like
beaker or test tube, or the system may simply be defined by a set
of Cartesian coordinates specifying a particular volume in space.
It is necessary to think of the system as separated from the
surroundings by some sort of wall which may be real or
imaginary. The wall that separates the system from the
surroundings is called boundary. This is designed to allow us to
control and keep track of all movements of matter and energy in
or out of the system.
Classification of systems.
 Open system: In an open system, there is exchange of energy and
matter between system and surroundings .The presence of
reactants in an open beaker is an example of an open system*.
Here the boundary is an imaginary surface enclosing the beaker
and reactants.
 Closed system: In a closed system, there is no exchange of
matter, but exchange of energy is possible between system and
the surroundings. The presence of reactants in a closed vessel
made of conducting material e.g.copper or steel is an example of
a closed system.
Isolated system:-
 In an isolated system, there is no exchange of energy or matter
between the system and the surroundings . The presence of
reactants in a thermos flask or any other closed insulated vessel is
an example of an isolated system.
 The system must be described in order to make any useful calculations
by specifying quantitatively each of the properties such as its pressure
(p), volume (V), and temperature (T ) as well as the composition of the
system. We need to describe the system by specifying it before and
after the change.
 The state of a thermodynamic system is described by its measurable or
macroscopic (bulk) properties. We can describe the state of a gas by
quoting its pressure (p), volume (V), temperature (T ), amount (n) etc.
Variables like p, V, T are called state variables or state functions
because their values depend only on the state of the system and not on
how it is reached. In order to completely define the state of a system it
is not necessary to define all the properties of the system; as only a
certain number of properties can be varied independently.
Internal energy as state function
 Internal energy of a system is defined as U
 This internal energy may be electrical chemical or mechanical.
the internal energy, U of the system, which may change, when:-
 • heat passes into or out of the system,
 • work is done on or by the system,
 • matter enters or leaves the system.
work
 We take a system containing some quantity of water in a thermos
flask or in an insulated beaker. This would not allow exchange of
heat between the system and surroundings through its boundary
and we call this type of system as adiabatic. The manner in which
the state of such a system may be changed will be called
adiabatic process. Adiabatic process is a process in which there is
no transfer of heat between the system and surroundings. Here,
the wall separating the system and the surroundings is called the
adiabatic wall.
 Let us bring the change in the internal energy of the system by
doing some work on it. Let us call the initial state of the system
as state A and its temperature as TA . Let the internal energy of the
system in state A be called UA . We can change the state of the
system in two different ways.
 First way: We do some mechanical work, say 1 kJ, by rotating a
set of small paddles and thereby churning water. Let the new
state be called B state and its temperature, as TB . It is found that
TB > TA and the change in temperature, ∆T = TB–TA. Let the
internal energy of the system in state B be UB and the change in
internal energy, ∆U =UB– UA .
 Second way: We now do an equal amount (i.e. 1kJ) electrical
work with the help of an immersion rod and note down the
temperature change. We find that the change in temperature is
same as in the earlier case, say, TB – TA .
 the internal energy U, whose value is characteristic of the state
of a system, whereby the adiabatic work, wad required to bring
about a change of state is equal to the difference between the
value of U in one state and that in another state, ∆U i.e, ∆U=U2-
U1=Wad
 Therefore, internal energy, U, of the system is a state function.
The positive sign expresses that Wad is positive when work is
done on the system. Similarly, if the work is done by the system,
Wad will be negative
 Some of other familiar state functions are V, p, and T. For
example, if we bring a change in temperature of the system from
25°C to 35°C, the change in temperature is 35°C–25°C = +10°C,
whether we go straight up to 35°C or we cool the system for a
few degrees, then take the system to the final temperature. Thus,
T is a state function and the change in temperature is independent
of the route taken. Volume of water in a pond, for example, is a
state function, because change in volume of its water is
independent of the route by which water is filled in the pond,
either by rain or by tubewell or by both.
Heat
 We can also change the internal energy of a system by transfer of heat from
the surroundings to the system or vice-versa without expenditure of work.
This exchange of energy, which is a result of temperature difference is called
heat, q. Let us consider bringing about the same change in temperature by
transfer of heat through thermally conducting walls instead of adiabatic
walls.
 We take water at temperature, TA in a container having thermally conducting
walls, say made up of copper and enclose it in a huge heat reservoir at
temperature, TB . The heat absorbed by the system (water), q can be
measured in terms of temperature difference , TB – TA . In this case change in
internal energy, ∆U= q, when no work is done at constant volume.
The q is positive, when heat is transferred from the surroundings to the system
and q is negative when heat is transferred from system to the surroundings.
Explanation First law of thermodynamics
 Let us consider the general case in which a change of state is
brought about both by doing work and by transfer of heat. We
write change in internal energy for this case as: ∆U = q + w For
a given change in state, q and w can vary depending on how the
change is carried out. However, q +w = ∆U will depend only on
initial and final state. It will be independent of the way the
change is carried out. If there is no transfer of energy as heat or
as work(isolated system) i.e., if w = 0 and q = 0, then ∆ U = 0.
 The equation, ∆U = q + w is mathematical statement of the first law
of thermodynamics, which states that
The energy of an isolated system is constant.

 It is commonly stated as the law of conservation of energy i.e, energy

can neither be created nor be destroyed.
 Example: Express the change in internal energy of a system when
 (i) No heat is absorbed by the system from the surroundings, but
work (w) is done on the system. What type of wall does the system
have ?
 (ii) No work is done on the system, but q amount of heat is taken out
from
 the system and given to the surroundings. What type of wall does the
system have?
 (iii) w amount of work is done by the system and q amount of heat is
supplied to the system. What type of system would it be?
 Answers
 (i) ∆ U = wad, wall is adiabatic
 (ii) ∆ U = – q, thermally conducting walls
 (iii) ∆ U = q – w, closed system.
APPLICATIONS
Work-pressure volume work:
For understanding pressure-volume work, let us consider a cylinder
which contains one mole of an ideal gas fitted with a frictionless
piston. Total volume of the gas is and pressure of the gas inside is
p. If external pressure is pex which is greater than p, piston is
moved inward till the pressure inside becomes equal to pex. Let
this change be achieved in a single step and the final volume be
Vf .
 During this compression, suppose piston moves a distance, l and
is cross-sectional area of the piston is A then, volume change = l
× A = ∆V = (Vf-Vi)
we know that pressure =

Therefore, force on the piston = pex . A If w is the work done on the

system by movement of the piston then
W= force x displacement = pex x A .l

Pex x(-∆V)= -pex∆V= -pex(Vf-Vi)

 The negative sign of this expression is required to obtain
conventional sign for w, which will be positive. It indicates that
in case of compression work is done on the system. Here (Vf – Vi
) will be negative and negative multiplied by negative will be
positive. Hence the sign obtained for the work will be positive. If
the pressure is not constant at every stage of compression, but
changes in number of finite steps, work done on the gas will be
summed over all the steps and will be equal to − ∑ ∆p V.
 If the pressure is not constant but changes during the process
such that it is always infinitesimally greater than the pressure of
the gas, then, at each stage of compression, the volume decreases
by an infinitesimal amount, dV. In such a case we can calculate
the work done on the gas by a relation as given in the next slide.
Here, pex at each stage is equal to (pin + dp) in case of compression In an
expansion process under similar conditions, the external pressure is
always less than the pressure of the system i.e., pex = (pin– dp). In general
case we can write, pex = (pin + dp). Such processes are called reversible
processes.
A process or change is said to be reversible, if a change is brought out in
such a way that the process could, at any moment, be reversed by an
infinitesimal change. A reversible process proceeds infinitely slowly by a
series of equilibrium states such that system and the surroundings are
always in near equilibrium with each other. Processes other than
reversible processes are known as irreversible processes.
Relation of work to internal pressure
Free expansion
 Expansion of a gas in vacuum (pex= 0) is called free
expansion. No work is done during free expansion of an
ideal gas whether the process is reversible or irreversible.
 We know that w= -pex∆V(we substituted in equation of area
of piston and integration (6.3)
therefore the internal energy ∆U=q-pex∆V
therefore ∆U=qv
qv denotes that heat Is supplied at constant volume.
Isothermal and free expansion of a ideal
gas
 For isothermal (T = constant) expansion of an ideal gas into
vacuum ; w = 0 since pex = 0. Also, Joule determined
experimentally that q = 0; therefore, ∆U = 0 Equation 6.1, ∆ U =
q +w can be expressed for isothermal irreversible and reversible
changes as follows:

 (a) for isothermal irreversible change:

q = -w = pex(vf -vi)