Актюбинский региональный университет им. К.

Жубанова
Физико-математический факультет
кафедра физики

Предмет: Molecular physics

Тема: Cyclic processes

Шугаева Т.Ж.
старший преподаватель, PhD
 The first law of thermodynamics.

1. Internal energy.
2. Macroscopic work.
3. Heat.
4. The first law of thermodynamics.
5. Heat capacity of an ideal gas. Mayer's theorem.
6. Adiabatic process.
7. Reversible and irreversible processes
8. Conditions for converting heat into mechanical
work
 Internal energy. U
The most important characteristic of a
thermodynamic system is its internal energy. This
is the energy of the chaotic (thermal) movement of
microparticles of the system (molecules, atoms,
electrons, nuclei, etc.) plus the energy of
interaction of these particles.
From this definition it follows that internal energy
does not include the kinetic energy of motion of
the system as a whole and the potential energy of
the system in external fields.
 Internal energy is a function of state, that is, in each of
the states characterized by the parameters P, V, T, the
system has a very specific internal energy (it does not
depend on how the system came to this state). When a
system transitions from one state to another, the change in
internal energy is determined only by the difference in the
values of the internal energy of these states and does not
depend on the process (on the transition path).

So, in each state the system has a certain value of

internal energy, U
and its change can be calculated:
2
U   dU  U 2  U1
1
A small change in internal energy is mathematically
written as a total differential. dU

If we consider a circular process, during which the

system goes through a series of states and returns to
its original state, the change in internal energy is

 
zero:
dU 0.
This follows from the fact that U is a state function. When
returning to the initial state, U also returns to its original
value. The internal energy is determined up to an additive
constant: the energy of one of the states can be taken as
zero (U = 0).
 For an ideal gas, internal energy means only the energy of
thermal chaotic motion of molecules, since the interaction
between molecules is negligible.
Internal energy of a gas containing N molecules:
U  N  Ek 
where  Ek  - average kinetic energy of a molecule,
where  - mole number. N   N A
For monatomic gas
3 3 3
U  N A kT  RT  Ek  kT
2 2 2
For gas with more complex molecules
i
 Ek  kT
2
U  i RT i — number of degrees of freedom of
2 molecules (depends on their structure)
 Macroscopic work A
(work related to moving bodies).
Let us consider the gas located under the piston in a
cylindrical vessel. If a gas, expanding, moves the piston an
-

infinitesimal distance dl, then it does elementary work on it

A  Fdl  pSdl  pdV

whereS - piston area,
Sdl  dV - change in volume.
Thus, A  pdV
The total work A done by the gas when its volume
changes from V1 to V2 is found by integrating the
formula for elementary work
V2

A  pdV
V1
The result of integration is determined by the nature of the
dependence of pressure on gas volume. The work produced
by a particular process can be depicted graphically using a
curve in coordinates p, V .
 Only equilibrium processes can be
depicted graphically - processes
consisting of a sequence of
equilibrium states.
When the volume increases by dV
, the work done by the gas is equal to

A  pdV
that is, determined by the area of the green stripe.
Therefore, the total work as the sum of all elementary
works δA is numerically equal to the area bounded by the
abscissa axis, the curve p(V) and the straight lines
lines V and V (colored yellow in the figure).
1 2
 Work is a function of the process, that is, its value depends
on the progress of the process as a result of which it is
accomplished. The following diagrams clearly show this.

The first graph shows examples of possible processes of transition of

the system from the 1st to the 2nd state. In the second graph: isobaric
and isochoric processes; on the third - an isothermal process; on the
fourth – isochoric and isobaric processes. Works A are different
everywhere.
As an example, let us calculate the work done by a gas
in an isothermal process. By definition
V2

From the M-K equation: A  pdV

V1
V2
m m
T m dV
PV  RT P R A12  R  T
  V  V1 V
In an isothermal process T=const, therefore
V2
m dV
A12  RT 
 V1
V
m m V2
A12  RT ln V V2
 RT ln
 
V1
V1
We examined the work of a gas performed under the
influence of its pressure Pgas. For quasi-static processes,
the pressure Pgas is balanced by external pressure Pext,
therefore
pгаз   рвнеш

Aвнеш  Агаз

Definition of macroscopic work:

the work of external forces associated with the
movement of the shell (movement of the piston) is
called macroscopic work.
Heat. Quantity of heat Q.
A change in internal energy U is possible due to:
1) the work of external forces and Aвнеш
2) the transfer of internal energy from a more heated body
to a less heated one.
The process of exchange of internal energies between
bodies in contact, not accompanied by the performance of
macroscopic work, is called heat transfer or heat
exchange.
The energy transferred as a result of heat exchange is
called heat quantity or simply heat.
 The process of energy transfer occurs as a result of
collisions of molecules of a more heated body with
molecules of a less heated one - that is, as a result of
microscopic work.
The amount of heat Q is a function of the process, that
is, it depends on the nature of the process in which it is
transferred.
The SI unit of heat is [Q] = J.
A less common unit of heat measurement today is the
calorie.
The relationship between a calorie and a joule is called
the mechanical equivalent of heat:
1 cal = 4,18 J
 The first law of thermodynamics.
The first law of thermodynamics is the law of
conservation of energy as applied to thermal processes.
A change in the internal energy of a thermodynamic
system is possible as a result of imparting heat to it and
performing external work on the system:

U  Q  Aвнеш

This is one of the formulations of the first principle.

Using, Aвнеш  Агаз , we get:
U  Q  Aгаз
Then finally:

Q  U  Aгаз
The amount of heat imparted to a thermodynamic
system is used to increase its internal energy and
to perform work on external bodies by this system.
We will use exactly this formulation of the first law of
thermodynamics. In addition, in what follows we denote.
Aгаз  А
 For quasi-static processes, when the parameters
experience infinitesimal changes, the first principle takes
the form:
Q  dU  A
In this expression, dU is the total differential (increment
of the function of the state of the system), Aand Q
and is the elementary work and elementary heat
(depending on the type of process).
Q  U  A
IF Q  0 , this means the system is receiving heat
IF Q  0 - the system gives off heat.
IF А>0 — the work is done by the gas.
IF А<0 — work done on the gas.
Consequences from the first principle.
Q  U  A
1) In a circular process (in Fig.
abcd) U  0  Q  A
This means that the first principle does not impose any
restrictions on the transformation of heat into
mechanical work, and as a result of a circular process,
work can be performed.
2) If U  0 and Q  0 then A  0 . This means
that a process is impossible whose only result is the
production of work without any changes in other bodies.
That is, a perpetual motion machine of the first kind is
impossible.
 Heat capacity of an ideal gas. Mayer's
equation.
Heat capacity is the ability of a system to accumulate
heat.
Numerically, the heat capacity of a body is equal to the
amount of heat required to heat this body by one Kelvin.
Q
C
dT
Heat capacity dimension: [C] = J/K.
The heat capacity of bodies depends on their mass,
so the concepts of specific and molar heat capacity are
used.
Specific heat capacity Csp - is the amount of heat
required to heat a unit mass of a substance by 1
kelvin: Q
C уд  с  ;
dT  m
For gases it is convenient to use the molar heat capacity
Cμ This is the amount of heat required to heat 1 mole of
gas by 1 kelvin
Q
Q
C  с  
mdT dT ,

[Cμ] = J/(mol K), [Csp] = J/(kg K).

Heating of gas can be done under conditions of constant
volume or pressure. Accordingly, heat capacities are
distinguished at constant volume and constant pressure.

Let us write down the expression for the first law of

thermodynamics for one mole of gas, taking into account
the expressions for heat capacity and work
C 
Q
 Q  C dT
in the same time dT
 Q  dU  A so C dT  dU  pdV
   
If a gas is heated at a constant volume, then the work
done by external forces is zero (dVμ=0) and the heat
imparted to the gas from the outside only goes to increase
its internal energy: dU 
C V 
dT
Further СμV for brevity we will denote СV
dU 
CV 
dT
If a gas is heated at constant pressure, then the heat
capacity can be written as:

dQ dU  pdV pdV
Cp     CV 
dT dT dT dT
Differentiating the Mendeleev-Clapeyron equation
PVμ = RT по Т (with p = const), we get:
dV
p R
dT
Then finally:
C p  CV  R
The equation is called Mayer's equation. It shows that it
is C p always greater than CV the molar gas
constant.
This is explained by the fact that when heating a gas at a
constant pressure, an additional amount of heat is
required to perform the work of gas expansion, since the
constancy of the pressure is ensured by an increase in the
volume of the gas.
From the above it follows that the physical meaning of the
universal gas constant is that R is numerically equal to the
work done by one mole of gas when heated by one degree in
an isobaric process.
 Adiabatic process
Adiabatic is a process that occurs without heat exchange
with the environment.: Q  0
Q  dU  A
A  dU
work is done by changing the internal energy of the
system.
Let us derive the equation of the adiabatic process
For one mole of gas, we rewrite the above equation as:
pdV  C dT V
(1)
Differentiate the equation of state for an ideal gas
pV  RT
pdV  Vdp  RdT (2)
pdV  CV dT (1)

Dividing equation (2) by (1) term by term, we obtain

pdV  Vdp R C p  CV
 
pdV CV CV
It is taken into account here that Ср- СV =R. In addition, we

C p / CV   Vdp
denote we get  
pdV
dp dV
or  
p V
Integrating this equation over the range from p1 to p2
and, respectively, from V1 to V , we arrive at the
2
expression: 
p2
  ln
V2 then we potentiate: p2  V1 
ln  
p1 V1 p1 V2 
 
Eventually p V  p2V2
1 1
Since states 1 and 2 are chosen arbitrarily, we can write

pV  const
The resulting expression is the equation of the adiabatic
process, also called the Poisson equation.
 Reversible and irreversible processes
All thermodynamic processes are divided into two
groups: reversible and irreversible.
A reversible process is a change in the state of a system
(or one body), which, when carried out in the opposite
direction, returns it to its original state so that the system
passes through the same intermediate states as in the
direct process, while the state of bodies outside the system
remains unchanged .
In particular, mechanical movements in the absence
of friction forces are reversible.
 In thermodynamics, only equilibrium processes have
the property of reversibility. Each intermediate state is a
state of thermodynamic equilibrium, insensitive to
whether the process proceeds in the forward or reverse
direction.

For example, the process of adiabatic expansion or

compression of a gas can be considered reversible.
During adiabatic expansion of a gas, the condition of
thermal insulation of the system excludes direct heat
exchange between the system and the medium.
Therefore, by performing adiabatic expansion of the gas
and then compression, it is possible to return the gas to
its original state so that no changes will occur in the
environment.
 A process is called irreversible if it proceeds in such a way
that after its completion the system cannot be returned to its
initial state through the previous intermediate states.
All processes occurring naturally in nature are
irreversible:
equalization of temperature differences (thermal
conductivity);
pressure equalization
equalization of concentrations (diffusion).
All these are processes of transition to a state of
thermodynamic equilibrium.
 Not only in nature, but also in technology, in real
conditions there is always some irreversibility of the
process, due, for example, to imperfect thermal
insulation, friction during piston movement, etc.

Only in reversible processes is heat used for its

intended purpose and is not wasted.

In irreversible processes, partial dissipation

(dissipation) of energy occurs.
 Conditions for converting heat into
mechanical work
All practice shows that mechanical energy can be
completely converted into heat. Is it possible to do it the
other way around: completely convert heat into mechanical
motion? This question arose during the creation of heat
engines.
Let's go back to the first beginning of t/d Q  dU  A
If dU  0 , then A  Q. So for an isothermal
process, the work on gas expansion

 V2 
A12  RT ln   Q
 V1 
 It would seem that there are no restrictions on the
transformation of heat into mechanical work. However,
the case considered refers to a single act of heat transfer.
Heat engines operate cyclically, that is, the processes of
transferring heat and converting it into work are
periodically repeated.
Let us consider the properties of circular processes that
are implemented in heat engines.

A circular process, or cycle, is a process as a result of

which a thermodynamic system returns to its original
state.
In state diagrams, circular processes are depicted as closed
curves (for example, curve abcda). When a gas expands (section
abc), it does positive work equal to the area shaded in pink.
When gas is compressed (section cda), the work is negative
(performed by external forces). It is equal to the shaded area.
Positive work will exceed negative work in absolute value if in
the gas expansion section the pressure P1 is higher than the
pressure P2 with the same volume of gas in the compression
section. To do this, the gas must be heated during the expansion
process, and cooled during the compression process.
Summarize. For a circular process:

Expansion work (1a2) - positive (dV >0)

The compression work (2b1) is negative (dV < 0).
The work done per cycle is determined by the area
covered by the curve.
 A   PdV  0 A   PdV  0
It is easy to verify: if the traversal along the cycle is done
clockwise, the work is positive;
if counterclockwise, the work is negative.
As a result of the circular process, the system returns to its
original state and, therefore, the total change in the
internal energy of the gas is zero: U  0
Then the first law of thermodynamics for a circular
process gives
Q  U  A  A  Q  A
However, during a circular process, the system receives
heat in one section of the process and releases heat in
another, therefore

Q  Q1  Q2 ,
Q1 – amount of heat received by the system;
Q2 is the amount of heat given off by the system.
  Q1

 Q2

Indeed, at stage (1a2) the system performs work during

gas expansion A  0 due to the amount of heat
entering the system Q1. And at stage (2b1) the work of
external forces is done on the system ( A  0 ), in this
case, the system releases the amount of heat Q2 .
Experience and practice show that all the heat
taken from the thermal reservoir cannot be
completely converted into mechanical work in
any cyclic process.
 Thermal machines.
A heat engine is a periodic operating engine that performs
work using heat received from outside.

Any heat engine consists of three parts:

Н 1) Heater - Н

РТ 2) Working fluid- РТ

Х 3) Fridge - Х
 Operating principle of heat engines

T
A heater with temperature 1 transfers an amount of heat Q1 to
the working fluid during its expansion without changing the
temperature.
When the working fluid is compressed, the amount of heat Q2 is
T
transferred to the refrigerator with a lower temperature
2
without

A  Q Q
changing its temperature.
At the same time, work is done: 1 2
The most important characteristic of a heat engine is the
efficiency factor:
Aполезн

Q1
 - heat
efficiency factor - efficiency -
engine;
Аполезн - useful work done by the engine, J;
Q1 - amount of heat received by the engine from the
heater J.
Why do you need a refrigerator? Since a circular
process is implemented in a heat engine, it is possible to
return to the original state at a lower cost if you give up
some of the heat.
 Q1

 Q2
If you cool the steam, the pressure will decrease and it
will be easier to compress it, therefore, the work of
compression will be less than the work of expansion,
and the total work as a result of the entire cycle will be
positive.
Heat engine efficiency
Steam engine efficiency = 15%
Turbojet engine efficiency = 20 -30%
Internal combustion engine efficiency = 25-30%
Gas turbine efficiency = 25 – 29%
Steam turbine efficiency = 25 - 40%