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REVERSIBLE AND

IRREVERSIBLE PROCESSES
Process reversible if both system and surroundings can
be restored to their respective initial states, by reversing
the direction of the process.

Example of factors that cause process to be irreversible


Friction, Unrestrained expansion, Mixing of two gases,
Heat transfer across a finite temperature difference,
Spontaneous chemical reactions, Expansion or
Compression with finite pressure difference, Mixing of
matter at different states

first law can be applied to a system to evaluate the


changes in its energy when it undergoes a change of
state while interacting with its surroundings.
Processes in thermo analysis of systems - one or a
combination of the following elementary processes:
(i) Constant volume (isochoric)
(ii) Constant pressure (isobaric)
(iii) Constant temperature (isothermal)
(iv) Adiabatic process.
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Reversible Non-Flow Process

Constant volume process

Gas enclosed in a rigid vessel interacting with the


surroundings and absorbs energy Q as heat
The vessel is rigid - work done W due to expansion or
compression is zero.

first law for unit mass


Q W  u  u
2 1
since no work we get
Q  u  u or for mass m - Q U U
2 1 2 1

Heat interaction is equal to the change in internal


energy. If the system contains a mass m of a perfect
gas, then
 
Q  U  mcvT T 

 2 1

pressure rises as heat is applied

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A 0.1 m3 rigid tank contains steam initially at 500 kPa
and 200oC. The steam is now allowed to cool until the
temperature drops to 50oC.
Determine the amount of heat transfer during this
process and the final pressure in the tank.

A constant volume chamber of 0.3 m3 capacity contains


1 kg of air at 5°C. Heat is transferred to the air until the
temperature is 100°C.
Find the work done, the heat transferred, and the
changes in internal energy.

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Constant pressure process

boundary moves against external resistance as heat is


applied – work done by the fluid
𝑣2
𝑊 = − ∫𝑣 𝑝 𝑑𝑣 for any reversible process
1
𝑣2
since p is constant 𝑊 = − ∫𝑣 𝑝 𝑑𝑣 = −𝑝(𝑣2 − 𝑣1 )
1

from the non-flow equation Q W  u  u


2 1
for a reversible const pressure process
       
Q  u u   pv  v   u  pv   u  pv 
      

 2 1  2 1  2 2  1 1
𝑄 = ℎ2 − ℎ1 for unit mass, or
𝑄 = 𝐻2 − 𝐻1
in a constant pressure process, the heat interaction is
equal to the increase in the enthalpy of the system.

for a perfect gas


 
Q  H  mc pT T 

 2 1
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Air at 1 bar and 298.15K (25℃) is compressed to 5 bar
and 298.15K by the mechanically reversible process of
cooling at constant pressure followed by heating at
constant volume.

Calculate the heat and work requirements and ΔU and


ΔH of the air for each path and for the entire process.

The following heat capacities for air may be assumed


independent of temperature:
cv= 20.78 and cp=29.10 J mol-1K-1
At 298.15K and 1 bar the molar volume of air is
0.02479 m3mol-1.

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Constant temperature process or isothermal process

Suppose a gas enclosed in the piston cylinder assembly


is allowed to expand from p1 to p2 (temp will fall) – to
keep temperature constant, heat must be added.
for isothermal compression heat must be removed

from state 1 to state A, const pressure


𝑄1−𝐴 = ℎ𝐴 − ℎ1
from A to 2, Q found from entropy change
then W from Q W  u  u
2 1

for a perfect gas - pv = RT and u = u(T)


then for an isothermal process,
pv = constant = c, and dU = u2 – u1 = 0

Q W  0 and Q W
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𝑣2 𝑣2
𝑐 𝑣1
𝑊 = − ∫ 𝑝 𝑑𝑣 = − ∫ 𝑑𝑣 = 𝑐 ln ( )
𝑣1 𝑣1 𝑣 𝑣2
𝑝2 𝑣1 𝑣1
= 𝑐 ln ( ) = 𝑝1 𝑣1 ln ( ) = 𝑝2 𝑣2 ln ( )
𝑝1 𝑣2 𝑣2
only for a perfect gas

One kilogram of air undergoes a thermodynamic cycle


consisting of three processes.
Process 1–2: constant specific volume
Process 2–3: constant-temperature expansion
Process 3–1: constant-pressure compression

At state 1, the temperature is 300K, and the pressure is


1 bar. At state 2, the pressure is 2 bars. Employing the
ideal gas equation of state.

(a) sketch the cycle on p–v coordinates.


(b) determine the temperature at state 2, in K
(c) determine the specific volume at state 3, in m3/kg
(d) determine the work and heat interactions for each
path and for the overall process

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Reversible adiabatic (Isentropic process) non-flow
process

an adiabatic process – no heat transferred to or from the


fluid during the process, Q = 0
A reversible adiabatic process is also known as an
isentropic process, property entropy remains constant.

from the non-flow equation


𝑄 + 𝑊 = 𝑢2 − 𝑢1
for adiabatic process 𝑊 = 𝑢2 − 𝑢1
in adiabatic compression all the work done goes to
increasing the internal energy u

for a perfect gas a simple relatinship between p and v


may be obtained for areversible adiabatic process
𝑝𝑣 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
each perfect gas having its own value of 

a relationship between T and v and p may be derived


𝑇1 𝑣2 𝛾−1 𝑇1 𝑝1 (𝛾−1)⁄𝛾 𝑝1 𝑣2 𝛾
=( ) ; =( ) ; =( )
𝑇2 𝑣1 𝑇2 𝑝2 𝑝2 𝑣1

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𝑣2
−𝑊 = ∫ 𝑝 𝑑𝑣 = 𝑠ℎ𝑎𝑑𝑒𝑑 𝑎𝑟𝑒𝑎
𝑣1

𝑣2 𝑣
𝑐𝑑𝑣 𝑣 −𝛾+1 2
𝑊 = −∫ 𝛾
𝑑𝑣 = −𝑐 [ ]
𝑣1 𝑣 −𝛾 + 1 𝑣
1
−𝛾+1 −𝛾+1 −𝛾+1 −𝛾+1
𝑣2 −𝑣1 𝑣1 − 𝑣2
= −𝑐 ( ) = −𝑐 ( )
1−𝛾 𝛾−1
𝛾 𝛾
substituting for 𝑐 𝑎𝑠 𝑝1 𝑣1 𝑜𝑟 𝑝2 𝑣2
𝑝2 𝑣2 − 𝑝1 𝑣1
𝑊=
𝛾−1

9
Air is compressed adiabatically from p1= 1 bar, T1=300
K v1= 0.849 m3/kg to p2=15 bar,. The air is then cooled
at constant volume to T3= 300 K. Assuming ideal gas
behavior, calculate
a) the temperature and volume after the first process
b) the work for the first process and the heat transfer
for the second process.
 for air = 1.4
at 300K cv for air = 0.718 kJ/kg•K

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Polytropic Process

many processes approximate to a reversible law of the


form 𝑝𝑣 𝑛 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 – n is polytropic index
both vapours and perfect gases obey this type of law in
many non-flow processes

can derive
𝑝2 𝑣2 − 𝑝1 𝑣1
𝑊=
𝑛−1

for perfect gas sometimes work input expressed in


terms of temperatures of end states
𝑛 − 𝛾 𝑅(𝑇2 − 𝑇1 )
𝑄=( )
𝛾 − 1 (𝑛 − 1)

also
𝑛−𝛾
𝑄=( )𝑊
𝛾−1
in compression process W>0,
then if n> then Q>0 – heat supplied during process
if n< then Q<0 – heat rejected by the gas

11
Air (ideal gas with γ = 1.4) at 1 bar and 300K is
compressed till the final volume is one sixteenth of the
original volume, following a polytropic process
pv1.25 = const.

Calculate
(a) the final pressure and temperature of the air,
(b) the work done and
(c) the energy transferred as heat per mole of the air.

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