Thermo - First Second Law
Thermo - First Second Law
Thermo - First Second Law
Heat Pumps
Surroundings
System
The frontier of the system is
arbitrarily chosen
Another method of
doing work.
Electrical work is
done on the
system by the
generator, which is
driven by the
falling weight.
PV n R T
How the confined gas
interchange energy (heat and
work) with the surroundings?.
What is the value of the internal
energy for the gas in the cylinder
First Law
Quasi static processes: a type of processes where the gas moves through a
series of equilibrium states. Then, we can apply the IGL. In practice, if we move
slowly the piston, will be possible to approximate quasi-static processes fairly well.
ET
CO2
Energy fluxes:
Rn :
Ph
Ph
Rn H ET G D - Ph = Eint
Eint Qin
Qin CV T
and
dEint CV dT n cV dT
Internal Energy is a state function, i.e. it is not dependent on the
process, only it depends of the initial and final temperature
QP CP T
QP CP dT
Qin ,V CV dT n cV dT
Qin ,V CV T n cV T
and
P const dP 0
CP CV n R
The expansion is usually negligible for solids
and liquids, so for them CP ~ CV.
Ideal Gas
QV CV T ; QV CV dT
- At constant pressure
QP C P T ; QP C P dT
CP CV n R
Relationship of Mayer
3
3
J
CV n R; cV R 12.47
2
2
mol K
5
5
J
CV n R cV R 20.79
2
2
mol K
Work done on the system, Won , is the energy transferred as work to the system.
When this energy is added to the system its value will be positive.
The work done on the gas in an
expansion is
V2
Won gas P dV
V1
P- V diagrams
Constant pressure
V2
P- V diagrams
Isothermal
V2
V2
Constant Volume
Won gas P dV 0
V1
V2
Constant Temperature
Won gas
V1
n RT
V2
dV n R T ln
V
V1
Diagrams
Diagrams
CP
P V const ;
CV
T V 1 const
T P1 const
adiabatic coefficient
Pf V f Pi Vi
Diagrams
For certain indices n, the process will be synonymous with other processes:
if n = 0, then PV0=P=const and it is an isobaric process (constant pressure)
if n = 1, then for an ideal gas PV= const and it is an isothermal process (constant
temperature)
if n = = cp/cV, then for an ideal gas it is an adiabatic process (no heat transferred)
if n = , then it is an isochoric process (constant volume)
Diagrams
Two moles of an ideal monoatomic gas have an initial pressure P 1 = 2 atm and an initial
volume V1 = 2 L. The gas is taken through the following quasi-static cycle:
A.- It is expanded isothermally until it has a volume V2 = 4 L.
B.- It is then heated at constant volume until it has a pressure P 3= 2 atm
C.- It is then cooled at constant pressure until it is back to its initial state.
(a) Show this cycle on a PV diagram. (b) Calculate the head added and the work done by
the gas during each part of the cycle. (c) Find the temperatures T1, T2, T3
Diagrams
Diagrams
Diagrams
Diagrams
Heat Engines.
Internal-Combustion Engine
Heat Engines.
W Qh Qc
Qc
1
Qh
Qh
Qh
It is impossible to make a heat engine
with a efficiency of 100 per cent
It is impossible for a heat engine
working in a cycle to produce only the
effect of extracting heat from a single
reservoir and performing an equivalent
amount of work
Schematic representation of a
refrigerator.
COP. Coefficient
of Performance
of a Refrigerator
Qc
COP
W
Refrigerators.
A process whose only net result is to
transfer energy as heat from a cooler object
to a hotter one is impossible.
SECOND LAW, CLAUSIUS STATEMENT
COP. Coefficient
of Performance
of a Refrigerator
Qc
COP
W
Heat Pump
Qh
COPHP
W
COPHP. Coefficient of
Performance of a Heat
pump
W Qh Qc
Qc
1
Qh
Qh
Qh
W Qh Qc
Q
1 c
Qh
Qh
Qh
Isothermal processes
V2
Qh Wby gas
V1
V2
P dV n R Th ln
V1
V4
Qc Won gas P dV n R Tc ln
V3
Adiabatic processes
1
2
1
1
Th V
Th V
V2
Qc
V1 Tc
Qh T ln V3 Th
h
V4
Tc ln
1
3
1
4
Tc V
Tc V
V3
V4
V2 1 V3 1
V2 V3
1
1
V1
V4
V1 V4
W Qh Qc
Qc
Tc
1
1
Qh
Qh
Qh
Th
W Th Tc
C
Qh
Th
Qc
Tc
COPmax
W Th Tc
Q
Th
COPHP max h
W Th Tc
A steam engine works between a hot reservoir at 100 C and a cold reservoir at 0C. (a)
What is the maximum possible efficiency of this engine? If the engine is run backwards
as refrigerator, what is its maximum coefficient of performance? If the engine is running
as heat pump, what is the maximum coefficient of performance?
Irreversibility, desorder:
Entropy
The free expansion of an idealgas: No work, no heat, no
change of internal energy,
But, is it the same state after
and before of the free
expansion?
Entropy, S: a physical magnitude whose net increment (system +
surroundings) indicates the irreversibility of a process:
In a irreversible process, the entropy of the universe increases
For any process, the entropy of the universe never decrease
A spontaneous heat transfer (from hotter body to a colder one) implies
an increment of entropy (It is a irreversible process)
Entropy: a thermodynamic function of disorder
Qrev
dS
T