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Symbol
T
P
S.I. Unit
Kelvin (K)
Pascals (Pa)
Definition
Volume of a
Volume
substance
The translational,
rotational and
Internal Energy vibrational kinetic
energy of a
substance
Enthalpy
U + PV
The entropy is a
measure of the
lack of structure or
Entropy
the amount of
disorder in a
system
Gibbs free energy
H - TS
Symbol
S.I.Unit
m3
Joules (J)
Joules (J)
Joules/Kelvin (J /
K)
Joules (J)
Standard States
If the temperature and pressure of a pure substance are known then
its thermodynamic state is defined. So that measured
thermodynamic data can be compared, standard values of the
Enthalpy
The temperature that is most often used for recording
thermodynamic data is 298.15 K, and by international convention
the enthalpy of a pure element at 298.15 K and standard pressure is
zero.
Internal energy
Since the enthalpy has been set to zero at 298.15 K then the intenal
energy at standrd pressure and 298.15 K is calculated from the
definition of enthalpy
Entropy
The entropy has a standard that is fixed by the Third Law of
Thermodynamics. This states that for a pure substance, the entropy
of the substance at standard pressure and zero K is zero
In the same way that the value of the enthalpy for a compound was
found from the heat of formation, the Gibbs free energy of a
compound can be found by working out the Gibbs free energy
change for the reaction where it is formed from its elements.
The Gibbs free energy change for reactions are most frequently
(1)
An open system is one where material can flow across the boundaries of the
system, as well as heat and work.
In the process shown above, gas is entering the system and being heated in
the heat exchanger where its temperature pressure and volume increase. The
gas then passes through an expansion turbine, where it cools down and the
pressure decreases. During the expansion process work is extracted from
the gas.
The first law written for an open system, with the assumption that the
potential and kinetic energy of the gas are the same at the inlet and out is
(1)
Where
is the enthalpy flowing in through the dotted boundary line and
is the enthalpy flowing out through the dotted boundary line. The sign
conventions are:
Heat transferred to the system is POSITIVE
Work done on the system is NEGATIVE
The first law for a flow process is written in terms of the enthalpy H,
because the enthalpy includes the PV work done on the system by the gas
flowing in and the PV work done by the system as the gas flows out.
If the processes by which heat is transferred or work done on/by the system
are reversible, then it is possible to calculate numerical values of for the Q
and W in equation (1) and work out the internal energy change.
If the processes by which heat is transferred or work done on/by the system
are irreversible then, values at the start and end of the irreversible process
are required to calculate the change in internal energy.
Entropy Change
Starting with the first law expression for the process
dH = dQ
and replacing dH from the definition of specific heat at constant
pressure and Dq from the definition of entropy
and finally integrating between the start and end of the process
This is done because the ratio of specific heats does not vary with
temperature.
and
For an adiabatic process, the work done on or by the gas causes the
temperature, pressure and volume to vary as shown in the graphs
above
Entropy Change
There is no heat transfer to or from the gas and the process is
reversible so that