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SYSTEMS
system
I. law of thermodynamics
If a system is doing a work or the surroundings is doing
a work on the system, its internal state is changed.
E.g. if we compress a gas in a cylinder with a piston
the temperature of the gas increases. Similarly, if there is
a chemical reaction between the components of the
system, its temperature changes. Or, if you consider an
iceberg moving on rocky surface, the friction produces
heat and the iceberg changes its phase it melts. The
cause producing the change of the state is called energy.
Energy can be thus defined as the ability to change given
(equilibrium) state of matter.
H = U + PV
where P is pressure and V volume of the system
qP = H2 - H1 = H
This expression says that the change of enthalpy in
any process is dependent only on the initial and final
state of the system. In the case of chemical reaction it
is the state of the reactants at the beginning of the
reaction and the state of products in the end of the
reaction.
dS = dq/T
According to Carnot theorem the efficiency of reversible
machine is maximum. Thus, the irreversible machines
have always lower efficiency. For the irreversible process
we get:
dS > dq /T
dS > 0
and for reversible process:
dS = 0
It means that entropy is growing under irreversible
processes and in equilibrium, when only reversible
processes can proceed, it does not change. Entropy can
be looked upon as a measure of spontaneousness, as it
increases during spontaneous processes.
dU = dqrev - dwrev
For dqrev we substitute from the definition of entropyTdS:
dU = TdS - dwrev
(U - TS) = -dwrev
F = U - TS
(U - TS + PV) = -w,rev
We can see another state function (U - TS + PV), the
decrease of which indicates maximum useful work that
can be done by the system under constant pressure and
temperature. It is called Gibbs function and labeled G:
G = U + PV - TS = H - TS
- G = RT ln K.
dS = deS + diS
For the rate of entropy change we obtain:
dS = dqrev/T + diS
diS = dS - dqrev /T
and after aritmetical rearrangement we get:
diS = - dG/T
That can be expressed in words:
The increase in entropy of open system due to internal
nonequilibrium processes is proportional to the decrease
of the Gibbs function of the system.
=
=
=
=
(i)S,V
(i)S,P
(i)T,P
(i)T,V
Concomitantly:
(i)S,V = (i)S,P = (i)T,P = (i)T,V = i
dni = i d
and
d = 1/ i dni
The reaction rate is given:
v = 1/ i (dni/dt)
After substituting for dni we get:
v = d/dt
For the change of mols of reacting substance we get:
dni/dt = i v = i (d/dt)
W = - i i = (dG/ d)T,P
which represents work done by the system after all
reactions run through
diS/dt = Wv/T
This can be expressed in words:
the rate of entropy production in open system under
constant temperature and pressure is given by product of
reaction rate and the work done by the system.
= 1/V (dS/dt)
and function :
= T
The function is proportional to the rate of entropy in
unit volume and is called dissipative function
= T = J i Xi > 0
where Ji ...... rate of flux of the process
Xi ..... driving force of the process
depends on the rate of flux and driving force of the
process, which are time-dependent parameters, therefore
is also a function of time:
J = J(X)
and it holds:
J(X) = L(X)
This equation represents linear phenomenological
relationship between the parameters of generalized
fluxes and forces, and the coefficient L is called
linear phenomenological coefficient
diS'/dt = 1/T Jk Xk 0
i.e. there are processes during which the entropy of
the system decreases
= n + d
where
n ..... function of bound dissipation
d ..... function of outer dissipation
According to the principle of the least outer dissipation
of energy:
In the stationary state of any thermodynamics system, the
function of outer dissipation reaches the least possible
values.