[bionet.neuroscience] free energy news

leo@zelator.uucp (Stefan Hartmann) (05/21/91)

Workshop for decentral energy research e.V. proudly presents:
-------------------------------------------------------------
******************************************************************************
*  How to win FREE energy with an                                            *
*  Adiabatic-isochoric-adiabatic-isochoric cycle over labile states of the   *
*  P-V-diagram                                                               *
******************************************************************************

from B.Schaeffer and W.D.Bauer
     DKOWA Gmbh 
     Pasewaldtstr.7 W-1000 Berlin 37, Germany

keywords: 
free energy, violation of the second law of thermodynamics,
spontaneous condensation,thermodynamic cycle, second law of thermodynamics 

Abstract:

Measurements with a benzene-water mixture at 154 deegrees Celsius show that 
a adiabatic-isochoric-adiabatic-isochoric cycle through the supersaturated 
states of the vapour phase during expansion allows a machine to be built, which 
in contrary to an equilibrium cycle does not need two temperature poles, 
but only one. 
Other substances will be proposed, which allow the same process to proceed at 
environmental temperatures.
Thus it will be possible to build a refrigirator which produces electrical 
power when operated !



1.Introduction

The concept of entropy was created by R.Clausius. He showed that the expression
for the entropy

                    dS=dQ/T=(dU+PdV)/T

applied to an ideal gas leads to the result that S is a potential.
With the development of the first real equations of state the usual concept of 
entropy was again introduced. However, in deriving thermodynamic potentials 
the assumption was then built into the theory that the entropy has to be a 
potential[1]. Regarding dynamic phenomena of phase transitions (for instance 
spontaneous condensation), however, the potential concept of entropy becomes 
senseless, because the labile states a gas can reach with a fast adiabatic 
expansion do not fulfil a unique equation of state. Thus, the thermodynamic 
potentials become ambiguous and lose the mathematical character of a potential. 
Therefore, the question arises, whether the second law of thermodynamics 
(in the versions of Planck[2] and Caratheodory[3]) remains valid for labile 
states. We will answer this question in this article empirically with 
a clear NO !


2.Experimental procedure

In order to test the dynamic P-V-behaviour of vapours as working media in 
machines we built an apparatus, which consisted of a cylinder with a movable 
piston, see fig.1. The diameter of the piston was 10 cm. The starting volume 
was 10 cm3 ,the end point volume was 1200 cm3. At the entry of the cylinder 
there was a valve, which opened and closed the conduit pipe from the boiler 
which contained a heating coil with a maximum power of 300 W. The fluid 
(300 cm3 benzene (Merck), 3 l bidistilled water) was cycled continously 
through glass beads in order to get a uniform evaporation of the non-miscible 
fluids, see fig.1. Boiler and cylinder were embedded in a heat insulation.
The piston of the cylinder was driven by a second larger piston moving in a 
cylinder(diameter 14 cm), whose pressure was delivered from a 12 bar compressor. 
The velocity of compression could be regulated by needle valves in the exhausts 
of both sides of the driving cylinder. The housing of the cylinder with the 
smaller piston was thermostated by cycling the fluid of the boiler through it 
with a pump. The difference in temperature between inlet and outlet was about 
0.1 degrees Celsius. The temperature of the lid of the cylinder could be 
regulated separately by a thermostated electric heating of maximal 100 W power. 
Cooling down could be improved by removing the heat insulation.
In order to measure the pressure a fast piezoelectric sensor was
built into the lid of the cylinder. It showed maximum deviations
of 0.01 bar when measuring the adiabate of air.
Data collection and regulation of the apparatus were achieved with a personal 
computer.


3.Measurement

At a fixed temperature of 154 degrees Celsius and a pressure of 11.4 bar the 
starting point was set. Then the valve to the cylinder was closed and the 
piston was expanded over about 0.3 sec, see fig.2. First the pressure went down 
and then rose again to a certain level with an increase in volume. In most cases 
a maximum was reached and the
curve went slowly down until it reached the end point.
At the end point of the expansion a pause interval of 3 sec was
set. This time was the optimum to get a maximum decrease in pressure about 
4 bar.
Then the piston was recompressed in a time of 0.3 sec and reached
again the starting volume. The pressure at this point was slightly
higher than the starting volume, but decayed and reached again the
starting level after some seconds. The net work area of this cycle was 
typically 200-300 J.
A necessary condition to get these results was that the lid of the cylinder 
was cooler than the housing (optimum difference 4 degrees Celsius). 
Performing periodically cycles with the cylinder closed the net work area 
decreased in time, but after refreshing the vapour by opening the valves of 
the cylinder the higher values could be achieved again.


4.Discussion

a)experimental
Our apparatus has the disadvantage that the pressure of the cycle can not be 
measured under conditions when the pressure is higher than the starting 
pressure. Nevertheless, it can be shown that with this cycle a net work yield 
is obtained. 
If we assume that the pressure of the working medium before reaching the end 
point would be so high that the work area becomes zero or even reverses sign, 
then the excess pressure pex can be estimated from the formula  
pex=work area/(vB-vA). Inserting values from fig.2 (work area 452 J,vB-vA=30cm3) 
we get an excess pressure pex of over 100 bar. This would overcome the driving 
compressor or would exceed the absolute maximum ratings of the apparatus which 
is designed for a maximum pressure of 20 bar. Neither is the case. It can also 
be shown that the small temperature gradient in the cylinder cannot be 
responsible for the work produced in the cycle. If we assume that the cycle is 
driven by this difference T1-T2 it would have an efficiency | of

               | = (Q2-Q1)/Q2 = (T2-T1)/T2 = -W/Q2 ,

where Q1/2 are the heats and T1/2 temperatures and -W the work.
Then our machine would have an efficiency | of |< 1%. This means for the cycle 
of fig.2 that heat amounts of at least Q2>45.2KJ and Q1<-44.75KJ would be 
exchanged between the wall and the working medium (mass<10 g) in about 4 sec. 
These amounts of heat are enough to heat up or to cool down the temperature of 
the fluid of the whole boiler (mass=3.3 kg) by about 3 oC, where we assumed, 
that the temperature change could proceed during the cycle in 4 sec instead of 
some minutes as actually observed by the temperature detection system of the 
thermostat (sampling time 1 sec) in the lid. Both heatings of our system 
(together max. 400 W) are too weak to compensate such amounts of heat in these 
times. 
The temperature difference works as a cooling trap collecting fluid in the 
cylinder and is responsible for the point where the evaporation begins in the 
expansion phase, but has nothing to do with the production of work in the sense 
of a Carnot cycle. 
Even if we accept the opinion that the work is due to the temperature 
difference, then the observed over-Carnot efficiency means that, according to 
the considerations of the Carnot theorem, in a machine this temperature 
difference could be maintained by a part of the work the machine delivers [1]. 
From this follows that the second law of thermodynamics is in fact violated.

b)theoretical
We explain the measured cycle in the following manner:
The fast decay at the beginning of the expansion adiabate is
"normal" adiabatic behaviour of the gas. The increasing pressure
with increasing volume expansion is caused by the evaporation of
the fluid under vacuum situated mainly on the warm wall of the
lid. If the evaporated fluid enters the cylinder it becomes
labile. The plateau region of the pressure and the often following
slow decrease is caused by the dynamic equilibrium between
evaporating fluid and expanding volume. The breakdown of the
pressure at the end point of the expansion is due to the return to
equilibrium.
There are two different ways to explain qualitatively the labile state of the 
expansion adiabate.
The first is the hypothesis of Doczekal[4], which says that benzene and water 
have different temperatures at the end of the adabatic expansion. For this 
interpretation some arguments can be found. The vapour pressure curve of 
water-benzene mixtures can be calculated simply, like ideal gases, by adding 
the partial pressure of water and benzene respectively [5]. This means that 
the gases are independent and do not interact because of the hydrophobicity of 
the benzene. The diffusion and the heat exchange between water and benzene is 
therefore hindered. Thus, in a fast adiabatic expansion both gases have 
different temperatures at the end point.
The second usual way to explain the expansion adiabate is that both components 
are at one temperature in the supersaturated and supercooled state and return 
to equilibrium via spontaneous condensation [6][7][8], changing the pressure 
energy of the gas into inner heat. 
The higher pressure at the end of the compression adiabate can be understood 
more easily. It is caused first by the fact that during the time interval 
between expanding and compressing heat enters the cylinder, and second by the 
fact that in a fast compression the applied energy is unequally distributed 
between the fluid and the gas because of the different moduli of compression.
Now we have to characterize the difference between our cycle and the carnot 
cycle, see fig.3a-c:
At the beginning of the cycle the working medium is in thermal contact with the
environment. This means in our case that the working medium of the cylinder is 
connected to the boiler as environment. Then the working medium is decoupled 
from the environment, i.e. the valve is closed. 
The first three steps of the cycle, including the isochoric part1), we assume 
to proceed totally adiabatically (dQ=0), because in effect no amount of heat 
can be exchanged in this short times with the environment. Assuming the first 
law of thermodynamics to be valid, we have to conclude that the temperature 
level of the working medium should be lower, when the piston reaches again the 
the end point A of the cylinder, because a net amount of work has been 
subtracted from the internal energy of the medium during the cycle. In order to
close the cycle the cooled down working medium is brought again in contact with
the environment (i.e. we open again the valve to the boiler) and after an 
isochoric influx of heat, the working medium reaches again the original 
temperature of the environment. The efficiency | of such a cycle should be 1.


5.Outlook

The described adiabatic-isochoric-adiabatic-isochoric cycle needs only one heat
reservoir in contrary to an equilibrium cycle. Our system, however, is not 
directly suited to building a machine which gains energy from cooling down the 
environment, because the starting temperature of the cycle is too high. 
Therefore, we have to look for substances, which show similar behaviour to 
benzene - water but at environmental temperatures.

________________________________________________________________________________
Footnote:
1) The word isochoric (dV=0) we have taken over from equilibrium thermodynamics. 
One should be aware of the difference that in equilibrium thermodynamics an 
isochoric change of state is bound to an exchange of energy with the working 
medium. We see here that in non-equilibrium thermodynamics this has not to be 
the case.
________________________________________________________________________________

We looked for such substances with the following strategy:
1)The substances must not be hazardous to the environment. Regarding mixtures, 
the substances must not react chemically. 
2)The critical temperature should not be too greatly in excess of
the environment temperature.
3)The critical pressure should be high enough to allow enough
energy to be produced.
If one looks at well ordered tables of materials [9] one finds on the polar side 
methanol, ethanol and ammonia, on the non-polar side propane, ethane and carbon 
dioxide.
Using binary and higher component mixtures of these substances it may be
possible to adapt them to each technical problem.



references:

[1]Sommerfeld A., Thermodynamik und Statistik  Harri Deutsch  Frankfurt,
Thun  1977 
[2]Planck M., Vorlesungen ber Thermodynamik   Leipzig  1897
[3]Caratheodory C.,Untersuchungen ber die Grundlagen der Thermodynamik. 
Math.Ann.67(1909),355-366
[4]Doczekal R., Deutsches Patent Zweigstelle sterreich 
17.10.37  Nr.155744
[5]Karapetyants M. Kh., Chemical Thermodynamics  Mir Publisher Moscow 1980
[6]Katz J.L.,Ostermier B.J., Journ.Chem.Phys. 47(2) (1967),478
[7]Zettlemoyer A.C.(ed.) Nucleation Phenomena Adv.Coll.Phen.7 Elsevier 1977
[8]Ehrler F., Spontane Kondensation VDI-Wrmeatlas 1988  
VDI-Verlag Dsseldorf 1988
[9]Reid R.C.,Prausnitz J.M., Poling B.E.  The properties of gases and liquids  
McGraw Hill  New York  1986 
[10]Schaeffer B.,Bauer W.D.   How to win energy with an adiabatic-isochoric-
adiabatic cycle over the labile states of the P-V-diagram     
WDB-Verlag  Berlin  1990 

figure legends:

These pictures follow in an uuencoded file which is still packed with LHARC.
These are fig1.pcx, fig2.pcx and fig3.pcx. You can view these Paintbrush
(Z-Soft)-pics with any viewer which can handle PCX format. They are scanned
black and white pics, no grayscale. Try it with vpic.exe, graphics workskop
or the paintbrush.exe program within the windows 3.0 package on the PC.

To unpack the pics: uudecode the scrambled ASCII-code and then type:
lharc e pics.lzh 

fig.1: schematic sketch of the apparatus:
 
1)lid with heating and piezo-electric sensor 2)valve 3)static pressure sensor 
4)boiler with heating and glass beads 5)pump
6)driving piston 7)position sensor 8)piston in cylinder


fig.2: P-V-diagram of an adiabatic-isochoric-adiabatic-isochoric cycle going 
over supersaturated states in the expansion phase. Work yield 452J 

fig.3a: Realization of the adiabatic-isochoric-adabatic-isochoric cycle 
phase 1: coupling of the working medium to the environment

fig.3b: Realization of the adiabatic-isochoric-adiabatic-isochoric cycle  
phase 2: decoupling from the environment, performing adiabatically the first 
three steps of the cycle and lowering the temperature of the medium

fig.3c: Realization of the adiabatic-isochoric-adiabatic-isochoric  cycle  
phase 3: coupling again the working medium to the environment, equating the 
temperature difference by an influx of heat into the working medium

And now the pics:
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``
end
sum -r/size 8885/47520 section (from "begin" to "end")
sum -r/size 11231/33922 entire input file

-- 
 
*******************************************************************************
*  EMAIL: leo@zelator.uucp     Stefan Hartmann                                *
*  COMPUSERVE: 72017,3216      GEnie: S.HARTMANN                              *
*  Phone : ++ 49 30 344 23 66      FAX : ++ 49 30 344 92 79                   *
********************************************************************************