WO1991001493A1

WO1991001493A1 - Method and device for the determination of the obtained energy during electrolytic processes

Info

Publication number: WO1991001493A1
Application number: PCT/US1990/004062
Authority: WO
Inventors: Vesselin Christov Noninski; Christov Ivanov Noninski
Original assignee: Vesselin Christov Noninski; Christov Ivanov Noninski
Priority date: 1989-07-20
Filing date: 1990-07-19
Publication date: 1991-02-07
Also published as: BG50838A3; AU6549190A

Abstract

A method and apparatus for use in determining the quantity of energy obtained during electrolytic processes is disclosed. The apparatus includes a Dewar vessel (1) containing a measured quantity of distilled water (3). An electrolyte cell (4) is hermetically sealed in the vessel. A plurality of thermocouples (10, 11) are positioned within the vessel (1) for purposes of measuring temperatures within the vessel (1). A magnetic stirrer (12) is mounted in the bottom of the vessel (1).

Description

METHOD AND DEVICE FOR THE DETERMINATION OF THE OBTAINED ENERGY DURING ELECTROLYTIC PROCESSES

BACKGROUND OF THE INVENTION

Field: The invention is related to a method and device for the determination of the energy obtained during electrolysis processes. The invention is designed for the determination and study of new energy sources and especially for studies in cold nuclear fusion.

State of the Art; A method is known for determining the quantity of energy obtained during the electrolysis of heavy water wherein the heavy water and the electrodes are situated directly in a calorimetric vessel. The evolving deuterium and oxygen freely exit during the electrolysis cell (calorimetric vessel) , the electrolyte is stirred by the electrolytically obtained gases. The heat released during electrolysis is determined by applying known calorimetric measurements.

A device is also known for measuring the energy obtained during electrolysis processes involving an electrolytic cell (e.g. a Dewar vessel) . Such cells generally contain pure heavy water or a solution of LiOD in heavy water, stirred by the electrolytically-evolving gases. The cell may include sensors for measuring the temperature. The cathode has the form of a plate or rod.

The known method and device have the following disadvantages. They do not provide for the deuterium and the oxygen, evolved during the electrolysis, and the vapors of D O carried away by them to be kept in the electrolysis cell thus averting energy loss from the Dewar vessel. They do not provide stirring of the solution in the Dewar vessel outside the electrolys s cell b. which heat loss from the vessel is precluded.

In conventional devices and methods, the temperature of the calorimetric liquid is measured at only one location. The temperature reading is suspect since it does not account for the efficiency of the stirring or for the temperature differences throughout volume of the vessel. The Dewar vessel is not sealed hermetically. It is therefore possible that the vessel directly transfers heat to the environment. A comparatively small specific surface of the

Pd (Palladium) cathode is used. It follows that the cathodes saturated with deuterium and the desorption of deuterium proceeds for an extended amount of time.

The conventional devices and methods do not make it possible to measure the volumes of the evolving gases and to evaluate the character of the electrochemical reaction. Further, these devices and methods do not provide an indication whether absorption or desorption of D is taking place or whether there is an interaction between the D and the O . The aim of the invention is to create a method and a device for the determination of the energy obtained during electrolysis which avoids the disadvantages of the existing apparatus. The invention achieves its objectives with a device in which the electrolytic cell is hermetically sealed. The cell has a measured, changeable (variable) volume. Alternatively, a cell having constant volume is connected with a vessel of changeable (variable) volume. The cell is entirely immersed in calorimetric liquid in a Dewar vessel having a known heat capacity. After the cell's hermetization and its retention for at least a half an hour in the Dewar vessel the continuous monitoring of the temperature begins. The monitoring of the temperature occurs before, during and subsequent to the electrolysis. Simultaneously with the monitoring of the temperature, a continuous stirring of the calorimetric liquid, by means of a magnetic stirrer, is carried out. The temperature is monitored by measuring the calorimetric liquid's temperature in various regions of the vessel. The measurement of the temperature continues until complete equilibration of the temperature of the calorimetric liquid and that of the electrolyte occurs. This equilibration is achieved upon a coincidence of the temperature-time curve with that taken in absence of electrolysis. Thereafter the cell is removed from the Dewar vessel, and a secondary measurement of the volume of the respective cell or the vessel of changing (variable) volume connected with it is made. The volume measurement yields the total volume of D and O calculated on the basis of the quantity of electricity passed. During the electrolysis the changing quantities which determine the input and the obtained energy are measured continuously. The objective of the invention is addressed by a device for determining the energy obtained during electrolysis .processes. The device includes of a Dewar vessel containing calorimetric liquid in which the electrolytic cell is entirely immersed. The Dewar vessel and the electrolytic cell are hermetically sealed with stoppers. The stopper of the electrolytic cell is provided with several metal members which communicate with both the interior of the electrolytic cell and the calorimetric liquid. The electrolytic cell may be of changeable (expandable) volume. Alternatively, a cell of constant volume may be connected with an expandable vessel of variable volume by means of a metal tube which also functions as a cooler. Several sensors for measuring temperature are situated within different regions of the calorimetric liquid. Located at the bottom of the Dewar vessel is a magnetic stirrer. In the vessel an ampoule with a resistive heater is positioned for use in determining the heat capacity of the calorimeter. The electrolytic cell is usually made of glass but can also be fabricated of inert material having high specific electroconductivity. The cathode is fabricated to have a high specific surface area. The cathode is configured to have surfaces having very low radii c curvature.

The advantages of the invention include the precise measurement of the heat actually produced during the electrolysis. This measurement is attained by avoiding the various heat losses. The invention also ensures an equality of the temperature in the different regions of the calorimetric liquid. The quantities, measurements of the volume of the gases evolved during electrolysis on whose basis the input energy and the energy obtained are calculated, are recorded continuously. The use of these measurements ensures that no ancillary processes are taking place which can effect the calculations. This avoids any addition of heat effects, attributable to ancillary processes to the heat obtained during the electrolysis. By working with an electrode of high specific surface area the cathodes fast saturation with deuterium is ensured. The invention is illustrated by the device shown in FIG. 1 in which a set-up for the determination of the obtained energy during electrochemical processes is presented. The set up includes a Dewar vessel 1 in which a certain measured quantity of distilled water 3 is contained. Entirely immersed in the distilled water is an electrolytic cell 4 consisting of a test-tube 5 with a stopper 6 fitted with metal members 7. The electrolytic cell 4 is connected with a plastic, expandable vessel of variable volume 8 through means of a metal tube 9 which serves as a cooler. The weldings 10 and 11 of two thermocouples are respectively situated above and below the electrolytic cell. The electrolytic cell and the Dewar vessel are hermetically sealed by stoppers 2 and 6 respectively. At the bottom of the Dewar vessel a magnetic stirrer 12 is situated. Through the stopper of the Dewar the leads 13 are 14 are passed respectively for the cathode and the anode, connecting the electrolytic cell with the power supply. Three wires 15, 16 and 17 pass through the stopper 2 and connect the two thermocouples separately with a microvoltmeter. Below the electrolytic cell an ampoule 20 is situated. In the ampoule 18 and 19 is a resistor of thin constantan wire. The ends of that wire pass through the stopper 2 and can be connected with a power supply. All the leads situated in the Dewar vessel are insulated. The wires pass through the stopper 2 in such a way that a maximum hermeticity of the Dewar vessel is ensured. The leads are very thin and are thickened only at the upper surface of the stopper 2. As a result, they have little influence on the thermal conductivity of the latter.

The electrolytic cell contains D₂0 (Merck, 99.7%) + 0.01 M K₂S0₄. The cathode is made of Palladium (Pd) wire (Koch-Light Laboratories, 99.99%) of 0.05 cm diameter and 0.76 g weight bent many times into the configuration shown in FIG. 1. The anode was of Pt wire of 0.05 cm diameter spirally wound around the cathode. Care is taken to avoid any contact between the two electrodes. The constant current is applied by a PAR 273 potentiostat-galvanostat (working as a galvanostat) . The current was additionally controlled by a milliampermeter of class 0.5 (Czechoslovakia) or with a Hewlett-Packard 3465B Digital Multimeter. During the process the voltage applied to the cell is registered continuously with the assistance of a Sony-Tektronix 336 digital storage oscilloscope. At the conclusion of each experiment, the data from the memory of the oscilloscope was dumped through a GPIB (IEEE-488) interface bus into the memory of the Apple lie microcomputer with whose assistance a numerical integration is completed and the mean value of the voltage E applied during the time of the experiment is determined. With the help of cursors the time (t) is measured (at ±0.05 second accuracy) during which time the voltage is applied to the cell. The time of 0.01 seconds accuracy is read also with the help of a timer in a Casio fx-7100 scientific calculator. The temperature was measured with the assistance of a copper-constantan thermocouple. Its thermoemf was read with a Hewlett- Packard 3465B digital multimeter of 1.10^"6 V accuracy. The thermocouple was calibrated beforehand with a thermostat and its constant 0.0256 grad μV^""1 was determined. The electrolytic cell was immersed in distilled water contained in a closed Dewar vessel of 200 ml volume supplied with a magnetic stirrer. For measuring the thermal capacity a coil was manufactured of resistive constantan wire having a 1.7xl0~⁴ m dia and 22.8 Ω m^"1 specific resistance wound on teflon and situated in an ampoule. The method for the determination of the obtained energy during electrolysis processes was accomplished with the assistance of the above described device in the following manner. The heat capacity of the above-described calorimeter, shown in FIG. 1 was measured. To achieve this objective, the known method was applied when current is passed through the resistor 20 which is situated in the Dewar vessel. While stirring the liquid in the Dewar vessel with the magnetic stirrer 12 the temperature

(thermoemf)-time curve was recorded with the assistance of the thermocouples 10 and 11. The temperature time curve is recorded continuously before, during and after passing of current. The temperature (thermoemf)-time curve obtained at current of 0.5990 amps for 181.25 seconds at 9.76 volts is shown in FIG. 2. From figure 2 it is seen that the corrected temperature (change of the thermoemf times the thermocouple constant) at the mentioned current, voltage and time was equal to 1.26°C. The quantity of heat calculated according to Joule's law

^T2

^Tl

which would be released during the passing of this quantity of current is 0.5990 x 9.76 x 181.25 = 1060 J. From this calculation for the heat capacity, 1060/1.26 = 841 J grad is obtained.

After determining the heat capacity of the calorimeter the electrolytic cell is connected with the power supply and the same measurements are carried out - recording the temperature (thermoemf)-time curve before during and after completing the electrolysis of D₂0. After concluding the process the temperature of the Dewar vessel is monitored until the curve's run reaches the run of the same curve in the absence of electrolysis. The quantity Q obtained as a result of the electrolysis process is determined by the formula

where K is the heat capacity and At is the experimentally found temperature difference due to the processes that have taken place in the electrolytic cell.

In FIG. 3 a voltage-time curve is shown taken during electrolysis of heavy water at galvanostatic conditions - current 0.1280 A applied during 181.32 seconds. Under these conditions, the mean voltage of 44.0 V was calculated. From this data for the input energy, 1020 J was obtained.

In FIG. 4 the temperature (thermoemf)-time is shown taken before, during and after the same electrolysis process. On the basis of the curve shown in FIG. 4, it was determined that At = 1.44°C. Taking into account the measured value of the heat capacity of 841 J grad^"1 for the heat released as a result of passing of current, the value 1210 J was obtained according to eq. (2) .

To compare the obtained energy with the input energy it is necessary to take into account that the output energy consists not only of the obtained heat Q = 1210 J, but also the chemical energy which can be obtained during the interaction of the D₂ and the 0₂ which result from the electrolysis of D₂0. Usually, this chemical energy is the only useful energy which results from the electrolysis of water, in the present case. This energy is released by the formation of water from the hydrogen (deuterium) and oxygen. In referring to the total obtained energy, this chemical energy, which results from the interaction of deuterium and oxygen, should be added to the measured thermal energy (heat) . For determining the energy necessary for the iecomposition of water (heavy water) , reference is made to the well-established reaction

2D₂0 = 2D₂ + 0₂ (3)

This reference is made without resorting to any particular mechanisms for evolving D₂ and 0₂. The energy necessary for this reaction to take place is well established and is

AH = 70.4133 kcal mol^-1 = 294.6 kJ mol^"1 at 25°C. Referring to FIGS. 3 and 4, it is taken into account that constant current I = 0.1280 amps for 181.32 seconds for the quantity of electricity passed through the electrolytic cell is obtained IT = 23.2 C. When this quantity of electricity is divided with the quantity corresponding to the decomposition of one gram mol D O, according to eq. (3), 2F = 192986 C it is found that during electrolysis 1.2 x 10^~4 gram mols of heavy water have been decomposed. The energy input for the decomposition of this quantity of heavy water is equal to

294.6 X 1.2 X 10^"4 = 35

Therefore, in the present case the obtained energy is 1210 + 35 = 1245 J. If it is remembered that the entire quantity of the input energy is 1020 J, it is seen that the quantity of the energy obtained is 1245 J. The energy obtained therefore exceeds the input energy by 225 J. This means that the quantity of the energy obtained during the electrolysis of the heavy water energy exceeds the input energy by approximately 700% versus the expected 35 J.

When hydrogen (deuterium) is obtained electrochemically for use as fuel, the referenced 35 J are considered adequate. No attention is paid to the energy losses for overcoming of the ohmic resistances of the solution, the leads, the electrodes, the contacts, etc., because in principle these losses can be eliminated to a great extent. Likewise, no attention is paid to the losses connected with overcoming the over-potential of deuterium and oxygen since these over-potentials can be decreased and even eliminated. The only quantity of energy whose input is inevitable and cannot be decreased is the quantity necessary for the very electrolytic process (decomposition) of H₂0 in D₂0. In the best case it can be surmised that the chemical energy obtained when using H (D₂) as 1.ιel would be 100% versus the input energy for the decomposition of H O (D O) . In the case observed here considerably greater energy was obtained. This energy obtention cannot be connected with the electrochemical process of decomposition of H O (D O) or with any other known electrochemical or chemical process.

It is seen from the above data that during electrolysis which lasted about three minutes for the very decomposition of D O and obtaining of D and O 35 J energy was input while energy equal to 225 J was obtained. For the electrolysis 0.2 W power or 3.2 W cm^-3 specific power was used. The electrolytic cell acted as an energy source (heat + chemical energy) in producing 1.43 W power or 22.8 W cm^"3 specific power. If only the excess energy (225 J) is considered, 1.24 W or 19.7 W cm excess specific power was made available.

Claims

CLAIMS What is claimed:

1. A method for the determination of the energy obtained during the electrolytic processes at which the obtained heat is measured calorimetrically whose characteristics are: carrying said measurement out in a hermetically sealed electrolytic cell of predetermined variable volume, immersing said cell in a calorimetric liquid of a calorimeter - (a Dewar vessel of known heat capacity) after its hermetization and retention in the Dewar vessel for at least for one-half an hour, measurement of the temperature of the system before, during and after completion of the electrolysis, while simultaneously continuous stirring is ensured with a magnetic stirrer until control by measuring the calorimetric liquid's temperature in different regions of the calorimetric liquid at which the measurement continues until an entire equalization of the temperature of the calorimetric liquid with the temperature of the electrolyte for which it is judged by the coincidence of the temperature-time curve with a corresponding curve obtained in an absence of electrolysis, thereafter removing the cell from the Dewar vessel, measuring the volume of the cell including the vessel with the variable volume connected therewith and calculating the released quantity of energy by the established increase of the volume of the cell resp. of the variable volume vessel connected therewith, equal to the total volume of D₂ and O , calculated on the basis of the quantity of electricity that has passed, during the electrolysis, the changing quantities, determining the input and the obtained energy, are measured continuously.

2. A device for the determination of the obtained energy during electrolytic processes by the method according to Claim 1 comprising a Dewar vessel, an electrolytic cell and temperature sensors immersed in the cell whose characteristics are: that the Dewar vessel (1) contains calorimetric liquid in which the electrolytic cell (4) is entirely immersed, the Dewar vessel (1) being hermetically sealed with a stopper (2) and the electrolytic cell with stopper (5) , supplied with metal members (7) which communicate with the interior of the cell and with the calorimetric liquid at which the cell can be of variable volume and when it is not, the cell is connected with a vessel of variable volume (8) through a metal tube (5) which serves as a cooler a plurality of the temperature sensors 10 and 11 situated in different regions of the calorimetric liquid, a magnetic stirrer (12) situated at the bottom of the Dewar vessel, and an ampoule with an electroresistive heater (20) situated in the Dewar vessel for the determination of the heat capacity of the calorimeter at which the cathode having the lead (13) is of high specific surface, some regions of its surface being of very low radius of curvature.

3. A device according to Claim 2 whose characteristic is: that the electrolytic cell (4) is manufactured of inert material of high specific thermal conductivity.