Inobatsira Work kubudikidza kupisa Zvakatipoteredza

Part 1. Vamwe mashoko uye tsanangudzo.

The electromotive simba (emf) ibasa zvokunze simba munda mugove dzine kuitika tsime ... zvokunze simba kuita electroplating masero ari miganhu pakati electrolyte uye electrodes. Naivowo ushande muganhu pakati dissimilar simbi mbiri uye kuziva kuonana zvinogona musiyano therebetween [5, p. 193, 191]. Amount akasvetuka potentials pamusoro hukawanika dzose redunhu chikamu akaenzana dzingangoitika musiyano pakati conductors, riri panguva cheni mativi, uye anonzi electromotive simba emf kondakita redunhu ... cheni zvaisanganisira chete conductors wokutanga mhando akaenzana dzingangoitika kusvetuka pakati wekutanga newekupedzisira kondakita zvakananga taura navo (Volta mutemo) ... Kana redunhu iri zvakanaka rakazaruka, kuti emf Dunhu iri razero. Kuti agadzirise hayo-redunhu kondakita, izvo zvinosanganisira zvinenge imwe electrolyte, zvinoshanda mutemo volts ... Zviri pachena chete kondakita redunhu kuitika kamwe kondakita rechipiri mhando vari electrochemical masero (kana ngetani electrochemical okunze) [1, p. 490 - 491].

Polyelectrolytes muri Polymers vanokwanisa dissociating kupinda ions zviri mhinduro, saizvozvi macromolecule, vakawanda nekorasi mhosva ... crosslinked polyelectrolytes (Ion exchangers, Ion-Exchange nebwe) asingaiti kuiparadza, chete kuzvimba, apo rarinoshevedzwa kukwanisa dissociate [6, p. 320 - 321]. Polyelectrolytes dissociate kupinda isakarurama mhosva macroion uye H + ions dzinonzi polyacids uye dissociates kupinda chokwadi mhosva ions uye OH- macroion inonzi poliosnovaniyami.

Donnan zvakanyatsoenzana zvinogona ndiye zvinogona musiyano kuti ndepana Pasika muganhu pakati electrolytes maviri kana muganhu uyu haasi permeable kune ions zvose. Impermeability miganhu dzimwe ions anogona kukonzerwa Somuenzaniso, kuvapo membranes vane yakatetepa chaizvo pores izvo safambika kuti inoramba pamusoro imwe saizi. Kusarudza permeability pakati inowanikwa kunoitika uye kana paine ions zvakasimba saka kwakabatana mumwe maitikiro kuti kusiya kazhinji asingagoni. Chaizvoizvo ingozvibatai Ionic Ion Exchange Inogadzirwa nemasiridzi anobuda mumiti, kana Ion-Exchange boka wakaiswa homopolar chisungo ari samolecular zvakachinjikwa kana chizvaro. The mhinduro, ari mukati vakadaro matrices nezvimiro pamwe chete naro rimwe danho; mhinduro, iri kunze, - wechipiri [7. 77].

The yemagetsi kaviri rukoko (EDL) iri kuitika panguva inowanikwa pakati maitikiro mbiri wakaiswa pakati oppositely mhosva akaturikidzana dzinongoda pane imwe kure nomumwe [7. 96].

Peltier pave voga ichi kana Absorção de Água nokupisa panguva kuonana kubva conductors zviviri zvakasiyana zvichienderana pamusoro kutungamirirwa Magetsi ruchiyerera napakati kuonana [2, p. 552].

Part 2: Kushandisa kupisa svikiro iri electrolysis mvura.

Funga mashandiro pakati panowanikwa mudunhu iri electrochemical sero (hereinafter chaikosha), kuratidzwa schematically muna Fig. 1, zvakawanda emf nokuda womukati kuonana zvinogona musiyano (PKK) uye migumisiro Donnan (tsanangudzo pfupi pamusoro musimboti wenyika Donnan maturo, womukati PKK uye akabatanidza Peltier kupisa inopiwa muna chetatu nyaya).

Muonde. 1. kumiririrwa Schematic ane sero electrochemical: 1 - the cathode iri kushanyirwa ane mhinduro 3, ari electrochemical rutapudzo maitiro electrolyte cations musiwa pechiso wayo, wakaitwa mishonga inert kuvanzwira tsitsi doped N-semiconductor. Part of cathode unobatanidza kuti ive zvokunze voltage bhuku, metallized; 2 - kuti anode iri kushanyirwa ane mhinduro of 4, pamusoro pemvura yaro kuitika electrochemical oxidation maitiro electrolyte anions, akagadzirwa mishonga inert kuvanzwira tsitsi doped peji-semiconductor. Part of anode unobatanidza kuti ive zvokunze voltage bhuku, metallized; 3 - cathode nzvimbo, polyelectrolyte mhinduro, dissociating mumvura panguva macroion R- isakarurama mhosva uye chokwadi mhosva counterions K duku + (ari muenzaniso aripo hydrogen Ion H +); 4 - anode mupanda polyelectrolyte mhinduro mumvura dissociating kupinda chokwadi mhosva macroion R + uye okusafarira mhosva counterions diki A- (mu muenzaniso iyi hydroxide ions OH-); 5 - kuti Kamudzira (diaphragm), ndiko impermeable kune macromolecules (macroion) polyelectrolytes, asi chose permeable kune counterions duku K +, A- uye mvura mamorekuru pekupedzisira nzvimbo 3 uye 4; Evnesh - imwe kwokunze voltage kunobva.

Emf ne Donnan kushanda

Kuti zvijeke, ari electrolyte ari cathode nzvimbo (. 3, Figure 1) anosarudzwa aqueous polyacid mhinduro (R-H +), kuti electrolyte uye anode mupanda (4, muonde 1.) - aqueous poliosnovaniya (R + OH-). Somugumisiro dissociation polyacids vari cathode mupanda, pedo pemvura cathode (1, Fig. 1), pane zvakawanda Kuwanda H + ions. Positive mutariri dzinowanika kunharaunda cathode pamusoro haisi ndanyarara hangu isakarurama mhosva macroions R-, kubva havagoni kuuya pedyo pemvura cathode nokuda kwayo ukuru uye kuvapo imwe chokwadi mhosva Ionic chadenga (nokuti mashoko ona. Description Donnan kushanda muna mupanda №1 pamusoro chetatu nyaya). Saka, muganhu paiva kugadzirisa zvakananga neVadzidzi cathode pamusoro ane mhosva akanaka. Somugumisiro, mumwe electrostatic induction pamusoro cathode pamusoro, contiguous pamwe mhinduro, pane akaipa mutariri conduction maerekitironi. kureva panguva inowanikwa pakati cathode nomumativi Des mhinduro kunoitika. Munda Des achisunda maerekitironi kubva cathode - kusvikira mumushonga.

Saizvozvowo, pamusoro anode (2, Fig. 1), muganhu rukoko chemhinduro iri anode mupanda (4, Fig. 1) zvakananga neVadzidzi anode pamusoro ane kunaka nokuchengeta, uye pamusoro anode pamusoro, contiguous pamwe mhinduro, pane zvakanaka mutariri. kureva panguva inowanikwa pakati anode pemvura uye mhinduro uyewo kunoitika des. Munda Des achisunda maerekitironi kubva mhinduro - a anode.

Saka, munda Des nenguva interfaces ari cathode uye anode pamwe mhinduro, vachitsigirwa chafariz mhinduro Ion diffusion, muri vaviri womukati emf bhuku, kuita konzati ane zvokunze bhuku, i.e., kukuvadza akaipa mhosva iri loop counterclockwise.

Dissociation poliosnovaniya polyacids uye kunokonzera chafariz diffusion kuburikidza Kamudzira (5, Figure 1) H + ions kubva cathodic nzvimbo -. Kune anode, uye OH- ions kubva anode mupanda - a cathode. Macroion R + uye R- polyelectrolytes havagoni kufamba kubudikidza Kamudzira, saka kubva cathode nzvimbo pane zvakawandisa akaipa nokuchengeta, uye kubva anodic nzvimbo - doro zvakanaka kupomera, i.e., pane mumwe DPP nokuda Donnan kushanda. Saka Kamudzira uyewo kunoitika mukati emf, kuita konzati ane zvokunze tsime kupisa diffusion uye vakaramba mumushonga pamusoro ions.

In muenzaniso wedu, voltage mhiri Kamudzira anogona kusvika 0,83 volts, sezvo ichi unoenderana nokuchinja aikwanisa neezvitendero rehydrogen electrode kubva - 0,83 kusvika 0 volts panguva kuchinja kubva alkaline svikiro iri anode mupanda iri cathode mupanda acidic ezvinhu. Kuti mashoko, ona. In mupanda №1 ari chetatu nyaya.

Emf PKK kubva mukati

The Element emf It kunoitika, kusanganisira vari kuonana semiconductor anode uye cathode kwavo simbi kushumira kubatanidza kwokunze voltage kunobva. emf This nokuda pezviri PKK. Internal IF asingagari kusika, mukusiyana kune kwokunze munda yakapoteredza kubatana conductors vari muchadenga, i.e. Hazvina chokuita rakaramba kuti mhosva nezvimedu kunze conductors. Construction N-semiconductor / simbi / p-semiconductor iri zvakakwana kuzivikanwa uye rinoshandiswa Somuenzaniso, imwe thermoelectric Peltier module. Kwakakura pamusoro emf kwakadaro chivako pa nzvimbo tembiricha inogona kusvika tsika sezvakarayirwa 0,4 - 0,6 Volt [5, p. 459; 2, p. 552]. Muminda contactsGoogle tinotungamirirwa nenzira yakadaro kuti Vanosundira maerekitironi counterclockwise ari loop, i.e. kuita konzati pamwe kwokunze kunobva. Maerekitironi simudza simba zvakadini svikiro rokutora richipisa Peltier.

Internal KANA anomuka nokuda diffusion pakati maerekitironi vari kubatana nzvimbo electrodes uye mhinduro, nekusiyana, achisunda maerekitironi ari Kutenderera dzaizotungamirira loop. kureva rakaramba kuti maerekitironi muna Element counterclockwise mu vokukurukura izvi zvinofanira dzinounzwa Peltier kupisa. asi nekuti kuchinjwa maerekitironi kubva cathode kupinda mhinduro uye mhinduro iri anode zvinenge pamwe ane endothermic maitiro generating sehydrogen okisijeni, richipisa Peltier haina asunungurwa kupinda svikiro, uye kuti kuderedza endothermic chaizvoizvo, i.e. se "conserved" iri enthalpy kuti paumbwe rehydrogen uye okisijeni. Kuti mashoko, ona. In mupanda №2 chetatu nyaya.

vatakuri (maerekitironi uye ions) kufamba muna Element redunhu kwete namahwindo migwagwa, mhosva iri chinhu hakusi ari namahwindo redunhu. Mumwe Erekitironi anode yakawanikwa kubva mhinduro (mukufamba oxidation pamusoro OH- ions kuti okisijeni mamorekuru), uye akapfuura kuburikidza kwokunze wedunhu kuti cathode, iri volatilized pamwe rehydrogen mamorekuru (mu nedanho kuzoita ions H +). Saizvozvowo ions OH- uye H + haifambi mune namahwindo redunhu, asi chete kune runoenzanirana electrode, uye ipapo sasana muchimiro samolecular rehydrogen uye oxygen. kureva uye ions uye maerekitironi mumwe kufamba kwayo ezvinhu ari kuwedzera mumunda Des, uye kuguma nzira, kana vanosvika pemvura electrode ikashandiswa ari Morekuru, unoponesa yose inochengeterwa simba - nesimba makemikari ukama, uye kubva loop!

Zvose dzomukati zvinopa emf Eremendi, kuderedza tinorasikirwa zvokunze kunobva mvura electrolysis. Saka, kupisa ambient rokutora zvinhu panguva huchishanda kuramba diffusion pamusoro Des, ndiko kuderedza mari zvokunze tsime, i.e., Kunowedzera electrolysis kunyatsoshanda.

Electrolysis mvura pasina kwokunze kunobva.

In pokuongorora pezvakaitwa kuitika chinhu kuratidzwa Fig. 1, imwe zvokunze rine parameters hadzina kufungwa nezvazvo. Ngatitii dzomunyika nemishonga akaenzana Rd uye voltage pamusoro 0. Kuti Evnesh Chaikosha electrodes vari shorted kuti kungotarisa mutoro (ona Fig. 5). Panyaya iyi, mirayiridzo uye kwakakura Des minda yomuka panguva inowanikwa iri okunze kuramba chete.

Muonde. 5. Pane Evnesh (Fig. 1) kusanganisira pusa mutoro RL.

Kuona zvinhu zviri kwatangwa kuitika chokubuda mu maatomu akafanana izvi. Changing Gibbs mukana, maererano yemaitiro (1) kuti mupanda №1 ari chetatu nyaya:

Δ G Arr = (Δ H Arr - n) + Q Mod

Kana P> Δ H + Q Mod Mod = 284,5 - 47.2 = 237.3 (KJ / mol) = 1.23 (EV / Morekuru)

ari Δ G Arr <0 uye vaingoerekana muitiro zvinogoneka.

Tichakurukura mberi kuti zvinhu rehydrogen chizvarwa maitiro kunoitika nenzira acidic svikiro (electrode rine 0 volts), uye okisijeni ari alkaline (electrode rine 0,4 volts). Kwakadaro electrode potentials inopa Kamudzira (5, Fig. 5), asi voltage panguva iyo ichi 0,83 volts. kureva simba zvinodiwa paumbwe sehydrogen okisijeni iri kuderedzwa 0.83 (EV / Morekuru). Ipapo ezvinhu mukana vaingoerekana muitiro cha:

P> 1.23 - 0.83 = 0,4 (EV / Morekuru) = 77.2 (KJ / mol) (2)

Tinoona kuti simba Chipingamupinyi hydrogen uye okisijeni mamorekuru nzvengeka uye pasina kushandisa chinhu kwokunze voltage kunobva. kureva kunyange n = 0,4 (EV / Morekuru), i.e. kana yomukati electrode HPDC 0,4 volts, maatomu akafanana achava ezvinhu simba zvakanyatsoenzana, uye chero (kunyange diki) achinje pachiyero ezvinhu achaita zviri kuitika mudunhu.

Chimwe chipingamupinyi zvinoitwa panguva electrodes ndiye activation simba, asi panobviswa nokuda mugero wacho chaizvoizvo, anomuka nokuda smallness iri musiyano pakati electrodes uye mhinduro [7, p. 147-149].

Saka, nemhaka simba nezvavanofunga, tingati kuti vaingoerekana kuitika mune chinhu kuratidzwa Fig. 5, zvinokwanisika. Asi chii chaiko zvikonzero zvinogona kukonzera izvi iyezvino? zvikonzero izvi akarongwa pazasi:

1. Mukana yokuchinjira ose maerekitironi kubva cathode kupinda mhinduro kupfuura mukana yokuchinjira kubva anode kupinda mhinduro, kubva N-semiconductor cathode anezvakawanda chokuzvisarudzira maerekitironi rurefu simba sandara, uye peji-semiconductor anode - chete "mwena", uye izvi "maburi" vari pagungano simba pamwero pazasi cathode maerekitironi;

2. Kamudzira rinotsigirwa mune cathode nzvimbo ane acidic ezvinhu, uye ari anode - alkaline. Kana inert electrodes, ichi zvinotungamirira chokwadi kuti cathode electrode zvinogona kunova yakakura kupfuura anode. Somugumisiro, maerekitironi atama achishandisa remudunhu kwokunze kubva anode kusvika cathode;

3. pose chamakarairwa polyelectrolyte mhinduro anomuka nokuda Donnan zvazviri, anosika panguva electrode / mhinduro munda zvokuti munda nenguva cathode kunoita Erekitironi goho kubva cathode kupinda mhinduro, uye munda nenguva anode - Erekitironi kupinda anode kubva mhinduro;

4. pachiyero mberi uye kuzvishandura chinja panguva electrodes (Exchange dzenzvimbo) nekambani kuna H + ions zvakananga rutapudzo chinja panguva cathode uye oxidation pamusoro OH- ions panguva anode, kubva ivo pamwe paumbwe gasi (H2 uye O2) anokwanisa kusiya nyore kuita wenharaunda (Le Chatelier kuti Principle).

Kuedza.

For quantitative Maonero ari voltage mhiri mutoro nokuda Donnan zvazviri, kumwe kuedza kwakaitwa umo cathode Element kwaisanganisira ari kusashanda kabhoni pamwe rokunze graphite electrode uye anode - musanganiswa kusashanda kabhoni uye anion nebwe AB-17-8 pamwe rokunze graphite electrode. Electrolyte - aqueous NaOH mhinduro, anode uye cathode dzezvimwe vanoparadzaniswa ne chakaita zvokugadzirwa akanzwa. On rakazaruka kwokunze electrodes pane chinhu ichi aiva voltage vanenge 50 MV. Kana zvakabatana kuti chinhu pamusoro kwokunze mutoro 10 Ohm ngadzirambe kuitika vanenge 500 microamps. Kana ambient tembiricha inowedzerawo kubva 20 kusvika 30 0C voltage kune kwokunze electrode yakawedzera kusvika 54 MV. Kuwedzera voltage panguva ambient tembiricha zvinopupurira kuti kunobva emf ndiko diffusion, i.e. chafariz inofamba pakati inoramba.

For quantitative Maonero ari voltage mhiri mutoro kubva yomukati HPDC simbi / semiconductor kuedza chaiitirwa umo muchitokisi cathode chinosanganisira chakaita zvokugadzirwa graphite upfu pamwe rokunze graphite electrode uye anode - upfu pamusoro Boron carbide (B4C, peji-semiconductor) pamwe rokunze graphite electrode. Electrolyte - aqueous NaOH mhinduro, anode uye cathode dzezvimwe vanoparadzaniswa ne chakaita zvokugadzirwa akanzwa. On rakazaruka kwokunze electrodes ari chinhu voltage inenge 150 MV. Apo unobva kwokunze mutoro kune chinhu 50 kOhm voltage kwakadonha kusvika 35 MV., Yakasimba voltage donhwe kwakadaro nokuda yakaderera mukati Boron carbide uye, somugumisiro, yakakwirira womukati nemishonga Element. Investigation voltage maringe tembiricha ive chinhu mamiriro kwakadaro hakuna kuitwa. Izvi imhaka yokuti, kuti semiconductor, zvichienderana ayo makemikari anoumba, mwero doping nezvimwe zvivako, tembiricha shanduko dzakasiyana vanogona kufurira yayo Fermi chechetere. kureva tembiricha zvazvinoita emf Eremendi (kuwedzera kana kudzikisa), muchiitiko ichi kunobva zvakashandiswa, saka izvi hakusi INDICATIVE chiedzwa.

Panguva ino akaramba mumwe kuedza umo muchitokisi cathode chakagadzirwa musanganiswa kusashanda kabhoni upfu uye KU-2-8 pamwe rokunze Stainless simbi electrode uye anode kubva musanganiswa kusashanda kabhoni upfu uye anion nebwe AB-17-8 kuti zvekunze electrode kubva Stainless simbi. Electrolyte - aqueous mhinduro kubva NaCl, kuti anode uye cathode dzezvimwe vanoparadzaniswa ne chakaita zvokugadzirwa akanzwa. External electrodes kuti maatomu akafanana izvi October 2011 vanokwanisa pfupi-redunhu pusa ammeter. Current iyo inoratidza imwe ammeter, rinenge zuva pashure akatendeuka, yakaderera nezvikamu 1 Ma - kusvika 100 mkA (ndiro pachena nokuda polarization pakati electrodes), uye kubva ipapo kupfuura gore haachinji.

In dzinoshanda kuedza pamusoro apa maererano hubudirire zvinhu inaccessibility vakawana zvabuda substantially kudzika pane hunonzi zvinogoneka. Uyezve, ziva kuti chikamu zvachose womukati emf Eremendi nguva dzose ukapisa kuti tiine electrode zvakaitwa (kugadzirwa sehydrogen okisijeni) uye haagoni kuyerwa mudunhu kwokunze.

Mhedziso.

Achiratidza, tinogona kugumisa kuti hunhu anotibvumira kutendeutsa chafariz simba kupinda anobatsira simba kana basa vachishandisa se "hita" mamiriro ezvinhu uye asina "firiji". Saka Donnan kushanda uye nechomukati KANA vagotendeuka chafariz simba pamusoro mhosva inoramba iri yemagetsi mumunda simba DEL sezvo endothermic maitiro kupisa iri dzikwanise nemakemikari simba.

Vaiona kuonana chaikosha unopisa kupisa kubva svikiro uye mvura, uye allocates simba yemagetsi, hydrogen okisijeni! Uyezve, pfungwa simba zvinodyiwa uye kushandiswa rehydrogen sechinhu huni, uye mvura anodzoka shure kupisa svikiro!

Part 3 mupanda.

Chikamu ichi zvatowedzera kukurukurwa Donnan zvakanyatsoenzana zvazviri, panguva panosangana yomukati HPDC simbi / semiconductor uye Peltier kupisa pamusoro redox siyana uye electrode potentials ari chinhu.

Donnan zvinogona (Okuwedzera №1)

Funga mashandiro kuti panowanikwa Donnan zvaigona polyelectrolyte. Pashure dissociation polyelectrolyte counterions hutange duku, kubudikidza diffusion, vachisiya vhoriyamu maigara macromolecule. Directional diffusion pakati counterions vashoma vhoriyamu polyelectrolyte macromolecules ari solvent imhaka vawedzere wevasungwa munguva unorema kubva macromolecule sezvo kuenzaniswa navamwe mumushonga. Uyezve, kana Somuenzaniso, counterions duku vari isakarurama mhosva, izvi zvinoguma kuti yomukati mugove macromolecule vari chokwadi mhosva, uye mhinduro iri pakarepo yakabatana Vhoriyamu macromolecule - kunaka. kureva dzakapoteredza macroion vhoriyamu chokwadi mhosva, pane rudzi "Ion ezvinhu" duku pakaunda-ions - okusafarira mhosva. Kugumiswa Ionic chadenga mutariri kukura kunoitika apo electrostatic munda pakati Ion vhoriyamu macroion mhepo uye zviyero ari chafariz diffusion pamusoro counterions duku. The zvichiguma zvakanyatsoenzana zvinogona kusiyana mhepo uye Ionic macroions ndiye Donnan mukana. Donnan zvinogona Kunonziwo sezvo Kamudzira zvakawanda nekuti zvakadarowo kunoitika pamusoro semipermeable Kamudzira Somuenzaniso, kana Anopatsanura electrolyte mhinduro iyo ine ions nezvezvikwata zviviri - vanokwanisa uye kwete vanokwanisa kupfuura therethrough akachena solvent.

Donnan zvinogona anogona kunzi ave vakaomerwa zvakaitika diffusion mukana, apo mufambo rimwe ions (mu iyi macroion) ndiyo razero. Zvadaro, maererano [1, p. 535], achitora nokuchengeta pakaunda zvakaenzana mumwe:

E D = (RT / F) Dr ( A1 / A2), apo

Ed - Donnan zvinogona;

R - yezvisikwa gasi kuramba;

T - thermodynamic tembiricha;

F - Faraday kugara;

A1, A2 - pakaunda-basa iri kubatana maitikiro.

In nhengo iyi, sezvamakaropafadzwa Kamudzira anoparadzanisa poliosnovaniya zvinogadzirisa (ph = Lg 1 = 14) uye polyacid (ph = Lg 2 = 0), Donnan zvinogona mhiri Kamudzira pa nzvimbo tembiricha (T = 300 0 K) Hwaizova:

E D = (RT / F) (Lg ane 1 - Lg 2) Dr (10) = (8,3 * 300/96500 ) * (14 - 0) * Ln (10) = 0.83 Volts

Donnan zvinogona kuwedzera maererano tembiricha. Nokuti diffusion of electrochemical sero Peltier kupisa ndiye chete mabviro pagadzirwe anobatsira basa, hazvishamisi kuti zvakadaro zvinhu emf kunowedzera kuwedzera tembiricha. In diffusion Sero kuti kugadzirwa basa, Peltier kupisa anogara akatorwa zvakatipoteredza. Kana ano Rwako kuburikidza EDL akaumba Donnan zvazviri, mune mirayiridzo coinciding pamwe zvakanaka mirayiridzo romunda Des (i.e., kana munda Des anoita basa zvakanaka), kupisa wefodya kubva zvakatipoteredza pagadzirwe mapepa ichi.

Asi diffusion chinhu chiri kuramba uye unidirectional shanduko Ion wevasungwa, iyo pakupedzisira inotungamirira equalization kufungisisa uye kumisa rinotungamirirwa diffusion, kusiyana zvakanyatsoenzana Donnan, sezvamakaropafadzwa, pane nyaya idonhe quasistatic dzenzvimbo Ion wevasungwa, kamwe wakati asvika imwe ukoshi, anoramba kuzochinja .

Muonde. 2 inoratidza kuti chati iri redox potentials pakati zvinoitwa sehydrogen okisijeni kana kusandura acidity chemhinduro. The chati inoratidza kuti electrode zvinogona kuti okisijeni inotungamirwa maitiro pasina OH- ions (1.23 volts muimba acidic ezvinhu) rakasiyana chete zvinogona panguva mukuru wevasungwa (0,4 volts muimba alkaline svikiro) pa 0,83 volts. Saizvozvowo, electrode zvinogona rehydrogen-achiumba maitiro pasina H + (-0.83 volts mu alkaline svikiro) rakasiyana chete zvinogona panguva mukuru wevasungwa (0 V iri iine acid svikiro), uyewo panguva 0,83 volts [4. 66-67]. kureva pachena kuti 0,83 volts kunodiwa kuti vawane yakakwirira wevasungwa remvura nhengo ions. Izvi zvinoreva kuti 0,83 volts kunodiwa kuti vakawanda yokusava dissociation kwemvura mamorekuru kupinda H + uye OH- ions. Saka, kana Kamudzira zvinotsigirwa yedu Element cathode nzvimbo acidic svikiro uye nenzira alkaline anodic, kuti voltage kungakanganisa yayo DEL 0,83 volts, riri chibvumirano hwakanaka yokungotaura Masvomhu kukurukurwa ambotaurwa. voltage ichi inopa yakakwirira conductivity nzvimbo of Kamudzira nemvura dissociation kupinda ions mukati maro.

Muonde. 2. Dhiyagramu redox kuita potentials

manyowa mvura, uye H ions + uye OH- kupinda rehydrogen uye oxygen.

IF uye Peltier kupisa (Okuwedzera №2)

"The mhaka Peltier nezvinozoitika kuti avhareji simba dzavanofanira kuchengeta vatakuri (nokuti definiteness maerekitironi) munyaya yemagetsi conductivity mu conductors siyana akasiyana ... In kuchinja kubva imwe kondakita kupinda imwe Erekitironi kana fambisa zvakawandisa simba afoot kana kutsivira kusava simba panguva yayo mari (zvichienderana ano mirayiridzo).

Muonde. 3. Peltier zvainoita kuonana simbi uye semiconductor n-: ԐF - Fermi chechetere; ԐC - pasi conduction neboka semiconductor; ԐV - Valence bhendi; I - akanaka kutungamirirwa kuitika; madenderedzwa nemiseve dzakaratidza schematically maerekitironi.

Muchiitiko chokutanga pedyo kuonana asunungurwa uye wechipiri - vanonzi kunyura .. Peltier kupisa. Somuenzaniso, musi kuonana semiconductor - simbi (Figure 3) simba pamusoro maerekitironi vanopfuura kubva N-mhando semiconductor kuti simbi (kuruboshwe akagunzva) zviri kupfuura Fermi simba ԐF. Saka, vari kutyora chafariz zvakanyatsoenzana iri simbi. Zvakanyatsoenzana anodzorerwa somugumisiro kwemotokari, umo thermalized maerekitironi, achipa nekumwisa simba crystalline. afoot. The semiconductor simbi (kurudyi ikabatwa) runogona chete kupfuura akasimba maerekitironi, saka kuti Erekitironi gasi iri simbi inotonhodza. On kudzoreredzwa zvakanyatsoenzana kuparadzirwa oscillation simba vaparadzwa yekamuri "[2, p. 552].

Kuonana simbi / p-semiconductor zvazvakaitawo. nekuti peji-conductivity makomba semiconductor zvinopa ayo Valence bhendi riri pasi Fermi sandara, ipapo kuonana chichange dzaserera, umo maerekitironi dzinoyerera kubva S.-semiconductor kuti simbi. Peltier kupisa akasunungura kana yokuita zvinoitwa kuonana pakati conductors vaviri, nokuda kugadzirwa kunaka kana zvakanaka pamusoro pezviri KANA.

Vanobatanidzwa kuruboshwe kuonana pakakoromoka (Fig. 3), iri iyo Peltier kupisa yavaive, imwe sero electrolytic Somuenzaniso, aqueous NaOH mhinduro (Figure 4) uye simbi semiconductor uye N-ngazvive mishonga inert.

Muonde. 4. kuruboshwe kuonana N-semiconductor uye simbi yakazaruka uye akaisa mukati pakaputsika electrolyte mhinduro. Mazita zvakafanana muna Fig. 3.

Nokuti, kana iyezvino Rwako «Ini», ari semiconductor pakati N-maerekitironi nhetembo simba anosvika mhinduro pane anobuda mhinduro iri simbi, ichi nekumwisa simba (pakupisa Peltier) vanofanira kumira muchitokisi.

The kuitika kuburikidza sero kungava chete nyaya idonhe mairi electrochemical siyana. Kana exothermic maitiro muchitokisi, kuti Peltier kupisa ukasunungurwa muchitokisi, sezvo zvakawanda iye haana kuenda. Kana zvakaitwa muchitokisi - endothermic, kuti Peltier kupisa munongova kana pamwe kuti nekure endothermic chaizvoizvo, kureva, kuti vaumbe maitiro chigadzirwa. In muenzaniso uyu, yose sero maitiro: 2H2O → 2H2 ↑ + O2 ↑ - endothermic, saka kupisa (simba) of Peltier ndiko kusika mamorekuru uye H2 O2, vari yakaumbwa pamusoro electrodes. Saka, isu tiwane kuti kupisa Peltier kusarudzwa muna unosvikirwa zvakarurama N-kuonana semiconductor / simbi haisi asunungurwa shure kupinda zvakatipoteredza, uye anochengeterwa muchimiro kwemakemikari simba rehydrogen uye okisijeni mamorekuru. Zviri pachena, kushanda kwokunze voltage panobva wapera kuti electrolysis mvura, muchiitiko ichi chichava duku pane kuna dzakafanana electrodes, achiita hapana panowanikwa Peltier maturo ..

Pasinei zvivako zviri electrodes, sero electrolytic pachayo inogona kupinza kana chipise apo achipfuura Peltier ano nazvo. The quasi-kunofambira mberi ezvinhu, zvinogona yekupindurwa Gibbs masero [4, p. 60]:

Δ G = Δ H - T Δ S, apo

Δ H - enthalpy kuchinja muchitokisi;

T - thermodynamic tembiricha;

Δ S - yachinja entropy muchitokisi;

Q = - T Δ S - kupisa Peltier muchitokisi.

Nokuti rehydrogen-okisijeni electrochemical sero pa T = 298 (K), kuchinja enthalpy ΔHpr = - 284.5 (KJ / mol) [8, p. 120], kuchinja muna Gibbs zvinogona [4. a. 60]:

ΔGpr = - zFE = 2 * 96485 * 1.23 = - 237.3 (KJ / mol), apo

Z - Nhamba maerekitironi por Morekuru;

F - Faraday kugara;

E - emf Sero.

saka

Q St = - T Δ S St = Δ G etc. - Δ H etc. = - 237,3 + 47,2 = 284,5 (KJ / mol)> 0,

kureva rehydrogen-okisijeni electrochemical Sero zvinowanisa kupisa muna Peltier zvakatipoteredza, apo avandudze entropy kwayo richikwidibira ayo. Zvadaro, muna Ivan Kuchin kwacho, kuti electrolysis kwemvura, inova nyaya iri muenzaniso wedu, Peltier kupisa Q Mod = - Q St = - 47,3 (KJ / mol) kubva electrolyte kuchaita nyura kubva zvakatipoteredza.

Kureva P - Peltier kupisa akatorwa nharaunda iri kurudyi N-kuonana semiconductor / simbi. Kupisa P> 0 inofanira kumira muchitokisi, asi nekuti manyowa mvura muchitokisi endothermic maitiro (Δ H> 0), kuti Peltier kupisa P kuripa nokuda chafariz mugumisiro nemapinduriro:

Δ G Arr = (Δ H Arr - n) + Q Mod                                                                        (1)

Mod Q hunoenderana badzi Kuronga electrolyte, kubva Zviri tive electrolytic muchitokisi inert electrodes, uye N runotsamira chete pamusoro electrode zvinhu.

Mukana wokuti vanhu vanga (1) inoratidza kuti kupisa Peltier P uye Peltier kudziyisa Mod Q, muri kugadzirwa anobatsira basa. kureva Peltier kupisa rabviswa svikiro kunoderedza mari zvokunze simba panobva inodiwa kuti electrolysis. A mamiriro ezvinhu apo kupisa svikiro itsime simba nokuda pagadzirwe anobatsira basa, runozivisa diffusion, uyewo masero akawanda electrochemical, mienzaniso yakadaro zvinhu zvinoratidzwa mu [3, p. 248 - 249].

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