Work waxtar leh by kulaylka Deegaanka

Part 1. Ereyada iyo micnaha Qaar ka mid ah.

Ciidamada electromotive (emf) waa qayb muhiim field force dibadda ka kooban il hadda ... ciidan dibada ah ku simaha ee electroplating unugyada at xuduudaha u dhexeeya elektrolytka iyo electrodes ah. Sidoo kale waxay ku shaqeeyaan on soohdinta u dhaxaysa laba Biraha duwana oo loo ogaado xiriirka kala duwan yihiin laga yaabo in therebetween [5, p. 193, 191]. Inta ka bootin kara oo dhan dusha ka mid ah qaybta circuit waa loo siman yahay si ay u kala duwan yihiin laga yaabo in u dhexeeya kirishbooyada ah, ku yaal silsilad dhammaanaysaa, iyo waxaa loo yaqaan emf xoog circuit kaari ah electromotive ... silsilad ka kooban oo kaliya oo ka mid ah kirishbooyada nooc ugu horeysay ee waa loo siman yahay si boodi ka iman kara ee u dhexeeya hore iyo kaari ee la soo dhaafay in si toos ah la xiriir iyaga (sharciga kooxda Fluminense bisha) ... Haddii circuit waa si fiican u furan, emf ah circuit tani waa eber. Si aad u saxdo kaari-wareeg furan, oo ay ku jiraan ugu yaraan hal elektrolytka, volts sharciga lagu dabaqi karo ... Sida iska cad, oo kaliya circuit kaari ka kooban ugu yaraan hal kaari ah nooca labaad waa unugyo electrochemical (ama silsilado xubno electrochemical) [1, p. 490 - 491].

Polyelectrolytes waa polymers awood fogaanayo galay udhigo in xal, sidaas in macromolecule isla, tiro badan oo lagu eedeeyay ... polyelectrolytes crosslinked (exchangers ra'iyi, soo noqnoqda cusbi ra'iyi-exchange) ma milaan, kaliya barari, halka haysashada awood u leh inay beri [6, p. 320 - 321]. Polyelectrolytes beri galay macroion xun lagu soo eedeeyay iyo udhigo H + waxaa lagu magacaabaa polyacids oo iska fogeeyay arrinta galay udhigo si wanaagsan lagu soo eedeeyay iyo macroion OH- yeedhay poliosnovaniyami.

Donnan iman kara hoganaya waa kala duwan yihiin laga yaabo in dhacdaa at boundary wajiga u dhexeeya labada electrolytes haddii xadka tani ma aha permeable dhammaan udhigo. xadka Impermeability Runbaana qaar ka mid ah waxaa keeni kara, tusaale ahaan, joogitaanka xuubka la daloolada aad u cidhiidhi ah, kuwaas oo aan la mari karin, waayo qayb ka size gaar ah ka sarreeya. permeability Selective ee interface ka dhacdaa, oo haddii wax udhigo si xoogan loola xiriirinayay in mid ka mid ah waji ah in uu ka tago guud ahaan ma sheegi karo. Sida saxda ah u dhaqmaan Beeyada sarrifka ra'iyi Madbacada qaranka, ama koox ra'iyi-sarrifka go'an bond homopolar in daaqaddii kelli ama furta. Xalka ugu, iyagoo gudaha foomamka matrices sida wada waxaa hal waji leh; xal, oo ku yaalla meel ka baxsan, - labaad [7. 77].

The lakabka double korontada (EDL) waxaa dhaca interface ee labada weji dhigay of layers oppositely eedeeyay amro fogaan ah qaar ka mid walba [7 kale. 96].

Peltier saameyn go'doomin ama nuugista kulaylka at xiriir laba kirishbooyada kala duwan ku xidhan jihada hadda korontada dhex maraya xiriirka [2, p. 552].

Qeybta 2: Isticmaalka dhexdhexaad kulaylka in electrolysis biyaha.

Ka fikir hab ay of dhacdo Bannaanka ee gacanta electrochemical (element oran), muujisay schematically in berdihii. 1, emf badan sabab u ah xiriirka gudaha farqiga u iman kara (PKK) iyo saamaynta Donnan (sharaxaad kooban oo nuxurka saamayn Donnan ah, PKK gudaha iyo xidhiidha kulaylka Peltier waxaa lagu bixiyaa saddex meelood oo meel maqaalka).

Berdaha. 1. matalaad Schematic of cell ah electrochemical: 1 - cathode la xiriiray xal of 3, falcelinta yareynta electrochemical of siifilisku elektrolytka ee dhici ay dusha, ee ah kiimikada inert ah loola doped n-Semiconductor sameeyey. Qayb ka mid ah cathode waxaa xidhiidhinaya ilo danab dibadda, metallized; 2 - anode la xiriiray xal of 4, dushiisa oo dhan ku dhacaan fal-celin lagu qayilo electrochemical of anions elektrolytka ah, ee kiimikaad inert ah loola doped p-Semiconductor sameeyey. Qayb ka mid ah anode waxaa xidhiidhinaya ilo danab dibadda, metallized; 3 - meel cathode, xal polyelectrolyte, fogaanayo in biyo at macroion R- xun lagu soo eedeeyay iyo counterions wanaagsan eedeeyay K yar + (in tusaale ahaan la joogo waa ra'iyi hydrogen ka H +); 4 - anode xal polyelectrolyte qol biyo fogaanayo galay macroion R wanaagsan eedeeyay + iyo counterions xun eedeeyay A- yar (tusaale ahaan waxa hydroxide udhigo OH-); 5 - ka xuub (diaphragm), waa ka dusi karin in macromolecules (macroion) polyelectrolytes, laakiin gabi ahaanba permeable in counterions yar K +, A- iyo taagoo biyo meel la wadaago 3 iyo 4; Evnesh - an isha danab dibadda.

Emf by Donnan saamayn

Waayo, Hufnaan, elektrolytka ee meel cathode ah (. 3, Jaantuska 1) la doorto xal aqueous polyacid (R-H +), elektrolytka iyo qol ka anode (4, berde 1.) - poliosnovaniya aqueous (R + OH-). Sidaas darteed of polyacids dissociation in qol cathode ah, meel u dhow dusha sare ee cathode (1, berdihii. 1), waxaa jira fiirsashada kordhaysa oo ah H + udhigo. lacag Positive muuqashada u dhow dusha cathode waxaa waxba kama bedelin macroions xun eedeeyay R-, tan iyagu ma iman karo meel u dhow dusha sare ee cathode ah ay sabab u tahay baaxadda iyo joogitaanka jawi wanaagsan eedeeyay Madbacada qaranka (wixii faahfaahin ah ka eeg. Description saamayn Donnan ee Annex №1 ah saddex meelood oo meel maqaalka). Sidaas darteed, lakabka xuduud of xal si toos ah xiriir la dusha cathode leeyahay lacag fiican. Sidaas darteed, induction ah electrostatic dushiisa cathode ah, jiidda xal ah, waa lacag xun ee electrons tabinta ah. ie at interface u dhaxeeya dusha cathode iyo xal DES dhacdaa. Field of DES u riixo electrons ka cathode - si xal.

Sidoo kale, on anode (2, berdihii. 1), lakabka xuduud ah xalka in qol anode (4, berdihii. 1) si toos ah xiriir la dusha anode leeyahay amar diidmo ah, oo ku saabsan dusha anode ah, jiidda xal ah, waa lacag fiican. ie at interface u dhaxeeya dusha anode iyo xalka sidoo kale dhacda DES. Field of DES u riixo electrons ka xalka - anode ah.

Sayidka, berrinkii DES ee interfaces ah cathode iyo anode xal ah, oo ay taageerayaan xal kaamerada sida- ra'iyi, waa laba il emf gudaha, ku simaha riwaayad la il dibedda ah, i.e., riixaya ku eedeeyay negative in loop ku counterclockwise.

polyacids poliosnovaniya Dissociation iyo sidoo kale sababa sida- kaamerada dhex xuub (5, Jaantuska 1) H + udhigo ka bannaan ee cathodic -. si anode ah, iyo udhigo OH- ka qol anode ah - cathode ah. polyelectrolytes Macroion R + iyo R- ma dhaqaajin karo iyada oo loo marayo xuub, waxaa sidaas ka bannaan cathode halkaas waa kharash xad-dhaaf xun, oo ka bannaan anodic ah - lacag xad-dhaaf wanaagsan, i.e., waxaa jira DPP kale ay sabab u tahay saamaynta Donnan ah. Sayidka, xuub sidoo kale dhacda gudaha emf ah, ku simaha riwaayad la il dibadeed ah sida- kulaylka iyo dayactiro xalka of udhigo.

In aynu tusaale ahaan, danab oo dhan xuub gaari karaan 0,83 volts, sida this u dhiganta isbeddel ku iman kara ee koronto hydrogen caadiga ah ka - 0,83 0 volts at guurka ka dhexdhexaad ah xumadoodu in qol anode deegaanka acidic qol cathode ah. Wixii faahfaahin ah, ka eeg. In Annex №1 ah saddex meelood oo meel maqaalka.

Emf PKK gudaha

The emf Cunsurka Waxay dhacdaa, oo ay ku jiraan in anode xiriir Semiconductor iyo cathode in qaybo bir ah ay u adeegaya in ay ku xidhmaan il dibadda danab. emf Tani ay sabab u tahay gudaha PKK. Gudaha HADDII ma abuuro, in la barbardhigo berrinka dibadda ee meel bannaan oo ku wareegsan kirishbooyada xiriir ah, i.e. Waxa aanu saameyn ku yeelan doonin mooshinka qayb eedeeyay baxsan kirishbooyada ah. Dhismaha n-Semiconductor / biraha / p-Semiconductor waxaa ku filan loo yaqaan oo loo isticmaalo, tusaale ahaan, a thermoelectric module Peltier. baaxadda emf ah Qaab dhismeedka a heerkulka qolka sida ay gaari karaan qiimaha amarka of 0.4 - 0.6 Volt [5, p. 459; 2, p. 552]. Fields in xiriir toos ah ay yihiin sidan oo kale in ay ku hardiyi electrons counterclockwise in loop ka, i.e. fal riwaayad la il dibedda. electrons The kor loo qaado heerka tamarta ee dhexdhexaad ah ahmiyadda ugu kulaylka Peltier ah.

Gudaha HADDII timi sabab u sida- ee electrons meelaha xiriir ah electrodes iyo xal u, on lid ku ah, riixo electrons jihada bilow in loop ah. ie mooshinka ee electrons in Cunsurka ah counterclockwise in xiriirada waa in lagu qoondeeyay kulaylka Peltier. laakiin maxaa yeelay, kala iibsiga ee electrons ka cathode galay xalka iyo xalka ee anode waxaa qasab ku weheliyay falcelin endothermic guud hydrogen iyo oxygen, kulaylka Peltier aan la sii daayo dhexdhexaad ah, oo waa in la yareeyo saamaynta endothermic, i.e. sida "conserved" in enthalpy ee formation of hydrogen iyo oxygen. Wixii faahfaahin ah, ka eeg. In Annex №2 saddex meelood oo meel maqaalka.

sidayaal (electrons iyo udhigo) guurto circuit Cunsurka ma Waddooyinkiisa u xiran yihiin, lacag la'aan in element uusan u dhaqaaqin in circuit xidhan. anode electron kasta oo ka xalka (koorsada of qayilo ee atammada OH- in u taagoo oxygen) helay, iyo iyada oo wareeg dibadda ah si ay u cathode ka gudbay, waxaa wada volatilized la taagoo hydrogen (geedi socodka soo kabashada ee atammada H +). Sidoo kale udhigo OH- iyo H + aadan guurin circuit xidhan, laakiin kaliya in ay koronto u dhiganta, ka dibna uumi qaab hydrogen kelli iyo oksijiin. ie iyo udhigo iyo electrons kasta dhaqaaqin in ay deegaanka oo duurka ku dardar-of DES, iyo dhamaadka waddada, marka ay gaaraan dusha sare ee koronto ah lagu daro in Britain ay, diinta tamarta oo dhan lagu kaydiyaa - tamarta ee bond kiimikada ah, oo ka mid ah loop ah!

Dhamaan ilaha gudaha ee emf Cunsurka, yareeyo kharash il dibadda electrolysis biyaha. Sayidka, kulaylka daarmayaay'e ku aadeen xubno inta ay howlgalka ay u ilaaliyaan sida- of DES, waa in la yareeyo kharashka ku baxa isha dibadda, i.e., Waxa uu kordhiyaa oolnimada electrolysis ah.

Electrolysis oo biyo ah oo aan meel kasta dibadda.

In dib u geedi socodka ka dhacda element ku cad berdihii. 1, an oo xuduudaheedu il dibadeed aan xisaabta lagu darsadaa. Ka soo qaad in iska caabintii gudaha waa loo siman yahay si Rd iyo danab a of 0. Si Evnesh electrodes Cunsurka waxaa shorted si load a dadban (eeg berdihii. 5). Xaaladdan oo kale, ka jihada iyo magnitude of beeraha DES timi at interface ee canaasiirta isku.

Berdaha. 5. Halkii Evnesh (berdihii. 1) oo ay ku jiraan RL load dadban.

Go'aaminta xaaladda socodka hadda lama filaan ah in element this. Beddelidda iman kara Gibbs, sida ay caanaha (1) ee Annex №1 ah saddex meelood oo meel maqaalka:

Δ G Aar oo = (Δ Aar oo H - n) + Q mod

Haddii P> Δ H + Q mod mod = 284,5 - 47.2 = 237.3 (KJ / mol) = 1.23 (eV / Britain)

ka Δ G Aar oo <0 iyo habka lama filaan ah waa suurto gal.

Waxaan dheeraad ah ka fiirsan doonaa in xubno ka ab ka hydrogen reaction dhacdaa dhexdhexaad ah acidic (iman kara koronto 0 volts), iyo oxygen ee (iman kara koronto ee 0.4 volts) xumadoodu ah. kartiyo koronto noocan oo kale ah waxay bixisaa xuub (5, berdihii. 5), danab at kaas oo waa in ay ahaataa 0,83 volts. ie tamarta looga baahan yahay formation of hydrogen iyo oxygen waa la dhimay by 0.83 (eV / Britain). Markaas xaaladda suurtagalnimada ee nidaamka lama filaan ah waxay:

P> 1.23 - 0.83 = 0.4 (eV / Britain) = 77.2 (KJ / mol) (2)

Waxaan ka heli in caqabad tamarta ee hydrogen iyo oxygen u taagoo ka baaqsan karo oo aan la isticmaalayo isha dibadda ah danab. ie xataa n = 0.4 (eV / Britain), i.e. markii koronto gudaha HPDC 0.4 volts, element ku jiri doona xaalad hoganaya firfircoon, iyo wax kasta oo (xitaa yar) isbeddelka xaaladaha dheelitirka ka dhigi doonaa in hadda ee Bannaanka.

Caqabad kale oo dareen diidmo ee electrodes waa tamarta hawlgelinta, laakiin waxaa la ciribtiray by saamayn tunnel ah, oo sababo ay sabab u tahay smallness ee farqiga u dhaxeeya electrodes iyo xalka [7, p. 147-149].

Sayidka, iyadoo ay ku saleysan tixgelin tamarta, waxaannu ku tirinnaa in hadda lama filaan ah in element ku cad berdihii. 5, waxa suurto gal ah. Laakiin waxa sababaha jirka waxay keeni kartaa hadda this? Sababaha waxaa ku qoran yihiin hoos ku qoran:

1. itimaalka ee kala guurka ah electrons ka cathode galay xalka ka badan itimaalka ee guurka ka anode galay xalka, tan n-Semiconductor cathode leedahay wax badan oo electrons lacag la'aan ah heer sare tamarta, iyo anode p-Semiconductor ah - "godad" oo kaliya, oo kuwanu "godad" waa heerka tamarta hoos electrons cathode ah;

2. xuub waxaa taageeray in meel bannaan oo cathode ah deegaan acidic ah, iyo in anode ah - xumadoodu. In the case of electrodes inert, waxay keenaysaa in xaqiiqda ah in laga yaabo in koronto cathode noqdo ka badan anode ah. Sidaas awgeed, waa in electrons guurto iyada oo wareeg dibadda ka anode si cathode ah;

3. Kharashka dusha of xal polyelectrolyte ka kacay ay sabab u tahay saamaynta Donnan ah, abuuraa at beerta xalka koronto / sida in beerta at cathode ee kor u dhalid electron ka cathode galay xalka, oo beerta at anode ah - galo electron galay anode ka soo xalka,

4. dheelitirka Weeraryahanka iyo beddeli reactions at electrodes ah (hadda exchange) u janjeedhaan dhinaca H + udhigo dareen diidmo oo hoos u si toos ah ugu cathode oo lagu qayilo ee atammada OH- at anode ah, tan iyo markii ay ay la socdaan formation of gaaska (H2 iyo O2) oo awood u leh si fudud u tagay zone reaction (Le Chatelier ee Mabda'a).

Tijaabo.

Qiimaynta taranta ee danab oo dhan load ah by saamayn Donnan ah, tijaabo ayaa la sameeyaa oo Cunsurka cathode ka koobnaa carbon ka shaqeysiin la koronto dibadda graphite iyo anode ah - isku dar ah ee carbon firfircoonaan iyo cusbi anion AB-17-8 la koronto ah graphite dibadda ah. Elektrolytka - xal NaOH aqueous, anode iyo cathode meelaha kala dareemay a dardaro. On electrodes furan dibadda ee element this lahaa danab ah oo ku saabsan 50 MV. Marka xiran element ah load dibadda ee 10 Ohm go'an hadda ee ku saabsan 500 microamps. Marka daarmayaay'e heerkulka kordhay 20 ilaa 30 0C danab si koronto dibadda kordhay 54 MV. Kordhinta danab ee heerkulka daarmayaay'e Xaqiijiyay in isha emf waa sida-, i.e. mooshin kaamerada of qayb ka ah.

Qiimaynta taranta ee danab oo dhan load ka tijaabo biraha / Semiconductor HPDC gudaha la sameeyay kaas oo cathode unug ka kooban yahay oo ah budada graphite dardaro la koronto dibadda graphite iyo anode ah - budada ah carbide boron (B4C, p-Semiconductor) la koronto ah graphite dibadda ah. Elektrolytka - xal NaOH aqueous, anode iyo cathode meelaha kala dareemay a dardaro. On electrodes furan dibadda ee danab element ahaa 150 MV. Marka xira load dibadda u element 50 kOhm danab u dhacday 35 MV., Noocan oo kale ah hoos u xoog danab sabab u carbide hoose jaleelada boron iyo, iyada oo sababtu tahay, Cunsurka sare gudaha iska caabin ah. danab Baarista kasoo horjeeddo heerkulka for element ah ee qaab-dhismeedka sida aan la fuliyay. Tan waxa u sabab xaqiiqada ah in, waayo Semiconductor ah, taas oo ku xidhan Halabuurka kiimikada ay, degree dawooyinka iyo guryaha kale, isbedelka heerkulka siyaabo kala duwan saamayn ku yeelan karaan heerka ay Fermi ah. ie heerkulka saamayn on emf Cunsurka (korodhka ama hoos u dhac), haddii ay taasi ku xiran tahay agabka loo isticmaalo, sidaas darteed tani ma aha tijaabo tilmaan.

Halkaa marka ay marayso waxaa sii tijaabo kale ee cathode gacanta laga sameeyey oo isku dar ah ee budo kaarboon firfircoonaan iyo KU-2-8 la koronto dibadda ahama birta iyo anode ka soo dar ah ee budo kaarboon firfircoonaan iyo cusbi anion AB-17-8 in koronto dibadda ka ahama. Elektrolytka - xal aqueous of NaCl, meelaha anode iyo cathode kala dardaro ah dareemay. electrodes Dibadda ee element this la October 2011 ay awoodaan in ay gaaban-circuit ammeter ka dadban. Hadda taas oo muujinaysa ammeter ah, oo ku saabsan maalin ka dib markii dib u noqda, hoos u dhacay 1 MA - ilaa 100 mkA (taas oo sida muuqata waxaa sabab u ah kala fogaansho ee electrodes ah), iyo tan iyo markaas ka badan hal sano ah aysan waxba ka beddelin.

In tijaabo la taaban karo kor lagu sharaxay oo xidhiidh la leh qalabka helitaan natiijada helay wax ku ool ah si xooga ka hooseeya aragti ahaan macquul ah. Intaa waxaa dheer, in ay ogaadaan qayb ka mid ah emf guud gudaha Cunsurka mar walba baabbi'iyey, waayo, dayactirka reaction koronto ah (wax soo saarka ee hydrogen iyo oxygen) iyo aan la qiyaasi karin wareegi jiray dibadda.

Gunaanad.

Gebogebadii, waxaannu ku tirinnaa karaa nooca in oo noo ogolaadaa in loogu badalo tamar kulka galay tamarta waxtar leh ama shaqo, halka la isticmaalayo sida a "kululeeyaha" deegaanka iyo adigoo aan "qaboojiyaha". Sayidka Donnan saamayn iyo gudaha HADDII diinta tamarta kaamerada of Qurub lagu eedeeyay in ay tamarta korontada beerta DEL sida kulaylka reaction endothermic waxaa beddelay tamarta kiimikada.

Waxaa loo tixgeliyaa element xiriir gubtay, kulaylka ka dhexdhexaad ah iyo biyo, iyo qoondaysaa koronto, hydrogen iyo oxygen! Waxaa intaa dheer, geeddi-socodka isticmaalka tamarta iyo isticmaalka hydrogen sida shidaalka ah, iyo biyo ka soo noqdo dib u dhexdhexaad ah kulaylka!

Part 3 of lifaaqa ah.

qayb Tan waxaa sii wada hadleen Donnan saamayn kortay, at kulanka of biraha / Semiconductor gudaha HPDC iyo kulayl Peltier on reactions redox iyo kartiyo koronto ee element ah.

iman kara Donnan (Lifaaqa №1)

Ka fikir hab ay of dhacdo of iman kara Donnan for polyelectrolyte. Ka dib markii counterions polyelectrolyte dissociation ay yar bilaabaan, by sida-, taasoo ka dhigeysa mugga degan macromolecule ah. sida- jiho ah counterions of macromolecules polyelectrolyte mugga yar ee dareeraha ah waxaa sabab u fiirsashada ee bulk of macromolecule kordhay sida inta kale ee xalka marka la barbar dhigo. Dheeraad ah, haddii, tusaale ahaan, counterions yar waxaa si xun u eedeeyay, taas oo keenta in qaybta hoose ee macromolecule waxaa si togan ku amray, oo xalka waa isla markiiba ku xiga si ay mugga macromolecule ah - xun. ie agagaarka mugga a macroion wanaagsan eedeeyay, waxaa jira nooc ka mid ah "jawi ra'iyi" oo ka mid ah counter-udhigo yar - xun lagu soo eedeeyay. Joojinta koritaanka lacag jawi Madbacada qaranka wuxuu dhacaa marka ay duurka electrostatic dhexeeya jawi macroion mugga ra'iyi iyo kafado sida- ah kaamerada of counterions yar. taasoo keentay hoganaya Farqiga iman kara ee u dhexeeya jawiga iyo macroions Madbacada qaranka waa iman kara Donnan. iman kara Donnan waxaa sidoo kale loo yaqaan iman kara xuub, maxaa yeelay, xaalad la mid ah waxay dhacdaa on xuub semipermeable, tusaale ahaan, marka ay kala xal elektrolytka taas oo uu leeyahay udhigo of laba nooc ah - awood u ah oo aan awood u maraya therethrough ee dareeraha saafiga ah.

iman kara Donnan la oran karo waa sida xadidaysa kiis ee iman kara sida- ah, marka dhaqdhaqaaqa mid ka mid ah udhigo ah (in macroion kiiskan) waa eber. Markaas, sida uu [1, p. 535], qaadashada mas'uul ka ah counter loo siman yahay mid ka mid ah:

E d = (RT / F) lihida ( A1 / A2), halkaas oo

Ed - iman kara Donnan;

R - joogta gaaska universal,

T - heerkulka thermodynamic;

F - Faraday joogto ah;

A1, A2 - counter-waxqabad ee wejiyada xiriir ah.

In xubin this, kuna waari dhexdeeda xuub kala xal poliosnovaniya (pH = LG ah 1 = 14) iyo polyacid (pH = LG ah 2 = 0), iman kara Donnan guud ahaan xuub heerkulka qolka (T = 300 0 K) u noqon lahaa:

E d = (RT / F) (LG ah 1 - LG ah 2) lihida (10) = (8,3 * 300/96500 ) * (14 - 0) * lihida (10) = 0.83 Volts

Donnan korodhka ka iman karta saamiga si toos ah heerkulka. Waayo, sida- ee gacanta electrochemical ee Peltier kulaylka waa isha kaliya ee wax soo saarka ee shaqo waxtar leh, ma aha la yaab leh in xubno sida emf waxay kordhisaa la sii kordhaya heerkulka. In gacanta sida- wax soo saarka shaqada, kulaylka Peltier waxaa had iyo jeer laga soo qaaday deegaanka. Marka socodka hadda marayo EDL sameeyay Donnan saamayn, jihada a ku beegneyd jihada wanaagsan ee beerta DES (i.e., marka berrinkii DES u qabata shaqo wanaagsan), kulaylka nuugo ka deegaanka soo saarka ee warqad this.

Laakiin in element sida- tahay beddel joogto ah unidirectional iyo fiirsashada of udhigo, kaas oo ugu dambeyntii keenta in ek'eysiiyo fiirsashada iyo joojin sida- faray, ka duwan hoganaya Donnan, taas oo, in ay dhacdo dhacdo miliishiyada guurto ah hadda, fiirsashada ra'iyi, mar gaarey qiimo gaar ah, isma badelin .

Berdaha. 2 muujinaysaa jaantuska ah kartiyo redox of falcelinta of hydrogen iyo oxygen markii la beddelo ashitada ee xalka ah. shaxda waxay muujinaysaa in laga yaabo in koronto of falcelinta oxygen formation ay ka maqan yihiin udhigo OH- (1.23 volts jawi acidic) waa ka iman kara isku-fiirsashada sare (0.4 volts ee dhexdhexaad ah xumadoodu) ee 0,83 volts kala duwan. Sidoo kale, laga yaabo in koronto cadaanyo hydrogen-sameynta ay ka maqan yihiin H + (-0.83 volts ee dhexdhexaad ah xumadoodu) waa ka iman kara isku-fiirsashada sare (0 V ee dhexdhexaad ah acid) kala duwan, sidoo kale at 0,83 volts [4. 66-67]. ie cad in 0,83 volts ayaa loo baahan yahay si ay u helaan ka-fiirsashada sare ee biyaha ee udhigo kala. Taas macnaheedu waa in 0,83 volts waxaa looga baahan yahay mass ah dissociation dhexdhexaad ah u taagoo biyo H + iyo udhigo OH-. Sidaas darteed, haddii xuub waxaa lagu taageeray in our meel cathode Cunsurka dhexdhexaad acidic iyo anodic ah xumadoodu, danab ku gaari karaan DEL 0,83 volts ay, taas oo ah in heshiis wanaagsan la xisaabin teori soo bandhigay horaantii. danab waxa uu ku siinayaa meel conductivity sare DES xuub by dissociation biyo udhigo dhexdeeda.

Berdaha. 2. Jaantuska kara falcelin redox

daatay oo biyo ah, iyo udhigo + H iyo OH- galay hydrogen iyo oxygen.

HADDII iyo Peltier kulaylka (Lifaaqa №2)

"Sababta oo ah saamaynta Peltier waa in tamarta celceliska sidayaal ah lacag, (waayo, electrons definiteness) ku lug conductivity korontada ee kirishbooyada kala duwan ee kala duwan ... In kala guurka ah oo ka mid kaari galay electron kale ama gudbiyaan Roobka awood xad-dhaaf ah ama kabo la'aan ah tamarta at its kharashka (ku xiran tahay jihada hadda).

Berdaha. 3. saamayn Peltier The on biraha xiriir iyo n- Semiconductor ah: ԐF - heerka Fermi; ԐC - hoose ee band tabinta ee Semiconductor ah; ԐV - band valence; I - jihada wanaagsan ee hadda jirta, goobooyin fallaadho schematically muujiyay electrons.

Xaaladda hore u dhow xiriir la sii daayay, iyo tan labaad - waxa loogu yeero nuugo .. Peltier kulaylka. Tusaale ahaan, on Semiconductor xiriir - biraha (Jaantuska 3) tamarta ee electrons in ka Semiconductor nooca-n in biraha (bidix xiriiri) gudbayaa waa weyn u ka badan yahay ԐF tamarta Fermi. Sidaa darteed, waxay xad-hoganaya ee kaamerada in biraha. Hoganaya waa lay soo celiyey iyada oo sababtu tahay shilalka, kaas oo thermalized electrons, siinta crystalline tamarta xad-dhaaf ah. Roobka. biraha Semiconductor The (taabashada midig) u gudbin kartaa oo kaliya electrons ugu firfircoon, si gaas in electron in biraha qaboobeyso. On soo celinta qaybinta hoganaya tamarta oscillation daaqaddii baabbi'iyey "[2, p. 552].

Si aad ula xiriirto xaalada biraha / p-Semiconductor waa la mid. Maxaa yeelay, godad Semiconductor p-conductivity bixiyaan ay band valence in uu ka hooseeyo heerka Fermi ah, ka dibna xiriir la qaboojiyey doonaa, kaas oo electrons qulquli ka p-Semiconductor in ay biraha. Peltier kulaylka sii daayo ama nuugo by xiriir laba kirishbooyada, ay sabab u tahay wax soo saarka ee taban ama togan ee HADDII gudaha.

Waxaa ka mid ah in farqiga u bidix xiriir (berdihii. 3), kaas oo qoondaynta Peltier kulaylka, cell ah electrolytic, tusaale ahaan, xal aqueous NaOH (Jaantuska 4) iyo Semiconductor biraha iyo n-ha noqoto kiimikaad inert.

Berdaha. 4. xiriir bidix n-Semiconductor iyo biraha u furan yahay iyo kaalinta in farqiga of xal elektrolytka ah. Tilmaamood la mid yihiin in berdihii. 3.

Maxaa yeelay, marka socodka hadda «Waxaan», Semiconductor ee n-electrons ee tamarta sare yimaadaan xal ka badan ka soo baxay oo xal in biraha, tamarta this xad-dhaaf ah (kulaylka ee Peltier) waa in gacanta loogu istaago.

hadda waxa uu ku dhex gacanta waxaa laga yaabaa in kaliya kiis ee darroor dhexdeeda reactions electrochemical. Haddii falcelinta gube in gacanta, kulaylka Peltier la sii daayay gacanta, sida ka badan ayay u leedahay meel ay aadaan. Haddii dareen in gacanta - endothermic, kulaylka Peltier ah oo kulligiis ama qayb ahaan waa in ay mag-saamaynta endothermic, ie, si ay u sameeyaan wax soo saarka falcelin. Tusaalahaan, wadarta reaction gacanta: 2H2O → 2H2 ↑ + O2 ↑ - endothermic, si kulaylka (energy) ee Peltier ee waa in la abuuro taagoo iyo H2 O2, waxaa la aasaasay on electrodes ah. Sidaas darteed, waxaan aad u hesho in kulaylka Peltier ee la doortay ee dhexdhexaadka ah in xaq n-xiriir Semiconductor / biraha dib uma deegaanka la sii daayay, iyo waxa lagu kaydiyaa foomka tamarta kiimikada ee hydrogen iyo oxygen u taagoo. Sida iska cad, hawlgalka il dibadda danab ayaa la wada baabbi'iyey, waayo, electrolysis biyaha, haddii ay taasi ku noqon doonaan kuwo yar ka badan in ay dhacdo electrodes isku mid, taasoo keenta dhacdo ma saamayn Peltier ah ..

Marka laga sifooyinka electrodes ah, gacanta electrolytic laftiisa nuugo kartaa ama dhalin kulaylku markuu dhex daraa Peltier hadda marayo. The xaaladaha magaabo-guurto ah, isbedel ka iman kara unugyada Gibbs [4, p. 60]:

Δ G = Δ H - T Δ S, halkaas oo

Δ H - isbedel enthalpy of unug;

T - heerkulka thermodynamic;

Δ S - isbedelka entropy ee gacanta;

S = - T Δ S - kulaylka of cell Peltier ah.

Waayo, cell electrochemical hydrogen-oxygen a at T = 298 (K), isbedelka ku dhacay enthalpy ΔHpr = - 284.5 (KJ / mol) [8, p. 120], isbeddelka Gibbs ka iman kara [4. a. 60]:

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

z - tirada electrons per Britain,

F - Faraday joogto ah;

E - emf cell.

Sidaa darteed

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

ie hydrogen-oxygen cell electrochemical abuuraa kulayl jawi Peltier ah, halka hagaajinta entropy iyo hoos ay. Markaas, in nidaamka bedelka ah, electrolysis biyaha, taas oo kiiska ku jira tusaale ahaan, Peltier kulaylka Q mod = - Ave S = - 47.3 (KJ / mol) ee elektrolytka la nuugo doonaa deegaanka.

Yeero P - kulaylka Peltier laga soo qaaday deegaanka ee xaq n-xiriir Semiconductor / biraha. P The kulaylka> 0 waa in gacanta taagan, laakiin maxaa yeelay, daatay biyo ah oo gacanta falcelinta endothermic (Δ H> 0), P kulaylka Peltier waa in ay mag-saamaynta kaamerada of falcelinta:

Δ G Aar oo = (Δ Aar oo H - n) + Q mod                                                                        (1)

Ducooyinkii carabida Q ku xiran tahay kaliya ee curinta waxay elektrolytka ah, tan iyo markii ay Waa dabeecad u ah oo gacanta electrolytic la electrodes inert, iyo n ku xidhan tahay oo kaliya on qalab koronto ah.

Isla'egta (1) waxay muujinaysaa in kulaylka P Peltier iyo Peltier kululeeyo mod Q, waa wax soo saarka ee shaqo waxtar leh. ie kulaylka Peltier ka dhexdhexaad ka qaaday yaraynaysaa kharashka il awood dibadda looga baahan yahay electrolysis. Xaaladda A halkaas oo dhexdhexaad ah kulaylka waa il tamar wax soo saarka ee shaqo waxtar leh, waa dabeecadda u ah sida-, iyo sidoo kale for unugyada badan electrochemical, tusaalooyin xubno sida waxaa lagu muujiyey in [3, p. 248 - 249].

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