Umsebenzi eziwusizo ukushisa Imvelo

Ingxenye 1. Abanye imigomo izincazelo.

Amandla electromotive (EMF) ayincenye zangaphandle amandla emkhakheni ingxenye ehlanganisa umthombo wamanje ... amandla yangaphandle esebenza Electroplating amaseli imingcele phakathi electrolyte kanye electrode. Ziphinde ziphathe emngceleni ophakathi izinsimbi ezimbili ezingafani futhi ukucacisa contact umehluko ezingaba therebetween [5, k. 193, 191]. Inani kuzuba nekhono kuwo wonke evele esigabeni wesifunda ilingana umehluko ezingaba phakathi babashayeli, sise uchungechunge kuphelile, futhi ubizwa ngokuthi electromotive amandla EMF umqhubi wesifunda ... uchungechunge ehlanganisa kuphela babashayeli uhlobo lokuqala ilingana gxuma ezingaba phakathi lokuqala kanye umqhubi wokugcina ngqo uxhumane nabo (Volta umthetho) ... Uma wesifunda kuyinto efanele ovulekile, EMF lesi sifunda zero. Ukuze kulungiswe umqhubi evulekile-circuit, okubandakanya okungenani oyedwa electrolyte, kusebenza umthetho volts ... Ngokusobala, kuphela umqhubi wesifunda ehlanganisa okungenani oyedwa umbhidisi uhlobo lwesibili namangqamuzana electrochemical (noma amaketanga izakhi electrochemical) [1, k. 490 - 491].

Polyelectrolytes kukhona polymers uyakwazi dissociating ku ion e isixazululo, ngaleyo ndlela kuleli macromolecule esifanayo, inani elikhulu izinkokhiso ezenzeka ... polyelectrolytes crosslinked (ion kwabebhange, ion-exchange resin) akusho chaza, bandisa kuphela, kuyilapho esaziwa ikhono Nqamula [6, p. 320 - 321]. Polyelectrolytes Nqamula ku macroion omubi icala futhi H + ion abizwa ngokuthi polyacids futhi dissociates ku ion kahle icala futhi OH- macroion ngokuthi poliosnovaniyami.

Donnan ezingaba yakhoibrium umehluko ezingaba okwenzeka umngcele isigaba phakathi electrolyte ezimbili uma lo mkhawulo akuyona permeable bonke ion. Impermeability imikhawulo kwabanye ion kungase kubangelwe, isibonelo, ukuba khona olwelwesini nge ikhule ezimbotsheni iwumngcingo okuyinto ingahambeki ngoba izinhlayiya ngenhla osayizi abathile. permeability okukhetha esibonakalayo kwenzeka futhi uma kukhona ion kakhulu ngakho exhumene omunye izigaba ukuthi uyiyeka ngokuvamile abakwazi. Uqinisile liziphathe ionic ion exchange inhlaka, noma iqembu ion-exchange fixed isibopho homopolar e eheleni yamangqamuzana noma i-matrix. Isixazululo, ngokuba ngaphakathi matrices enjalo amafomu kanye ke isigaba esisodwa; isixazululo, engaphandle, - yesibili [7. 77].

I kagesi ungqimba double (EDL) kuyavla ekusebenzisaneni we izigaba ezimbili isethi izingqimba oppositely icala ngokufanele ngesikhathi ibanga elithile komunye nomunye [7. 96].

Peltier uwukwenza lokhu ngabodwa noma ukumuncwa ukushisa ngesikhathi contact babashayeli ezimbili ezahlukene kuye isiqondiso kagesi egeleza ngokusebenzisa zokuxhumana [2, k. 552].

Ingxenye 2: Ukusebenzisa medium ukushisa electrolysis yamanzi.

Cabanga indlela nesenzakalo kwe-circuit yeseli electrochemical (ngemuva kwalokhu elementi), kuboniswa schematically e Fig. 1, EMF ngaphezulu ngenxa contact yangaphakathi umehluko ezingaba (PKK) futhi umphumela Donnan (incazelo emfushane okushiwo Donnan umphumela, PKK yangaphakathi futhi ezihambisana Peltier ukushisa inikezwe ingxenye yesithathu sihloko).

Fig. 1. ukumelwa wokuhlelwa kwendikimba eyeseli electrochemical: 1 - i-cathode iyathintwa nge isixazululo of 3, electrochemical ukunciphisa ukusabela cations electrolyte senziwe ubuso bayo, yazalwa inert amakhemikhali kakhulu doped n-semiconductor. Ingxenye cathode yokuxhuma it i voltage wangaphandle, metallized; 2 - i-anode iyathintwa nge isixazululo of 4, phezu yalo zenzeka electrochemical namachibi ukusabela anions electrolyte, eyenziwe inert amakhemikhali kakhulu doped p-semiconductor. Ingxenye anode yokuxhuma it i voltage wangaphandle, metallized; 3 - cathode isikhala, isixazululo polyelectrolyte, dissociating emanzini at macroion R- omubi icala futhi counterions kahle icala K encane + (kulesibonelo samanje hydrogen ion H +); 4 - anode isixazululo gumbi polyelectrolyte emanzini dissociating ku omuhle icala macroion R + futhi counterions omubi icala A- ezincane (kulesi sibonelo ke hydroxide ion OH-); 5 - ulwelwesi (diaphragm), kuyinto eliqinile ukuze macromolecules (macroion) polyelectrolytes, kodwa permeable ngokuphelele counterions encane K +, A- namanzi molecule endaweni okwabelwana 3 no-4; Evnesh - i voltage wangaphandle.

EMF ngu Donnan umphumela

Ngokucaca, le electrolyte isikhala cathode (. 3 Figure 1) kuyakhethwa isixazululo aqueous polyacid (R-H +), i-electrolyte kanye gumbi anode (4, komkhiwane 1.) - poliosnovaniya aqueous (R + OH-). Ngenxa dissociation polyacids egumbini cathode, eduze kobuso cathode (1 Fig. 1), kukhona emakamu anda H + ion. icala Positive kokuvela eduze kwamanzi cathode akuyona ihlawulelwa omubi icala macroions R-, kusukela abakwazi isondela kakhulu ebusweni cathode ngenxa yobukhulu bayo kanye ukuba khona nakanjani icala umoya ionic (ngemininingwane ukubona. Incazelo Donnan umphumela Annex №1 we ingxenye yesithathu sihloko). Ngakho, ungqimba umngcele isixazululo ngokuqondile nabo ebusweni cathode has a icala omuhle. Ngenxa yalokho, i-lokungeniswa electrostatic phezu cathode, ohlanganisa ikhambi, kukhona icala engakhi electron conduction. okungukuthi ekusebenzisaneni phakathi komhlaba cathode futhi isixazululo DES kwenzeka. Field we DES odlulela electron kusukela cathode - ikhambi.

Ngokufanayo, phezu anode (2, Fig. 1), ungqimba umngcele ikhambi egumbini anode (4, Fig. 1) ngokuqondile nabo ebusweni anode has a icala ongathandeki, futhi phezu kobuso anode, ohlanganisa ikhambi, kukhona icala omuhle. okungukuthi ekusebenzisaneni phakathi komhlaba anode nesixazululo futhi kwenzeka DES. Field we DES odlulela electron kusukela isixazululo - a anode.

Ngakho, emkhakheni DES ngesikhathi interface we cathode futhi anode ikhambi, asekelwe ezishisayo isixazululo ion okusheshayo, ezimbili yangaphakathi umthombo EMF, esebenza ekhonsathini ne njengomthombo wangaphandle, ngamanye amazwi, baphokophelele amacala ezimbi kumjikelezo kwewashi.

Dissociation poliosnovaniya polyacids futhi kubangela okusheshayo ezishisayo ngokusebenzisa ulwelwesi (5, Figure 1) H + ion isuke endaweni cathodic -. Kuya anode, futhi OH- ion kusukela gumbi anode - a cathode. Macroion R + futhi R- polyelectrolytes Awukwazi ukuhambisa ngokusebenzisa ulwelwesi, ngakho-ke kusuke endaweni cathode kukhona icala ngokweqile ezimbi, futhi kusukela isikhala anodic - ukukhokhiswa omuhle ngokweqile, ngamanye amazwi, kukhona enye DPP ngenxa Donnan umphumela. Ngakho, ulwelwesi futhi kwenzeka ngaphakathi EMF, esebenza ekhonsathini ne njengomthombo wangaphandle ukushisa okusheshayo futhi zigcinwe ikhambi ion.

Ngo Isibonelo sethu, voltage yonkana ulwelwesi ongafinyelela 0.83 volts, njengoba lokhu oluhambisana ushintsho bezikhali ejwayelekile hydrogen electrode esuka - volts 0.83 ukuze 0 at aphuma medium ane-alikhali ku anode gumbi le cathode gumbi imvelo ene-asidi. Ukuze uthole imininingwane, bheka. Ngo Isijobelelo №1 we ingxenye yesithathu sihloko.

EMF PKK kusuka ngaphakathi

I-elementi EMF Kwenzeka, kufaka ekhatsi anode contact Semiconductor futhi cathode onesigqi zazo ekukhonzeni ukuxhuma zangaphandle voltage umthombo. Lokhu EMF ngenxa PKK yangaphakathi. Yangaphakathi UMA akudali, ngokungafani kuya ensimini zangaphandle Isikhala ezungezile babashayeli contact, isb It akuphazamisi motion izinhlayiya icala ngaphandle babashayeli. Ukwakhiwa n-semiconductor / metal / p-semiconductor ngokwanele eyaziwa futhi lisetshenziswa, isibonelo, i-thermoelectric Peltier mojuli. Ubukhulu bale EMF isakhiwo esinjalo ekamelweni lokushisa ongafinyelela amagugu komyalelo wokungabi 0.4 - 0.6 Volt [5, k. 459; 2, k. 552]. Fields koxhumana baqondiswa ngendlela yokuthi zenza ngihlehlise electron esiphikisa kumjikelezo, isb isenzo ekhonsathini ne wangaphandle. Amaelectrons ukukhulisa amandla ezingeni medium iyavuleka sokushisa kwemini Peltier.

Yangaphakathi UMA ezivukayo ngenxa nokuhanjiswa kwe- electron ezindaweni contact we electrode kanye nekhambi, kunalokho, odlulela electron isiqondiso ngokwewashi kumjikelezo. okungukuthi ukunyakaza electron elementi esiphikisa kulezi oxhumana kumele sandiswe Peltier ukushisa. kodwa ngoba ukudluliselwa electron kusukela cathode angena ikhambi kanye yesixazululo ku anode is ngempela ephelezelwa ukusabela endothermic odala hydrogen ne-oksijini, ukushisa Peltier hhayi kudedelwa ku medium, futhi ukunciphisa umphumela endothermic, isb efana "alondolozwe" ku enthalpy kumiswa e-hydrogen ne-oksijini. Ukuze uthole imininingwane, bheka. Ngo Isijobelelo №2 okwesithathu isihloko.

abathwali (ama-electron kanye ion) ukuhambisa e-elementi wesifunda hhayi izindlela avaliwe, ngaphandle kwemali ku-elementi asibahambeli ngesimiso somshini esivalekile. Ngamunye anode electron eyatholakala kusukela isixazululo (ngokuhamba namachibi of OH- ion ukuba izinhlayiya zomoya-mpilo), badabula i wesifunda zangaphandle cathode, is volatilized kanye hydrogen molecule (e inqubo yokutakula ion H +). Ngokufanayo ion OH- futhi H + ningazenzi ejikeleza avaliwe, kepha kuphela electrode ohambelana, bese shabalala efomini hydrogen yamangqamuzana ne-oksijini. okungukuthi kanye ion futhi electron ngamunye ezihambelayo imvelo yayo kule kuyashesha emkhakheni DES, futhi ekupheleni indlela, lapho efinyelela kobuso electrode ehlangana engqamuzaneni, ukuguqulela lonke amandla agcinwe - amandla kwebhondi zamakhemikhali, uphume ku-loop!

Konke imithombo yangaphakathi ye EMF I-elementi, ukunciphisa kubiza wangaphandle ngoba amanzi electrolysis. Ngakho, ngesikhathi sokushisa kwemini ambient iyavuleka izakhi ngesikhathi ukusebenza kwawo ukuze silondoloze nokuhanjiswa kwe- DES, ukunciphisa izindleko wangaphandle, ngamanye amazwi, It kwandisa ukusebenza kahle electrolysis.

Electrolysis yamanzi ngaphandle wangaphandle.

Ngo kokubukeza izinqubo ezenzeka esikhathini isici kuboniswe Fig. 1, sangaphandle umthombo imingcele kungukuthi kunakwe. Ake sithi ukumelana yangaphakathi ilingana rd futhi zinamandla ka 0. Lokho Evnesh Elementi electrode shorted ukuba umthwalo yokwenziwa (bheka Fig. 5). Kulokhu, isiqondiso nokubaluleka DES Amasimu ezivukayo ngesikhathi kubonwa izakhi akukashintshi.

Fig. 5. Kunalokho Evnesh (Fig. 1) kuhlanganise yokwenziwa umthwalo RL.

Anqume imibandela nokuguqulwa ukugeleza samanje lesi sici. Ukushintsha Gibbs ezingaba, ngokuvumelana formula (1) Isijobelelo №1 we ingxenye yesithathu sihloko:

Δ G Fika = (Δ H Fika - n) + Q mod

Uma P> Δ H + Q mod mod = 284,5 - 47.2 = 237.3 (kJ / Mol) = 1.23 (ev / i-molecule)

the Δ G Fika <0 nokucubungula nokuguqulwa kungenzeka.

Sizocabangela obengeziwe bokuthi izakhi hydrogen isizukulwane ukuphendula kwenzeka i osebenzelana esidi (electrode bezikhali 0 volts) nomoya-mpilo i (ezingaba electrode ka 0.4 volts) ane-alikhali. electrode okunjalo nekhono ihlinzeka ulwelwesi (5, Fig. 5), lo voltage lapho lokhu kufanele 0.83 volts. okungukuthi amandla adingekayo ukuze kwakhiwe i-hydrogen ne-oksijini kuyehla 0.83 (ev / i-molecule). Khona-ke isimo kungenzeka yenqubo nokuguqulwa kuthanda:

P> 1.23 - 0.83 = 0.4 (ev / i-molecule) = 77.2 (kJ / Mol) (2)

Sithola ukuthi umgoqo lukagesi hydrogen ne zomoya-mpilo ebesingagwenywa futhi ngaphandle kokusebenzisa i-voltage wangaphandle. okungukuthi ngisho ngesikhathi n = 0.4 (ev / i-molecule), isb lapho electrode kwangaphakathi HPDC 0.4 volts, isici kuyoba esimweni yakhoibrium ashukumisayo, futhi yimuphi (ngisho encane) ushintsho izimo ibhalansi kuzokwenza wamanje kulesi sifunda.

Esinye isithiyo esingenza ukusabela ngesikhathi electrode iyona energy ukusebenza, kodwa aqedwa emhubheni umphumela, ezivukayo ngenxa nobuncane igebe phakathi electrode nesixazululo [7, p. 147-149].

Ngakho, ngesisekelo yezakhi amandla, singaphetha ngokuthi zamanje sebengavela element kuboniswe Fig. 5, kungenzeka. Kodwa lokho izizathu ngokomzimba kungabangela lokhu zamanje? Lezi zizathu tibalwe lapha ngentasi:

1. Amathuba ukwedlulela electron kusukela cathode angena ikhambi ephakeme kunaleyo ematfuba ushintsho kusukela anode angena ikhambi, kusukela n-semiconductor cathode has a lot of electron mahhala nge high amandla ezingeni, kanye anode p-semiconductor - "izimbobo" kuphela, futhi lezi 'izimbobo "kukhona ezingeni amandla ngezansi electron cathode;

2. ulwelwesi kusekelwa esikhaleni cathode isimo esidi, futhi anode - ane-alikhali. Endabeni electrode inert, lokhu kuholela yokuthi abe cathode electrode iba kunenani anode. Ngenxa yalokho, ama-electron kumelwe uqhubekele ngokusebenzisa i wesifunda zangaphandle ezivela anode kuya cathode;

3. Inkokhelo kobuso izixazululo polyelectrolyte ezivukayo ngenxa Donnan umphumela, kudala ngesikhathi electrode / isixazululo ensimini yokuthi inkambu cathode ikhuthaza electron isivuno kusukela cathode angena ikhambi, kanye inkambu anode - entry electron phakathi anode kusukela isixazululo;

4. ibhalansi phambili bese ukuhlanekezela ukusabela ngesikhathi electrode (exchange imisinga) nganhlanye ngase H + ion oqondile ukunciphisa ukusabela ngesikhathi cathode kanye namachibi of OH- ion ngesikhathi anode, kusukela basuke ephelezelwa ukwakheka igesi (H2 kanye O2) uyakwazi kokushiya kalula ukusabela zone (Le Chatelier sika Isimiso).

Ukuhlolwa.

Ukuze kokuhlaziywa ambalwa of voltage yonkana umthwalo yi Donnan umphumela, ukuhlola okwenziwe lapho elementi cathode lalinabashumayeli carbon isebenze ne yangaphandle graphite electrode kanye anode - ingxube carbon ocushiwe futhi anion resin AB-17-8 ne yangaphandle graphite electrode. Electrolyte - isixazululo NaOH aqueous, anode futhi cathode izikhala zihlukaniswe zokwenziwa wawungathi. Ekuvuleni electrode zangaphandle kwalesi sakhi kwadingeka zinamandla mayelana 50 mV. Uma ixhunywe elementi umthwalo zangaphandle 10 Ohm fixed samanje microamps mayelana 500. Lapho kuma lokushisa inyuka kusuka 20 kuya 30 0C voltage kuya electrode zangaphandle lakhuphuka lafika ku-54 mV. Ukwandisa voltage ngesikhathi lokushisa kuma uqinisekisa ukuthi umthombo EMF kuyinto okusheshayo, isb ezinyakazayo ezishisayo we izinhlayiya.

Ukuze kokuhlaziywa ambalwa of voltage yonkana umthwalo kusukela kwangaphakathi HPDC metal / Semiconductor experiment lwenziwe lapho cathode iseli siqukethe graphite zokwenziwa powder ne yangaphandle graphite electrode kanye anode - powder boron Carbide (B4C, p-semiconductor) ne yangaphandle graphite electrode. Electrolyte - isixazululo NaOH aqueous, anode futhi cathode izikhala zihlukaniswe zokwenziwa wawungathi. Ekuvuleni electrode sangaphandle voltage isici kwaba ngu-150 mV. Uma uxhuma umthwalo zangaphandle kungxenye 50 kOhm voltage lehla 35 mV., Zinamandla iconsi olunjalo oluqinile ngenxa ongaphakeme eziwumgogodla boron Carbide futhi, ngenxa yalokho, i-high yangaphakathi ukumelana elementi. Investigation voltage kuqhathaniswa lokushisa-elementi isakhiwo esinjalo kwenziwe. Lokhu kungenxa yokuthi, ngenxa Semiconductor, kuye yawo yamakhemikhali Ukwakheka, degree of doping kanye nezinye izakhiwo, izinga lokushisa ushintsho izindlela ezingafani nomthelela Fermi ezingeni layo. okungukuthi lokushisa nomthelela EMF Elementi (ukwanda noma ukuncipha), kulesi simo incike zokwakha, ngakho-ke lokhu akuyona experiment Indlela.

Kuleli qophelo kwaqhubeka omunye isilingo lapho iseli cathode is wawenziwa ngengxube ye-carbon isebenze ubhuqu KU-2-8 ne yangaphandle engagqwali electrode kanye anode ingxube carbon isebenze ubhuqu anion resin AB-17-8 kuya electrode zangaphandle ezivela insimbi engagqwali. Electrolyte - isixazululo aqueous of NaCl, le anode futhi cathode izikhala zihlukaniswe zokwenziwa wazizwa. electrode sangaphandle kwalesi sakhi ne-October 2011 bayakwazi isekhethi ammeter yekwentiwa. Yamanje elibonisa i ammeter, cishe usuku emva kuyithuba, kwehle ngo-1 MA - 100 mkA (okuyinto ngokusobala ngenxa nokwehlukana we electrode), futhi kusukela ngaleso sikhathi esingaphezu konyaka akashintshi.

Ekuhloleni esisebenzayo ezichazwe ngenhla ngokuqondene ephumelela kakhudlwana izinto inaccessibility etholwe Imiphumela aphansi ukwedlula kwakuthiwa kungenzeka. Ngaphezu kwalokho, qaphela ukuthi ingxenye EMF Imininingwane yangaphakathi Elementi njalo kudliwe nokugcina ukusabela electrode (ukukhiqizwa kwe-hydrogen ne-oksijini) futhi singenakulinganiswa lesiguli elijikeleza ngaphandle.

Isiphetho.

Efingqa, singaphetha ngokuthi imvelo kusivumela ukuguqula energy ezishisayo zibe amandla ewusizo noma emsebenzini, ngenkathi usebenzisa njengendlela "heater" imvelo hhayi kokuba "esiqandisini". Ngakho Donnan umphumela futhi yangaphakathi UMA iguqulwe energy ezishisayo we izinhlayiya icala kagesi emkhakheni amandla DEL njengoba endothermic ukuphendula ukushisa iguqulwe ibe amandla amakhemikhali.

Kubhekwe contact isici ibusa ukushisa kusuka medium namanzi, futhi inike amandla kagesi, i-hydrogen ne-oksijini! Ngaphezu kwalokho, inqubo energy ukusetshenziswa kanye nokusetshenziswa hydrogen njengoba kubaswa ngazo umlilo, futhi amanzi ibuyisela emuva medium ukushisa!

Ingxenye 3 Annex.

Le ngxenye kuphinde okuxoxwe Donnan yakhoibrium umphumela, at kwalapho kuhlangana khona kwangaphakathi HPDC metal / Semiconductor futhi Peltier ukushisa ku ukusabela redox kanye electrode nekhono ku-elementi.

Donnan ezingaba (Isithasiselo №1)

Cabanga indlela nesenzakalo of Donnan lungaba polyelectrolyte. Ngemva dissociation polyelectrolyte counterions uqale encane yayo, ngu okusheshayo, kusale ivolumu elalihlala macromolecule. okusheshayo kokuqondisa ka counterions amancane macromolecules ivolumu polyelectrolyte e uketshezi kungenxa lokuhlushwa anda ngobuningi we macromolecule njengoba uma iqhathaniswa naso sonke yesixazululo. Ngaphezu kwalokho, uma, isibonelo, counterions ezincane omubi icala, lokhu kuphumela ukuthi ingxenye engaphakathi macromolecule kuthiwa kahle icala, futhi ikhambi ngokushesha eseduze umthamo macromolecule - ezingezinhle. okungukuthi babalelwa kahle icala macroion ivolumu, kukhona uhlobo "ion umoya" we encane esiphikisayo ion - omubi icala. Ukunqanyulwa ionic umoya icala kukhula kwenzeka lapho ensimini electrostatic phakathi ion ivolumu macroion umkhathi ezilinganisweni ukwanda okusheshayo ezishisayo counterions encane. I kwaphumela yakhoibrium umehluko ezingaba phakathi umkhathi macroions ionic kuyinto Donnan ezingaba khona. Donnan ezingaba ibizwa nangokuthi njengoba ulwelwesi ezingaba, ngoba nesimo esifanayo kwenzeka ku ulwelwesi semipermeable, ngokwesibonelo, lapho ihlukanisa ikhambi electrolyte esesikhundleni ion zezinhlobo ezimbili - lokhonako ayikwazi odlulayo therethrough we kuphela okumsulwa.

Donnan ezingase kubhekwe njengendlela icala nokukhawulela ngokuhlukumeza okunamandla okusheshayo, uma ukuhamba omunye ion (kuleli cala macroion) zero. Khona-ke, ngokuvumelana [1, k. 535], ukuthatha ophethe esiphikisayo lingana kuze fike:

E d = (RT / F) Ln ( a1 / A2), lapho

Ed - Donnan ezingase zivele;

R - jikelele igesi njalo;

T - lokushisa thermodynamic;

F - Faraday njalo;

a1, A2 - esiphikisayo umsebenzi e izigaba contact.

Kulesi ilungu, lapho ulwelwesi ehlukanisa poliosnovaniya izixazululo (pH = Lg a 1 = 14) futhi polyacid (pH = Lg 2 = 0), Donnan ezingaba yonkana ulwelwesi ekamelweni lokushisa (T = 300 0 K) kungaba:

E d = (RT / F) (Lg a 1 - Lg 2) Ln (10) = (8,3 * 300/96500 ) * (14 - 0) * Ln (10) = 0.83 volts

Donnan inyuka ezingaba ngokulingana ngqo lokushisa. Ukuze nokuhanjiswa kwe- iseli electrochemical Peltier ukushisa ungumthombo kuphela ukuze kukhiqizwe umsebenzi ewusizo, akumangalisi ukuthi izici eziningana ezinjengolwazi EMF kwandisa ne okwandisa izinga lokushisa. Ngo okusheshayo cell ukwenziwa komsebenzi, Peltier ukushisa njalo ethathwe imvelo. Lapho notshwala wamanje ngokusebenzisa EDL kwakhiwa Donnan umphumela, ohlangothini coinciding ne isiqondiso esihle yensimu DES (ngamanye amazwi, uma emkhakheni DES wenza umsebenzi omuhle), ukushisa amuncwa umzimba kusuka imvelo ukwenziwa lokhu ephepheni.

Kodwa isici ukwanda okusheshayo ushintsho okuqhubekayo kanye unidirectional e ion ukugxilisa ingqondo, okuyinto ekugcineni kuholela zokulinganiswa emakamu kanye Imisa okusheshayo iqondiswe, ngokungafani yakhoibrium Donnan wherein ecaleni ngombiko quasistatic imisinga ion okuhlushwa, kanye kokuba ifinyelele inani elithile, uhlala ingashintshiwe .

Fig. 2 sikhombisa idayagramu nekhono redox ukusabela hydrogen nomoya-mpilo uma kushintshwa asidi yesixazululo. Ishadi libonisa ukuthi engaba electrode oxygen kumiswa ukuphendula ngokungabi bikho OH- ion (1.23 volts endaweni azibukhali) lihlukile engaba efanayo ngesikhathi emakamu eliphezulu (0.4 volts e i medium ane-alikhali) e 0.83 volts. Ngokufanayo, ikhono electrode hydrogen-ukwakha ukuphendula ngokungabi bikho H + (-0.83 volts e medium ane-alikhali) lihlukile engaba efanayo ngesikhathi emakamu eliphezulu (0 V e i osebenzelana acid), futhi ngaleso 0.83 volts [4. 66-67]. okungukuthi sobala ukuthi 0.83 volts liyadingeka ukuze uthole emakamu eliphezulu yamanzi ion abafanele. Lokhu kusho ukuthi 0.83 volts iyadingeka mass dissociation hlangothi molecule yamanzi ku H + futhi OH- ion. Ngakho, uma ulwelwesi kusekelwa e-elementi cathode isikhala yethu naphakathi esidi i anodic ane-alikhali, voltage ongafinyelela yayo DEL 0.83 volts, elisetendeni sivumelwano obuhle izibalo theory awavezela. Lokhu voltage ihlinzeka okusezingeni eliphezulu conductivity isikhala DES ulwelwesi amanzi dissociation ku ion ngaphakathi kuwo.

Fig. 2. Umdwebo redox ukuphendula nekhono

yokubola amanzi, futhi H + ion futhi OH- ku-hydrogen ne-oksijini.

UMA futhi Peltier ukushisa (Isithasiselo №2)

"Imbangela yale Peltier umphumela wukuthi amandla isilinganiso abathwali icala (i definiteness electron) abathintekayo kulo conductivity kagesi e babashayeli ezihlukahlukene ezahlukene ... Ngo ushintsho komunye umqhubi kolunye electron noma badlulisele ngokweqile amandla igridi noma ukwelekelela ukuntula amandla ngezindleko zayo (kuye ngokuthi isiqondiso lamanje).

Fig. 3. Peltier ukusebenza ngomhla ka-metal lokuxhumana n- Semiconductor: ԐF - Fermi ezingeni; ԐC - phansi band conduction we Semiconductor; ԐV - Valence band; Mina - isiqondiso esihle zamanje; imibuthano ngemicibisholo kuboniswe schematically electron.

Esimweni sokuqala eduze contact ikhishwe, kanti eyesibili - okubizwa ngokuthi ugxile .. Peltier ukushisa. Ngokwesibonelo, ku-semiconductor contact - metal (Figure 3) amandla we-electron ukuthi kudlule kusukela n-uhlobo Semiconductor onesigqi (touch kwesokunxele) siphezulu ukwedlula Fermi amandla ԐF. Ngakho-ke, basuke kwephula yakhoibrium ezishisayo ku metal. Equilibrium kubuyiselwa ngenxa ukushayisana, lapho thermalized electron, enika ngokweqile amandla crystalline. Igridi. I metal Semiconductor (touch kwesokudla) izophela kuphela electron enamandla kakhulu, ukuze igesi electron ku metal epholisa. On nokubuyiselwa ukusatshalaliswa yakhoibrium ka ngehele oscillation amandla idliwe "[2, k. 552].

Ukuze uthintane isimo metal / p-semiconductor kuyafana. ngoba izimbobo Semiconductor p-conductivity ukunikeza Valence yayo band okungukuthi ngezansi ezingeni Fermi loxhumana ke uzobe selehlile, lapho ama-electron kuqhamuke njalo p-semiconductor kuya metal. Peltier ukushisa ezikhishwe noma amuncwa contact babashayeli ezimbili, ngenxa ukukhiqizwa negative noma positive we UMA yangaphakathi.

Afakwe kwesokunxele contact igebe (Fig. 3), lapho Peltier ukushisa ukwabiwa, eyeseli electrolytic, isibonelo, aqueous isixazululo NaOH (Figure 4) kanye Semiconductor zensimbi n-makube inert amakhemikhali.

Fig. 4. Oxhumana kwesokunxele n-semiconductor kanye metal ivuliwe futhi ibekwe esikhaleni yesixazululo electrolyte. Amagama ziyefana e Fig. 3.

Ngoba, lapho notshwala zamanje «I», le Semiconductor lika-n-electron amandla ephakeme ufika isixazululo kuka ephuma nekhambi metal, le energy ngokweqile (nokuvutha Peltier) Kumelwe ume kuseli.

Lamanje ngokusebenzisa cell kungenzeka kuphela uma ukuvuza therein ukusabela electrochemical. Uma ukusabela exothermic kuseli, ukushisa Peltier Kukhululwa kwengqamuzana, njengoba i ngaphezulu yena akanayo indawo lapho engaya. Uma ukusabela iseli - endothermic, ukushisa Peltier kuyinto ngokuphelele noma ngokwengxenye isinxephezeliso umphumela endothermic, okungukuthi, ukwakha umkhiqizo ukuphendula. Kulesi sibonelo, inani iseli yokusabela: 2H2O → 2H2 ↑ + O2 ↑ - endothermic, ngakho ukushisa (amandla) we Peltier ukudala molecule H2 O2, akhiwa phezu electrode. Ngakho, sithola ukuthi ukushisa Peltier akhethiwe naphakathi ngakwesokudla n-contact Semiconductor / isizinda hhayi kudedelwa emuva ku imvelo, futhi lilondolozwe hlobo luni lwamandla amakhemikhali hydrogen ne zomoya-mpilo. Ngokusobala, ukusebenza kwe-yangaphandle voltage umthombo edliwe ngokuba electrolysis yamanzi, kulesi simo kuyoba ezincane kuno esimweni electrode ezifanayo, okubangela kungekho indawo okuvela kuyo Peltier umphumela ..

Kungakhathaliseki izakhiwo electrode, iseli electrolytic ngokwayo ukubamba noma sikhiphe ukushisa lapho edabula Peltier nalokho zamanje. Imibandela athi static, ushintsho bezikhali Gibbs amaseli [4, p. 60]:

Δ G = Δ H - T Δ S, lapho

Δ H - ushintsho enthalpy yeseli;

T - lokushisa thermodynamic;

Δ S - ushintsho ku entropy yeseli;

Q = - T Δ S - sokushisa kwemini Peltier cell.

Ukuze uthole i-hydrogen--mpilo electrochemical iseli T = 298 (K), ushintsho enthalpy ΔHpr = - 284.5 (kJ / Mol) [8, k. 120], ushintsho Gibbs ezingaba [4. a. 60]:

ΔGpr = - zFE = 2 * 96485 * 1.23 = - 237.3 (kJ / Mol), lapho

z - nenani electron-molecule ngayinye;

F - Faraday njalo;

E - EMF iseli.

Ngakho-ke

Q ave = - T Δ S ave = Δ G njll - Δ H njll = - 237,3 + 47,2 = 284,5 (kJ / Mol)> 0,

okusho hydrogen--mpilo iseli electrochemical uphehla ukushisa in the Peltier imvelo, ngakolunye uhlangothi luthuthukisa entropy yayo uphinde wehlise yayo. Khona-ke, ngo-inqubo ephambene, le-electrolysis yamanzi, okuyinto kunjalo kusibonelo yethu, Peltier ukushisa Q mod = - Q ave = - 47.3 (kJ / Mol) we electrolyte abazokwazi kusukela imvelo.

Lumelela P - Peltier ukushisa ethathwe imvelo ngakwesokudla n-contact Semiconductor / metal. Ukushisa P> 0 Kumelwe ume kuseli, kodwa ngenxa noqhekeko yamanzi cell ukuphendula endothermic (Δ H> 0), P Peltier ukushisa kuyinto isinxephezelo umphumela ezishisayo we yokusabela:

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

Mod Q kuncike kuphela indlela yokwakheka electrolyte, kusukela Kuyinto isici iseli electrolytic nge electrode inert, futhi n kuncike kuphela izinto electrode.

Isibalo (1) ebonisa ukuthi ukushisa Peltier P no Peltier ukufudumeza mod Q, kukhona ukukhiqizwa umsebenzi ewusizo. okungukuthi Peltier ukushisa kuyasuswa naphakathi kunciphisa tindleko kumthombo wamandla ongaphandle adingekayo electrolysis. Isimo lapho medium ukushisa liwumthombo wamandla ukwenziwa umsebenzi ewusizo, kuyisici sobuntu okusheshayo, kanye amaseli amaningi electrochemical, izibonelo izici eziningana ezinjengolwazi ziboniswa [3, k. 248 - 249].

Izinkomba

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