Umsebenzi eluncedo yi ekufudumaleni Environment

Part 1. Abanye imigaqo kunye neenkcazelo.

Umkhosi electromotive (EMF) nomsebenzi lowo uyinxenye lwangaphandle inxalenye yentsimi amandla ziqulathe umthombo lwangoku ... amandla yangaphandle isenza electroplating iiseli imida phakathi electrolyte kunye electrode. Kwakhona asebenza kwi umda phakathi iintsimbi ezimbini ayaba kwaye isigqibo qha enokubakho umahluko therebetween [5, p. 193, 191]. Isixa utsiba nekhono kuzo zonke iindawo yecandelo yesekethe lilingana umahluko enokubakho phakathi izinikezeli, zibekwe iziphelo chain, yaye ibizwa ngokuba amandla EMF umqhubi yesekethe electromotive ... chain eyenziwa kuphela izinikezeli uhlobo lokuqala ilingana amandla utsibe phakathi yokuqala kunye umqhubi lokugqibela ngqo uqhagamshelane nabo (umthetho Volta) ... Ukuba le sekethe luvuleleke kakuhle, i-EMF lo elijikeleza zero. Ukuze kulungiswe umqhubi open-wesiphaluka, nto leyo equka electrolyte ubuncinane enye, esebenzayo volts umthetho ... Ngokucacileyo, kuphela yesekethe umqhubi equka ubuncinane enye umbexeshi uhlobo lwesibini iiseli electrochemical (okanye imixokelelwane izinto electrochemical) [1, p. 490 - 491].

Polyelectrolytes ke Iipholima ekwaziyo dissociating zibe ion e isisombululo, ngaloo ndlela kube macromolecule enye, kukho inani elikhulu ephindaphindekayo iintlawulo ... polyelectrolytes crosslinked (kubananisi ion, nentlaka ion-exchange) oko ukuluhlakaza, kudumba kuphela, lo gama kugcinwe ubuchule kwahlula [6, p. 320 - 321]. Polyelectrolytes kwahlula zibe macroion kakubi ityala kunye ion H + ibizwa ngokuba polyacids kwaye dissociates zibe ion ngokuqinisekileyo ityala kunye OH- macroion ebizwa poliosnovaniyami.

Donnan amandla sizinze umahluko enokubakho kwenzeka umda kwisigaba phakathi electrolytes ezimbini ukuba lo umda ayikho akubonakali kuzo zonke ion. Imida Impermeability for ezinye ion enokubangelwa, umzekelo, ubukho inwebu kunye pores emxinwa kakhulu leyo ivaleke ukuba amasuntswana ngentla ubukhulu ethile. permeability okukhetha zojongano kwenzeka ukuba naziphi ion kuhlanganiswa ngamandla ukuya kwenye izigaba ukuba uzakuwushiya ngokuqhelekileyo awukwazi. Ngqo aziphathe emahlamvini ion exchange ionic, okanye iqela ion-exchange esisigxina bond homopolar kwi emkhusaneni molekyuli okanye matrix. Isisombululo, ukuba ngaphakathi Iifomu matrices ezinjalo kunye nalo omnye ngokwesigaba; isisombululo, engaphandle, - owesibini [7. 77].

Umaleko electric kabini (EDL) zenzeka lojongano ye izigaba ezibini ibekwe lamanqanaba oppositely kuhlawuliswa ilahlwe kwi kumgama othile kwezinye [7 nganye. 96].

Peltier nomphumela bodwa okanye nokufunxwa ubushushu kwi ukuhlangana ababhexeshi ezimbini ezahlukeneyo ngokuxhomekeke phezu ulwalathiso umbane ayahamba qha [2, p. 552].

Icandelo 2: Ukusebenzisa ubushushu kwi electrolysis amanzi.

Cinga indlela elivela ukujikeleza yeseli electrochemical (emva koku element), eboniswe ngokwalo okuqashwa. 1, EMF ngakumbi ngenxa qha lwangaphakathi enokubakho umahluko (PKK) kunye nefuthe Donnan (inkcazo emfutshane kakuhle eli isiphumo Donnan, PKK lwangaphakathi ezinxulumene nobushushu Peltier lunikiwe isahlulo sesithathu eli nqaku).

Isazobe. 1. ukumelwa wesakhiwo se iseli electrochemical: 1 - le cathode adibane kunye nesisombululo-3, ukuncitshiswa indlela electrochemical ye ukuse- electrolyte kwenzeka kumphezulu wayo, othe wazalwa ngumntu iikhemikhali egalelwe kakhulu doped n-semiconductor. Inxalenye cathode uyidibanise kwi umthombo wamandla ombane wangaphandle, metallized; 2 - le anode adibane kunye nesisombululo ka-4, phezu kwayo kwenzeka electrochemical igcwala abasabela ngayo anions electrolyte, ezenziwe iikhemikhali egalelwe kakhulu doped p-semiconductor. Inxalenye anode uyidibanise kwi umthombo wamandla ombane wangaphandle, metallized; 3 - space cathode, umxube polyelectrolyte, dissociating emanzini macroion R- kakubi ityala kunye counterions ngokuqinisekileyo wamwisela K ezincinane + (kulo mzekelo ngoku ion hydrogen H +); 4 - anode gumbi polyelectrolyte isisombululo emanzini dissociating ibe ngokuqinisekileyo icala macroion R + yaye counterions kakubi wamwisela uA ezincinane (kulo mzekelo kuyo hayidroksayidi ion OH-); 5 - i inwebu (uvalo), into engena kungenwa ukuya macromolecules (macroion) polyelectrolytes, kodwa akubonakali ngokupheleleyo counterions ezincinane K +, uA kunye iimolekyuli zamanzi isithuba ekwabelwana 3 no-4; Evnesh - yangaphandle umthombo wamandla ombane.

EMF yi ukusebenza Donnan

Ecacileyo, ukuba electrolyte bendawo cathode (. 3, Umfanekiso 1) ikhethiwe isisombululo zolwelo polyacid (R-H +), lo electrolyte kunye gumbi anode (4, umkhiwane 1.) - poliosnovaniya zolwelo (R + OH-). Ngenxa polyacids dissociation kweli gumbi cathode, kufuphi komhlaba cathode (1, Isazobe. 1), kukho xi elingakumbi H + ion. intlawulo ezincumisayo evela kummandla wobuso cathode ayikho uyabhatalwa kakubi icala macroions R-, ekubeni abanako ukuza kufutshane kumphezulu cathode ngenxa yobukhulu kwaye kukho umoya ionic ngokuqinisekileyo icala layo (ukuba iinkcukacha kubona. Inkcazelo Donnan ukusebenza kwiSihlomelelo №1 inxalenye yesithathu nqaku). Ngenxa yoko, umaleko umda isisombululo ngqo wadibana kumphezulu cathode unalo ityala entle. Ngenxa yoko, i induction electrostatic phezu cathode, kunayo kunye nesisombululo, kukho intlawulo onganambithekiyo electron Uhanjiso. ie e esibonakalayo phakathi umphezulu cathode kunye ezintlantlu isisombululo kwenzeka. Field of the ezintlantlu utsalo electron ukusuka cathode - ukuya isicombululo.

Ngokufanayo, phezu anode (2, Isazobe. 1), umaleko kumda isicombululo kule gumbi anode (4, Isazobe. 1) ngqo wadibana kumphezulu anode kukho intlawulo elibi, naphezu komhlaba anode, kunayo kunye nesisombululo, kukho intlawulo positive. ie e esibonakalayo phakathi komhlaba anode kunye isisombululo kwakhona kwenzeka ezintlantlu. Field of the ezintlantlu utsalo electron ukusuka isisombululo - a anode.

Ngaloo ndlela, intsimi ezintlantlu kwi kujongano lwe cathode kunye anode ngesisombululo, inkxaso thermal umxube ion kwe-, ezimbini umthombo EMF lwangaphakathi, ukwenza kumboniso kunye umthombo wangaphandle, ngamanye amazwi, eliqhubela iintlawulo ezingalunganga kwi loop ebalwa.

polyacids Dissociation poliosnovaniya kwaye ubangela kwe- thermal ngokusebenzisa inwebu (5, Umfanekiso 1) H + ion ukusuka isithuba cathodic -. ukuya anode, kunye OH- ion ukusuka anode igumbi - a cathode. Macroion R + kunye R- polyelectrolytes awukwazi ukuhamba ngapha inwebu, ukusuka isithuba cathode ngoko kukho intlawulo kwemfuneko ezimbi, kwaye ukusuka isithuba anodic - intlawuliso kwemfuneko HIV, ngamanye amazwi, kukho omnye DPP ngenxa isiphumo Donnan. Ngoko ke, i inwebu kwakhona kwenzeka ngaphakathi EMF, esebenza kumboniso kunye umthombo yangaphandle kwe- ubushushu zigcinwe ngesisombululo ion.

Kumzekelo wethu, le ombane ngaphesheya inwebu unako ukufikelela 0.83 volts, njengoko oku uhambelana utshintsho isakhono electrode hydrogen eqhelekileyo ukusuka - volts 0.83 ukuya 0 kwi inguqu ukusuka eliphakathi obrak kwi anode gumbi le cathode gumbi bume asidi. Ukuze ufumane iinkcukacha, bona. Xa Isihlomelo №1 inxalenye yesithathu nqaku.

EMF PKK ngaphakathi

I elementi EMF Senzeka, kuquka anode zoqhagamshelwano semiconductor kunye cathode kwiindawo zabo metal bakhonza ukudibanisa umthombo ombane wangaphandle. le EMF ngenxa yangaphakathi PKK. Internal IF akudali, ngokuchaseneyo entsimini lwangaphandle kwisithuba ezingqonge izinikezeli contact, ngamanye Ayichaphazeli isindululo kwamasuntswana icala ngaphandle izinikezeli. Ukwakhiwa n-semiconductor / metal / p-semiconductor yaziwa ngokwaneleyo kwaye isetyenziswa, umzekelo, a thermoelectric imodyuli Peltier. Ubukhulu bale EMF isakhiwo enjalo bushushu unako ukufikelela amaxabiso komyalelo ka-0.4 - 0.6 Volt [5, p. 459; 2, p. 552]. Fields e abafowunelwa ibhekiswe ngendlela yokuba belwela electron ebalwa ngokwenzekayo, ngamanye sisebenze kumboniso kunye umthombo wangaphandle. Electron ayinyuse amandla kwinqanaba eliphakathi iyavuleka ekufudumaleni Peltier.

Internal IF ezivele ngenxa Ukuncitshiswa elektroni kwiindawo zoqhagamshelwano i electrode kunye nesisombululo, phezu koko, utsalo electron kwicala ngku kwi loop. ie isindululo of elektroni kwi Element ebalwa kwezi abafowunelwa kufuneka yabelwe Peltier ubushushu. kodwa ngenxa ukudluliselwa elektroni ukusuka cathode ukuya isisombululo kunye isicombululo kule anode ibithethwa zikhatshwe ukusabela endothermic ovelisa hydrogen neoksijini, ekufudumaleni Peltier ongakhululwanga kungena medium, kwaye ukunciphisa isiphumo endothermic, ngamanye efana "zilondolozwe" kwi enthalpy wesiseko hydrogen neoksijini. Ukuze ufumane iinkcukacha, bona. KwiSihlomelelo №2 isahlulo sesithathu nqaku.

zenethiwekhi (elektroni kunye ion) zihamba Element kwisekethe na umendo ezivaliweyo, akukho ntlawulo kwi element lo ihamba kwisiphaluka evaliweyo. anode electron ngasinye ingafumaneka kwi isicombululo (ngethuba igcwala of OH- nabo mpilo), wacanda isekethe yeyangaphandle cathode, kukho volatilized kunye iimolekyuli hydrogen (kwinkqubo kwakhona ion H +). Ngokufanayo ion OH- kunye H + musa ejikeleza evaliweyo, kodwa kuphela ukuba i electrode ehambisana, uze idliwa ngokohlobo hydrogen lwalusanda neoksijini. ie kunye ion kunye electron ngamnye ihamba eziyingqongileyo entsimini eyanda ezintlantlu, kunye nesiphelo sendlela, xa befikelela kumphezulu electrode adityaniswa molecule, ukujikwa lonke egcinwe eneji - amandla ngokuzikhanyeza imichiza, obuphuma ndzhendzheleko!

Zonke imithombo zangaphakathi EMF Isiqalelo, ukunciphisa iindleko umthombo lwangaphandle electrolysis amanzi. Ngoko ke, ubushushu kokugquma ukufunxa izinto ngexesha usebenzo ukugcina Kunikwa ezintlantlu, kukuba ukunciphisa iindleko umthombo wangaphandle, ngamanye amazwi, It kwandisa ukusebenza electrolysis.

Electrolysis amanzi ngaphandle nawuphi na umthombo wangaphandle.

Xa ukuhlola iinkqubo ezikhoyo kwi element eboniswe okuqashwa. 1, yangaphandle mthombo parameters azithathelwa ngqalelo. Masithi uxhathiso lwangaphakathi ilingana Rd kunye lombane 0 That Evnesh electrode Element ukuba shorted ukuya umthwalo nje (bona Isazobe. 5). Kulo mzekelo, ulwalathiso ubukhulu namasimi ezintlantlu evela kwi elilujongano nezinto kuhlala enye.

Isazobe. 5. Endaweni Evnesh (Fig. 1) kuquka RL umthwalo kwisixando sokwenziwa.

Ukumisela imiqathango yokumpompoza yangoku ezizenzekelayo kule element. Ukutshintsha Gibbs isakhono, ngokomgaqo wokubala (1) of Isihlomelo №1 inxalenye yesithathu nqaku:

Δ G Fika = (Δ H Fika - n) + Q mod

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

i Δ G Fika <0 kunye nenkqubo ezizenzekelayo kunokwenzeka.

Siza kuqwalasela kwakhona ukuba izinto sizukulwana hydrogen reaction yenzeka olune medium (electrode enokubakho 0 volts), kunye neoksijini an (amandla electrode 0.4 volts) obrak. nekhono electrode inikeze inwebu (5, Isazobe. 5), i-ombane apho oku kufuneka 0.83 volts. ie i-eneji efunekayo ukuze kwakhiwe hydrogen neoksijini yehliswa ngama-0.83 (eV / molecule). Ke imeko ithuba inkqubo ezizenzekelayo uya:

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

Sifumanisa ukuba amandla umqobo we-hydrogen neoksijini molekyuli babo ngaphandle kokusebenzisa i umthombo wamandla ombane wangaphandle. ie nokuba n = 0.4 (ev / molecule), ngamanye amazwi xa electrode engaphakathi HPDC 0.4 volts, Ingxenye kuba kwimo lwesilinganiso onamandla, kunye naluphi na utshintsho (nokuba elincinane) imiqathango lomncono kuzakubangela i yangoku kwisekethe.

Enye umqobo abasabela kwi i electrode na amandla kusebenze, kodwa iyapheliswa yi na isiphumo kwetonela, ezivela ngenxa ubuncinane we umsantsa phakathi electrode kunye nesisombululo [7, p. 147-149].

Ngenxa yoko, ngenxa lweengcinga amandla, sigqiba ukuba ngoku zidityaniswe kwi element eboniswe okuqashwa. 5, oko kunokwenzeka. Kodwa yintoni izizathu emzimbeni kungabangela le yangoku? Ezi zizathu zidweliswe apha ngezantsi:

1. Amathuba Incedisa elektroni ukusuka cathode isicombululo ngaphezu amathuba utshintsho ukusuka anode isicombululo, ekubeni n-semiconductor cathode has a lot of elektroni sesisa kwinqanaba eliphezulu amandla, kwaye anode p-semiconductor - "imingxuma" kuphela, yaye le "imingxuma" babe yinto inqanaba lamandla ngezantsi electron cathode;

2. I-inwebu ixhaswa kwisithuba cathode kokusingqongileyo asidi, kwaye anode - obrak. Kwimeko electrode egalelwe, oku kukhokelela kukuba ibe cathode electrode igcine ngaphezu anode. Ngenxa yoko, elektroni kufuneka ukuhamba ngapha isekethe lwangaphandle ukusuka anode ukuya cathode;

3. Intlawulo phezu izisombululo polyelectrolyte evela ngenxa isiphumo Donnan, kudala kwi electrode / ifildi isisombululo yokuba entsimini, xa cathode ikhuthaza electron hoxa ukusuka cathode isicombululo, intsimi kwi anode - entry electron kulo anode ukusuka isisombululo;

4. Imali phambili nokubuyela abasabela kwi i electrode (imisinga zotshintshiselwano) zityekele ngayo H + ion reactions ngqo ukwehla kule cathode kunye namachibi of OH- ion kule anode, ekubeni kokuba zihamba kunye ukubunjwa gas (H2 kunye O2) esikwaziyo ukushiya ngokulula zone reaction (Umgaqo Le Chatelier ngayo).

Imifuniselo.

Kuba uvavanyo ubungakanani ombane ngaphaya komthamo kwesiphumo Donnan, umfuniselo wenziwa apho Element cathode liqulethe le carbon yasebenza kunye electrode grafayithi engaphandle kunye anode - umxube carbon iyasebenza yaye anion intlaka AB-17-8 kunye grafayithi electrode engaphandle. Electrolyte - isisombululo NaOH zolwelo, anode kunye cathode izithuba ezahlulwa soboya zokwenziwa. On electrode open lwangaphandle lwesi sakhi waba lombane malunga 50 MV. Xa uqhagamshele i-elementi umthwalo lwangaphandle 10 Ohm fixed yangoku microamps malunga 500. Xa kokugquma lobushushu ukunyuka ukusuka 20 ukuya 30 0C ombane ukuya electrode lwangaphandle landile ukuya 54 MV. Ukwandisa ombane ikwiqondo lobushushu okukufutshane ungqina ukuba lo mthombo EMF na nokuhanjiswa, ngamanye isiphakamiso thermal ye amasuntswana.

Kuba uvavanyo ubungakanani ombane phesheya umthwalo ukusuka engaphakathi HPDC metal / semiconductor experiment kwaqhutywa apho cathode iseli siquka zokwenziwa powder grafayithi ne electrode grafayithi engaphandle kunye anode - ngumgubo ibhoroni khabhayithi (B4C, p-semiconductor) kunye grafayithi electrode engaphandle. Electrolyte - isisombululo NaOH zolwelo, anode kunye cathode izithuba ezahlulwa soboya zokwenziwa. On electrode open lwangaphandle ombane element malunga 150 MV. Xa uqhagamshela umthwalo lwangaphandle ukuya element 50 kOhm ombane lehla laya 35 MV., Loo nethontsi ombane ngamandla ngenxa eliphantsi okunexabiso carbide boron kwaye, ngenxa yoko, aphezulu lwangaphakathi amelane Element. Uphando ombane kuthelekiswa lobushushu ukuba elementi lwesakhiwo eso akwenziwanga. Oku kubangelwa kukuba, kuba semiconductor, kuxhomekeke nokubunjwa kwayo umchiza, degree of kweziyobisi kunye nezinye iimpawu, utshintsho ubushushu ngeendlela ezahlukeneyo nefuthe umgangatho walo Fermi. ie ukusebenza lokubanda EMF Isiqalelo (ukwanda okanye ukuncipha), kule meko ixhomekeke izinto ezisetyenzisiweyo, ngoko oku akuthethi experiment kubonisa.

Kweli nqanaba wawelela omnye ulingelo apho iseli cathode yenziwe ngomxube carbon isebenze ibe luthuthu KU-2-8 kunye electrode engaphandle insimbi kunye anode kumxube ngumgubo carbon iyasebenza yaye anion intlaka AB-17-8 ukuya electrode lwangaphandle oluvela steel stainless. Electrolyte - isisombululo zolwelo ze NaCl, izithuba anode kunye cathode ezahlulwa a zokwenziwa ngayo. electrode yangaphandle lwesi sakhi ne-Oktobha 2011 bayakwazi elifutshane-wesiphaluka ammeter kwisixando sokwenziwa. Yangoku ebonisa ammeter, malunga imini emva ukujika, kwehle nge-1 ma - ukuya ku-100 mkA (oko kubonakala ngenxa nokwehlukana i electrode), kwaye ukusukela ngaphezu koko ngaphezu konyaka akatshintshi.

Ekuhloleni practical ezichazwe ngasentla ngokunxulumene nezinto nokungafumaneki iziphumo ngempumelelo ngakumbi wafumana asezantsi kakhulu kunokuba isondlo kunokwenzeka. Ukongeza, kuba uyazi ukuba yinxalenye EMF lwangaphakathi iyonke Isiqalelo wayesoloko kudliwe nokugcina indlela electrode (imveliso hydrogen neoksijini) kwaye kulinganiswa kwisekethe ngaphandle hayi.

Isiphetho.

UPawulos, sinokuqonda ukuba indalo kusivumela ukuba ukuguqula amandla thermal ibe amandla luncedo okanye emsebenzini, lo gama usebenzisa njenge "imbawula" okusingqongileyo kwaye ungabinayo i "ifriji". Ngoko ke isiphumo Donnan kunye lwangaphakathi UKUBA waguquka amandla thermal ye amasuntswana amacala amandla entsimini yombane DEL njengoko ubushushu indlela endothermic iguqulelwa kwi amandla imichiza.

Izincomo element contact odla ubushushu ukusuka eliphakathi kunye namanzi, yaye yabela electric amandla, hydrogen neoksijini! Ngaphezu koko, inkqubo yokusebenzisa amandla kunye nokusetyenziswa hydrogen njenge amafutha, kunye namanzi ubuyela emva nobushushu medium!

Inxalenye 3 kwiSihlomelo.

Le nxalenye kuxoxwa ngakumbi isiphumo lizama Donnan, xa kudibana / engaphakathi HPDC metal semiconductor kunye Peltier ubushushu phezu reactions redox nekhono electrode kwi element.

Donnan amandla (iSihlomelo №1)

Cinga indlela isahlakalo Donnan amathuba polyelectrolyte. Emva counterions dissociation polyelectrolyte uqala ezincinane saso kwe-, eshiya ivolyum yile macromolecule. nokuhanjiswa zemiyalelo of counterions of macromolecules umthamo polyelectrolyte ezincinane isinyibilikisi kungenxa yokwanda ingqalelo isambuku macromolecule xa kuthelekiswa nabanye sisombululo. Ngokubhekele phaya, ukuba, umzekelo, counterions ezincinane kakubi ityala, oku kubangela ukuba kwinxalenye engaphakathi macromolecule ukuba ngokuqinisekileyo ityala, kwaye Isisombululo lukufutshane ivolyum macromolecule - negative. ie ezijikeleze umthamo macroion kakuhle ityala, kukho uhlobo 'ion umoya "ye amancinci counter-ion - kakubi ityala. Ukuyekiswa ukukhula emoyeni intlawulo ionic kwenzeka xa endle electrostatic phakathi ion umthamo macroion emoyeni kunye neentsalela ukudibana wobushushu of counterions ezincinane. Oku kubangela lizama Umahluko olunokubakho phakathi emoyeni kunye macroions ionic yi Donnan isakhono. Donnan olunokubakho ikwabizwa ngokuba inwebu isakhono, ngokuba nemeko efanayo lwenzeka kwi inwebu semipermeable, umzekelo, xa esahlula isicombululo electrolyte leyo ion yeentlobo ezimbini - ekwaziyo kwaye akakwazi yokuphumelela therethrough le sijike ecocekileyo.

Donnan enokwenzeka ingqalelo kwityala umda we isakhono kwe-, xa ukuhamba kwelinye ion (kule macroion mzekelo) ngu zero. Emva koko, ngokutsho [1, p. 535], ukuthatha isigxina sokubala alinganayo kwelinye:

E d = (RT / F) Ln ( A1 / A2), apho

Ed - Donnan amandla;

R - njalo igesi jikelele;

T - lobushushu thermodynamic;

F - Faraday njalo;

A1, A2 - counter-umsebenzi kwi kwizigaba contact.

Kule ilungu, apho inwebu eyohlula izisombululo poliosnovaniya (pH = LG 1 = 14) kunye polyacid (pH = LG a 2 = 0), Donnan amathuba ngaphesheya inwebu kubushushu igumbi (T = 300 0 K) iya kuba:

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

enokubakho Donnan ukunyuka ngokomlinganiselo ngqo lobushushu. Kuba nokuhanjiswa yeseli electrochemical Peltier ubushushu umthombo kuphela ekuveliseni umsebenzi luncedo, akumangalisi ukuba izinto ezinjalo EMF kwandisa ngokwandayo lobushushu. Xa iseli nokuhanjiswa ekuveliseni umsebenzi, Peltier ubushushu lisoloko kususwa kokusingqongileyo. Xa uhamba nge EDL kwakhiwa ukusebenza Donnan, kwicala coinciding nolwalathiso ezintle wentsimi ezintlantlu (ngamanye amazwi, xa intsimi ezintlantlu yenza umsebenzi HIV), ubushushu etsalwe kokusingqongileyo ngenxa yokuba kuveliswe le phepha.

Kodwa isiqalelo kwe- na utshintsho oluqhubekayo kunye oluthambileyo kwi lwee- ion, nto leyo ekugqibeleni kukhokelela ngokulinganiswa yoxinaniso kwaye ayeke kwe- ngqo, ngokungafaniyo lizama Donnan, apho, xa kukuvela miqulu eselugcinwe yokuzibophelela emile ngoku, ion ingqalelo, kanye efikelela ixabiso elithile, kuhlala ingatshintshanga .

Isazobe. 2 ubonisa umzobo nekhono redox le abasabela yeehidrojeni ioksijini xa ukutshintsha asidi sisombululo. Le tshati ibonisa ukuba amandla electrode ioksijini ukuyilwa reaction engekho OH- ion (1.23 volts kwimeko asidi) yahlukile amathuba enye kwi yoxinaniso eliphezulu (0.4 volts ngendlela obrak medium) kwi-0.83 volts. Ngokufanayo, amandla electrode yendlela hydrogen-ukwakha engekho H + (-0.83 volts in obrak medium) yahlukile amathuba enye kwi yoxinaniso eliphezulu (0 V ngendlela acid medium), kwakhona e-0.83 volts [4. 66-67]. ie kuyabonakala ukuba 0.83 volts ezifunekayo ukuze bafumane yoxinaniso omkhulu wamanzi unako ezichaphazelekayo. Oku kuthetha ukuba 0.83 volts ifunelwa nobunzima dissociation cala iimolekyuli amanzi H + kunye ion OH-. Ngoko ke, ukuba inwebu kuyaxhaswa kwi Element isithuba cathode yethu asidi aphakathi ngendlela anodic obrak, le ombane unako ukufikelela volts yayo DEL 0.83, nto leyo kwisivumelwano olungileyo izibalo theoretical component thaca ngaphambili. Le ombane inika isithuba conductivity eliphezulu ezintlantlu inwebu ngu dissociation amanzi ion ngaphakathi kuyo.

Isazobe. 2. Umzobo nekhono redox reaction

yokubola kwamanzi, kunye ion H + yaye OH- hydrogen neoksijini.

IF kunye Peltier ubushushu (iSihlomelo №2)

"Unobangela isiphumo Peltier kukuba amandla umndilili abathwali kwentlawulo (xa elektroni definiteness) inxaxheba conductivity yombane ababhexeshi ezahlukeneyo ezahlukeneyo ... In utshintsho ukusuka umqhubi enye ukuya kwenye electron okanye ayidlulisele igridi amandla kwemfuneko okanye ukongeza kukungabikho amandla ngeendleko zayo (ngokuxhomekeke ulwalathiso yangoku).

Isazobe. 3. I-Peltier ukusebenza metal zoqhagamshelwano kunye not translate the semiconductor: ԐF - level Fermi; ԐC - emazantsi Uhanjiso band le semiconductor; ԐV - Valence band; I - ingculaza olukhoyo; izangqa ngeentolo eboniswe ngokwalo electron.

Kwimeko yokuqala kufuphi umfowunelwa bekhululwe, kwaye eyesibini - ekuthiwa-ugxile .. Peltier ubushushu. Umzekelo, kwi semiconductor zoqhagamshelwano - metal (Figure 3) amandla electron abapasileyo ukusuka n-uhlobo semiconductor ukuya metal (kwebala ekhohlo) iphezulu kakhulu ngaphezu Fermi ԐF amandla. Ngoko ke, ukuba waphula lwesilinganiso wobushushu kwi yesinyithi. Lizama ubuyiselwa ngenxa kwezigaba, apho thermalized elektroni, enika crystalline amandla kwemfuneko. grid. I-metal semiconductor (touch ekunene) angadlula kuphela elektroni ezininzi ezingenamandla, ukuze igesi electron kwi intsimbi buyehla. Kwi ukubuyiselwa lonikezelo kuvuselele kwamandla oscillation ezinamanqwanqwa osetyenzisiweyo "[2, p. 552].

Ukuba uqhagamshelane imeko metal / p-semiconductor into efanayo. ngenxa imingxuma semiconductor p-conductivity zinika band Valence layo lingaphantsi kwinqanaba Fermi, ngoko qha uya lupholile, apho electron lusuka p-semiconductor ukuya metal. Peltier ubushushu sakhululwa okanye lilo zoqhagamshelwano ababhexeshi ezimbini, ngenxa ukuvelisa ezimbi okanye ezintle IF yangaphakathi.

Okuqukiweyo umsantsa zoqhagamshelwano ekhohlo (Fig. 3), apho ulwabiwo Peltier ubushushu, iseli electrolytic, umzekelo, NaOH isisombululo zolwelo (Umfanekiso 4) kunye semiconductor zentsimbi kunye n-mayibe afana egalelwe.

Isazobe. 4. I-contact lasekhohlo n-semiconductor kunye but is ivuliwe kwaye zibekwe umsantsa yezisombululo electrolyte. Amagama ziyafana okuqashwa. 3.

Ngokuba, xa uhamba «mna», lo semiconductor ka n-elektroni amandla aphezulu ukufika isisombululo kunokuba ephuma isisombululo kule intsimbi, mandla kwemfuneko (ubushushu of Peltier) kufuneka eme kwiseli.

Le ezikhoyo kwiseli inokuba ityala kuphela ukuvuza apho basabele electrochemical. Ukuba indlela exothermic esiseleni, ubushushu Peltier ngesi esiseleni, njengoko ngaphezulu yena akanayo ukuya. Ukuba ukusabela kwi iseli - endothermic, ubushushu Peltier ngokupheleleyo okanye inxalenye ukuze kubuyekezelwe isiphumo endothermic, ie, ukwenza imveliso reaction. Kulo mzekelo, iyonke iseli reaction: 2H2O → 2H2 ↑ + O2 ↑ - endothermic, ngoko ke ubushushu (energy) loMthetho Peltier kukudala molecule H2 O2, akhiwa ngayo i electrode. Ngenxa yoko, sithola ukuba ubushushu Peltier ekhethiweyo kwi eliphakathi kwi ekunene n-contact semiconductor / wentsimbi akayi kubuyela kokusingqongileyo, kwaye zigcinwa uhlobo lwamandla chemical hydrogen neoksijini iimolekyuli. Ngokucacileyo, ukusebenza umthombo wamandla ombane wangaphandle ucumkile ukuba electrolysis amanzi, kule meko iza kube incinane kakhulu kwimeko electrode ezifanayo, ebangela akukho isenzeko isiphumo Peltier ..

Kungakhathaliseki iimpawu i electrode, iseli electrolytic ngokwayo ukubamba okanye ukuphehla ubushushu xa edlula Peltier noko ngoku. Iimeko miqulu eselugcinwe yokuzibophelela emile, utshintsho okunokwenzeka iiseli Gibbs [4, p. 60]:

Δ G = Δ H - T Δ S, apho

Δ H - utshintsho enthalpy yeseli;

T - lobushushu thermodynamic;

Δ S - utshintsho entropy yeseli;

Q = - T Δ S - ubushushu yeseli Peltier.

Kuba hydrogen-oksijini iseli electrochemical kwi T = 298 (K), utshintsho enthalpy ΔHpr = - 284.5 (kJ / Mol) [8, p. 120], utshintsho kwi Gibbs enokubakho [4. a. 60]:

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

z - inani elektroni molecule nganye;

F - Faraday njalo;

E - EMF iseli.

ke

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

ie hydrogen-oksijini iseli electrochemical ivelisa ubushushu kwimeko-bume Peltier, ngelixa kuphuculwa entropy yayo, lisibekele yayo. Emva koko, kule nkqubo Ngokufanayo, le electrolysis amanzi, nto leyo bekunjalo kumzekelo wethu, Peltier ubushushu Q mod = - Q Ave = - 47.3 (kJ / Mol) loMthetho electrolyte iya etsalwe kokusingqongileyo.

Libhekisela P - Peltier ubushushu othatyathwe kokusingqongileyo kwi ekunene n-contact semiconductor / metal. Ubushushu P> 0 kufuneka ume esiseleni, kodwa ngenxa yokubola yamanzi esiseleni indlela endothermic (Δ H> 0), lo P Peltier ubushushu ukuze kubuyekezelwe isiphumo wobushushu basabela njani:

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

Mod Q uxhomekeke kuphela malunga nokuqulunqwa kwenqaku le electrolyte, ekubeni It luphawu yeseli electrolytic kunye electrode egalelwe, kwaye n ixhomekeke kuphela materials electrode.

Equation (1) ibonisa ukuba ubushushu Peltier P kunye Peltier ukufudumeza Q mod, zezona imveliso yomsebenzi luncedo. ie Peltier ubushushu lwasuswa eliphakathi kunciphisa iindleko njengomthombo wamandla wangaphandle ezifunekayo ukuze electrolysis. A imeko apho ubushushu medium ngumthombo wamandla ekuveliseni umsebenzi luncedo, ngaba uphawu kwe-, ngokunjalo iiseli ezininzi electrochemical, imizekelo izinto ezinjalo ziboniswe kwi [3, p. 248 - 249].

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