Zothandiza Ntchito ndi kutentha kwa chilengedwe

Gawo 1. mawu ndi matanthauzo.

Mphamvu electromotive (emf) ndi yofunika kunja mphamvu munda gawo chikukhudza gwero panopa ... kunja mphamvu kuchita electroplating maselo pa malire pakati pa electrolyte ndi maelekitirodi lapansi. Iwo ntchito pa malire pakati pa zitsulo ziwiri yosiyana ndi kudziwa kukhudzana angathe kusiyana therebetween [5, p. 193, 191]. Kuchuluka kudumpha Zoyenereza pa pamalo onse a chigawo dera chofanana ndi kusiyana ulipo pakati pa akuwauza kuti, ili ku malekezero unyolo, ndipo akutchedwa electromotive mphamvu emf wochititsa dera ... unyolo wopangidwa yekha wa ochititsa a mtundu woyamba ndi wofanana ndi kulumpha ulipo pakati pa woyamba ndi wochititsa lomaliza mwachindunji angawapeze (Volta lamulo) ... Ngati dera ndi bwino lotseguka, emf dera lino ndi ziro. Pofuna kukonza lotseguka-dera wochititsa, womwenso electrolyte chimodzi, malamulo applicable volts ... Mwachionekere, okhawo wochititsa dera chikukhudza wochititsa imodzi ya mtundu lachiwirili electrochemical maselo (kapena unyolo electrochemical zinthu) [1, p. 490 - 491].

Polyelectrolytes ndi ma polima angathe dissociating mu ayoni mu njira, motero mu macromolecule chomwecho, ambiri milandu ... crosslinked polyelectrolytes (ndi kuzizira ion, kumatchula ion-kuwombola utomoni) Kodi si kupasuka, kokha pathupi, pamene kusunga luso dissociate [6, p. 320 - 321]. Polyelectrolytes dissociate ku zoipa mlandu macroion ndi H + ayoni amatchedwa polyacids ndi dissociates mu ayoni ndithu mlandu OH- macroion otchedwa poliosnovaniyami.

Donnan mgwirizano angathe kusiyana amaona kuti kumachitika pa gawo malire pakati pa electrolytes awiri ngati malire izi si permeable kuti ayoni onse. Impermeability malire kwa ena ayoni ingayambe Mwachitsanzo, pamaso pa nembanemba ndi pores yopapatiza amene ali kuwoloka kwa particles pamwamba kukula ena. Kusankha permeability wa mawonekedwe kumachitika ndi ngati ayoni iliyonse kwambiri kumayambitsa mmodzi wa magawo kuti kusiya ambirife sindingakhoze. Chimodzimodzi zinthu amaayoni ion kuwombola resins, kapena ion-kuwombola gulu atathana homopolar chomangira mu latisi maselo kapena masanjidwewo. The njira, kukhala mkati mawerengetsedwe ngati njira pamodzi nazo gawo limodzi; njira, linali kunja, - wachiwiri [7. 77].

The magetsi wosanjikiza awiri (EDL) zikuchitika pa mawonekedwe a magawo awiri anapereka zigawo oppositely mlandu oyenerera pa mtunda wina ndi mzake [7. 96].

Peltier mavuto kudzipatula ichi kapena mayamwidwe kutentha pa mgwirizano wa ochititsa awiri osiyana malinga ndi malangizo a magetsi likuyenderera mu kukhudzana [2, p. 552].

Gawo 2: Kugwiritsa kutentha sing'anga mu electrolysis madzi.

Taganizirani limagwirira wa zosayembekezereka ya dera la selo electrochemical (hereinafter mchitidwe), asonyeza schematically mkuyu. 1, zambiri emf chifukwa kukhudzana mkati angathe kusiyana (PKK) ndi zotsatira za Donnan (imafotokoza mwachidule akamanena za Donnan tingati PKK mkati ndi kugwirizana Peltier kutentha amaperekedwa mu gawo lachitatu m'nkhani).

Mkuyu. 1. chojambula chifaniziro cha selo electrochemical: 1 - cathode ndi analankhulana ndi njira ya 3, electrochemical kuchepetsa anachita cations electrolyte zimachitika pamwamba pake, zopangidwa ndi mankhwala inert kwambiri doped N-michenga yopangira zida zamagetsi. Mbali ya cathode ochilumikiza ku anthu wamba voteji, metallized; 2 - anode ndi analankhulana ndi njira ya 4, padziko zake zimachitika electrochemical makutidwe ndi okosijeni anachita anions electrolyte, zopangidwa mankhwala inert kwambiri doped tsa-michenga yopangira zida zamagetsi. Mbali ya anode ochilumikiza ku anthu wamba voteji, metallized; 3 - cathode danga, polyelectrolyte njira, dissociating m'madzi pa macroion R- zoipa mlandu ndithu mlandu counterions yaing'ono K + (mu chitsanzo pamakhala ion wa hydrogen H +); 4 - anode chipinda polyelectrolyte yothetsera mu madzi dissociating mu ndithu mlandu macroion R + ndipo counterions zoipa mlandu yaing'ono A- (chitsanzo ichi hydroxide ayoni OH-); 5 - nembanemba (zakulera), ndi impermeable kuti macromolecules (macroion) polyelectrolytes, koma kwathunthu permeable kwa counterions yaing'ono K +, A- ndi tizidutswa madzi nawo malo 3 ndi 4; Evnesh - kunja kwa thupi voteji gwero.

Emf ndi Donnan zotsatira

Chifukwa ndi losavuta kumva, ndi electrolyte wa danga cathode (. 3, Chithunzi 1) amusankha amadzimadzi polyacid njira (R-H +), ndi electrolyte ndi anode chipinda (4, mkuyu 1.) - amadzimadzi poliosnovaniya (R + OH-). Chifukwa cha polyacids dissociation m'chipinda cathode, pafupi padziko cathode (1, mkuyu. 1), pali ndende kuchuluka kwa H + ayoni. Zabwino mlandu kuwonekera pafupi ndi pamwamba cathode si kulipidwa zoipa mlandu macroions R-, kuyambira iwo sangakhoze kubwera pafupi padziko cathode chifukwa kukula kwake ndi pamaso pa zabwino mlandu mlengalenga amaayoni (mwatsatanetsatane kuona. Kufotokozera Donnan anachita alumikiza №1 wa gawo lachitatu m'nkhani). Choncho, wosanjikiza malire a njira mwachindunji pokhudzana ndi pamwamba cathode ali ndi mlandu positive. Chifukwa, ndi kupatsidwa ulemu electrostatic padziko cathode, contiguous ndi njira, pali woyang'anira zinthu zoipa zimene ma elekitironi conduction. Ie pa mawonekedwe pakati pamwamba cathode ndi des njira amapezeka. Field ya des amakankhira ma elekitironi ku cathode wa - kwa njira.

Mofananamo, pa anode (2, mkuyu. 1), malire wosanjikiza yankho mu anode chipinda (4, mkuyu. 1) mwachindunji pokhudzana ndi pamwamba anode ali ndi mlandu oipa, ndi padziko anode, contiguous ndi njira, pali woyang'anira positive. Ie pa mawonekedwe pakati padziko anode ndi njira likugwiritsidwanso des. Field ya des amakankhira ma elekitironi ku njira - ndi anode.

Choncho, m'munda wa des pa polumikizira wa cathode ndi anode ndi njira, anathandiza matenthedwe njira ion mayamwidwe, awiri mkati emf gwero, zinthu konsati anthu wamba, i.e., kukankhira milandu zoipa mu kuzungulira counterclockwise.

Dissociation poliosnovaniya polyacids ndi kumachititsanso matenthedwe mayamwidwe mwa Kakhungu (5, Chithunzi 1) H + ayoni kwa danga cathodic -. Ku anode, ndipo OH- ayoni ku anode chipinda - ndi cathode. Macroion R + ndipo R- polyelectrolytes sangathe adutsa Kakhungu, kotero izo kwa danga cathode pali owonjezera zoipa mlandu, ndi ku anodic danga - ndi muyeso zabwino mlandu, i.e., pali wina DPP chifukwa Donnan kwenikweni. Choncho, Kakhungu komanso amapezeka mkati emf ndi zinthu konsati anthu wamba chifukwa cha kutentha mayamwidwe ndipo anakhalabe njira ya ayoni.

Chitsanzo chathu, voteji kudutsa nembanemba ndi angafikire 0,83 volts, monga izi limafanana ndi kusintha angathe elekitirodi muyezo wa hydrogen kwa - volts 0,83 0 pa kusintha kwa sing'anga zamchere mu anode chipinda cha cathode chipinda acidic chilengedwe. Kuti mumve zambiri, onani. Mu alumikiza №1 wa gawo lachitatu la nkhaniyi.

Emf PKK kuchokera mkati

Amafotokozera emf Zimachitika, kuphatikizapo mu kukhudzana michenga yopangira zida zamagetsi anode ndi cathode m'madera awo zitsulo kutumikira kulumikiza kunja voteji gwero. emf izi chifukwa PKK mkati. Internal NGATI Kodi kulenga, motsutsana ndi munda kunja mu malo ozungulira ndi ochititsa kukhudzana, i.e. Zilibe bwanji chisonyezo cha particles mlandu kunja ochititsa lapansi. Yomanga N-michenga yopangira zida zamagetsi / zitsulo / tsa-michenga yopangira zida zamagetsi ndi mokwanira amadziwika ndi ntchito, Mwachitsanzo, thermoelectric Peltier gawo. Ukulu wa emf ndi dongosolo ngati firiji angafikire mfundo za dongosolo la 0.4 - 0,6 Volt [5, p. 459; 2, p. 552]. Minda pochita akuuzidwa mu njira yakuti iwo kukankha ma elekitironi counterclockwise mu kuzungulira, i.e. Kugwila konsati ndi anthu wamba. The ma elekitironi kulera mlingo mphamvu sing'anga kungolandira kutentha kwa Peltier.

Internal NGATI akuwuka chifukwa mayamwidwe wa ma elekitironi m'madera mgwirizano wa maelekitirodi ndi njira M'malo mwake, amakankhira ma elekitironi mu mobwerera malangizo mu kuzungulira. Ie chisonyezo cha ma elekitironi mu mchitidwe counterclockwise pochita izi ayenera allocated Peltier kutentha. koma chifukwa kulanda ma elekitironi ku cathode mu njira ndi njira mu anode ali kwenikweni limodzi ndi anachita endothermic kupoletsa hydrogen ndi mpweya, kutentha kwa Peltier si anamasulidwa mu sing'anga, ndipo ndi kuchepetsa zotsatira endothermic, i.e. ngati "kokhazikika" mu enthalpy mapangidwe a hydrogen ndi oxygen. Kuti mumve zambiri, onani. Mu alumikiza №2 gawo lachitatu nkhaniyo.

onyamula (ma elekitironi ndi ayoni) kusuntha mbali dera si njira chatsekedwa, palibe mlandu mbali ya chikubwera mu dera chatsekedwa. Aliyense anode elekitironi kuwapeza njira (m'kupita kwa makutidwe ndi okosijeni wa OH- ayoni kuti okosijeni), ndipo anadutsa ndi dera kunja kwa cathode, ndi volatilized pamodzi ndi tinthu wa hydrogen (m'kati ayambe ayoni H +). Mofananamo ayoni OH- ndi H + Usaigwedezere mu dera chatsekedwa, koma kwa elekitirodi lolingana, kenako asanduke nthunzi mu mawonekedwe a haidrojini maselo ndi oxygen. Ie ndi ayoni ndi ma elekitironi lililonse chikusuntha zachilengedwe m'munda mofulumira a des, ndipo mapeto a njira, pamene iwo n'kufika pamwamba pa elekitirodi ndi amaphatikiza molekyulu ndi, akatembenuka lonse kusungidwa mphamvu - mphamvu ya mankhwala akapolo, ndi pa kuzungulira!

Onse magwero a mkati mwa emf Amafotokozera, kuchepetsa anthu wamba chifukwa electrolysis madzi. Choncho, kutentha kwa yozungulira kungolandira zinthu pa ntchito yake kukhalabe mayamwidwe wa des, ndi kuchepetsa mtengo wa anthu wamba, i.e., Izo kumawonjezera electrolysis dzuwa.

Electrolysis wa madzi popanda zochokera kwina.

Tionenso njira kunachitika zinthu zikusonyezedwa mkuyu. 1, gwero magawo kunja si n'komwe. Tiyerekeze kuti kukana mkati ndi wofanana Rd ndi voteji wa 0. Kuti Evnesh maelekitirodi amafotokozera ali shorted kuti katundu chabe (onani mkuyu. 5). Pankhaniyi, malangizo ndi kufunika kwa minda des akuwuka pa kugwiritsa ntchito zinthu sizinasinthe.

Mkuyu. 5. M'malo Evnesh (mkuyu. 1) kuphatikizapo chabe katundu RL.

Kudziwa zinthu mowiriza otaya panopa mbali imeneyi. Kusintha Gibbs osiyanasiyana, monga njira (1) ya alumikiza №1 wa gawo lachitatu la nkhani:

Δ G arr = (Δ H arr - n) + Q yamakono

Ngati P> Δ H + Q yamakono yamakono = 284,5 - 47.2 = 237.3 (KJ / mol) = 1.23 (EV / molekyulu)

ndi Δ G arr <0 ndi ndondomeko mowiriza n'zotheka.

Tikambirana zina kuti zinthu m'badwo wa hydrogen anachita amapezeka mu sing'anga acidic (elekitirodi angathe 0 volts), ndi mpweya mu (angathe elekitirodi wa 0.4 volts) zamchere. Chotero elekitirodi Zoyenereza imapereka Kakhungu (5, mkuyu. 5), ndi voteji pa zomwe ziyenera 0,83 volts. Ie mphamvu wofunikila mapangidwe hydrogen ndi mpweya yafupika ndi 0.83 (EV / molekyulu). Ndiye chikhalidwe cha kuthekera ndondomeko mowiriza atero:

P> 1,23 - 0.83 = 0.4 (EV / molekyulu) = 77.2 (KJ / mol) (2)

Ife tikupeza kuti mphamvu chotchinga wa hydrogen ndi mpweya mamolekyulu zitha kupewedwa ndi opanda ntchito kunja voteji gwero. Ie ngakhale pa N = 0.4 (EV / molekyulu), i.e. pamene lamkati elekitirodi HPDC 0.4 volts, mchitidwe adzakhala mu mkhalidwe wamphamvu mgwirizano ndi aliyense (ngakhale ang'ono) kusintha zinthu moyenera adzachititsa ziliri pa dera la.

Chinanso chimene zochita pa maelekitirodi ndi kutsegula mphamvu, koma likuchotsedwa ndi mmene mumphangayo, akuwuka chifukwa smallness a kusiyana maelekitirodi ndi njira [7, p. 147-149].

Choncho, pamaziko a tiganizira mphamvu, tinganene kuti mowiriza ziliri pa zinthu zikusonyezedwa mkuyu. 5, n'zotheka. Koma kodi zifukwa thupi zingachititse panopa izi? zifukwa zimenezi zili m'munsimu:

1. Mwina tinganene ma elekitironi ku cathode mu njira kuposa Mwina kusintha kwa anode mu njira, kuyambira N-michenga yopangira zida zamagetsi cathode ali zambiri ma elekitironi ufulu ndi mkulu mlingo mphamvu, ndi tsa-michenga yopangira zida zamagetsi anode - yekha "mabowo" ndipo izi "mabowo" ali pa msinkhu ndi mphamvu pansipa ma elekitironi ndi cathode;

2. Kakhungu The imayendetsedwa mu malo cathode zachilengedwe acidic, ndi anode wa - zamchere. Pankhani ya maelekitirodi inert zimenezi zimadzetsa choona kuti cathode elekitirodi angathe amakhala lalikulu kuposa anode lapansi. Choncho, ma elekitironi ayenera adutsa ndi dera kunja kwa anode kuti cathode ya;

3. mlandu pamwamba pa njira ya polyelectrolyte akuwuka chifukwa Donnan tingati amalenga pa elekitirodi / njira kumunda ngati munda pa cathode umalimbikitsa elekitironi zokolola kuchokera cathode mu njira, ndi m'munda pa anode - elekitironi kulowa mu anode ku njira;

4. bwino kutsogolo ndi chigamulocho zochita pa maelekitirodi ndi (kuwombola mafunde) nkani kwa H + ayoni zochita mwachindunji kuchepetsa pa cathode ndi makutidwe ndi okosijeni wa OH- ayoni pa anode, chifukwa iwo limodzi ndi mapangidwe mpweya (H2 ndi O2) amatha mosavuta kusiya zone anachita (Le Chatelier a Mfundo).

Zatsopano.

Pakuti kuwunika kachulukidwe wa voteji kudutsa katundu ndi Donnan tingati kuyesera anali anachita imene cathode mchitidwe wopangidwa ndi mpweya adamulowetsa ndi akunja graphite elekitirodi ndi anode - chisakanizo cha mpweya adamulowetsa ndi anion utomoni AB-17-8 ndi akunja graphite elekitirodi. Electrolyte - amadzimadzi NaOH njira, anode ndi cathode malo anasiyanitsidwa ndi mwake kupanga. Pa maelekitirodi lotseguka kunja mchitidwe uyu anali voteji pafupifupi 50 MV. Pamene chikugwirizana ndi mchitidwe kunja katundu 10 ohm atathana panopa pafupifupi 500 microamps. Pamene yozungulira kutentha ukuwonjezeka 20 mpaka 30 0C voteji kwa elekitirodi kunja ziwonjezeke kwa 54 MV. Kuwonjezeka voteji pa kutentha yozungulira, chikutsimikizira kuti gwero la emf ndi mayamwidwe, i.e. matenthedwe zoyenda particles.

Pakuti kuwunika kachulukidwe wa voteji kudutsa katundu kuchokera mkati HPDC zitsulo / michenga yopangira zida zamagetsi kuyesera kunachitidwa imene selo cathode imakhala kupanga graphite ufa ndi akunja graphite elekitirodi ndi anode - ufa wa boron carbide (B4C, p-michenga yopangira zida zamagetsi) ndi wakunja graphite elekitirodi. Electrolyte - amadzimadzi NaOH njira, anode ndi cathode malo anasiyanitsidwa ndi mwake kupanga. Pa maelekitirodi lotseguka kunja amafotokozera voteji anali pafupifupi 150 MV. Pamene polumikiza katundu kunja kwa mchitidwe 50 kOhm voteji amagwa 35 MV., Cholimba voteji dontho chifukwa otsika nacho boron carbide ndipo zotsatira zake, mkulu mkati kukana amafotokozera. Investigation voteji motsutsana kutentha kwa mchitidwe dongosolo choterocho si ikuchitika. Ichi ndi chifukwa chakuti, kwa michenga yopangira zida zamagetsi ndi, malingana ndi mankhwala ake zikuchokera, mlingo wa doping ndi zina kusintha kutentha m'njira zosiyanasiyana kumakhudza ake mlingo Fermi. Ie kutentha zimakhudzanso emf Mchitidwe (kuchuluka kapena kuchepa), mu nkhani iyi zimadalira zipangizo ntchito, kotero izi si zimasonyeza kuyesera.

Pa nthawi imeneyi anapitiriza kuyesera ina imene selo cathode unapangidwa osakaniza ufa adamulowetsa mpweya ndi Ku-2-8 ndi akunja zosapanga dzimbiri elekitirodi ndi anode kuchokera chisakanizo cha adamulowetsa mpweya ufa ndi anion utomoni AB-17-8 kwa elekitirodi kunja kwa zitsulo zosapanga dzimbiri. Electrolyte - amadzimadzi njira ya NaCl, ndi anode ndi cathode malo anasiyanitsidwa ndi kupanga ndi anamvera. maelekitirodi kunja chinthu ichi ndi October 2011 amatha yochepa dera la chabe ammeter. Current amene amaonetsa ammeter, pafupifupi tsiku Poyankha, anatsika ndi 1 MA - mpaka 100 mkA (zomwe zikuoneka chifukwa cha kugawanika kwa maelekitirodi), ndipo kuyambira pamenepo kuposa chaka sasintha.

Mu zatsopano zothandiza tafotokozazi mogwirizana ndi aluso zipangizo inaccessibility analandira zotsatira zayamba poyerekeza theoretically zotheka. Komanso, dziŵani kuti limaphatikizidwa emf mkati Mchitidwe nthawi chimadyedwa kukhala elekitirodi anachita (ulimi wa hydrogen ndi mpweya) ndi sangakhoze anayeza mu dera kunja.

Mapeto.

Polongosola mwachidule, tinganene kuti chikhalidwe amatilola kuti atembenuke mphamvu matenthedwe mphamvu zothandiza kapena ntchito, pamene akugwiritsa ntchito monga "chotenthetsera" chilengedwe ndi zopanda "firiji". Choncho Donnan zotsatira ndipo mkati NGATI atatembenuzidwa matenthedwe mphamvu ya particles mlandu wa magetsi kumunda mphamvu Del monga kutentha endothermic anachita ali n'kukhala mphamvu mankhwala.

Akuti kukhudzana mchitidwe amadya kutentha kwa sing'anga ndi madzi, ndipo allocates magetsi, hydrogen ndi mpweya! Komanso, ndondomeko ya mowa mphamvu ndi ntchito haidrojeni nkhuni, madzi umabwereranso kwa kutentha sing'anga!

Gawo 3 la alumikiza lapansi.

mbali zina takambirana Donnan mgwirizano tingati pamphambano ya lamkati HPDC zitsulo / michenga yopangira zida zamagetsi ndi Peltier kutentha zochita redox ndi elekitirodi Zoyenereza mbali ya.

Donnan kuthekera (Zakumapeto №1)

Taganizirani limagwirira wa zosayembekezereka ya Donnan lingathe polyelectrolyte. Pambuyo dissociation polyelectrolyte counterions kuyamba ang'ono ake, ndi mayamwidwe, kusiya buku wotanganidwa ndi macromolecule lapansi. Polozera mayamwidwe wa counterions ochepa macromolecules buku polyelectrolyte mu zosungunulira ndi chifukwa kuchuluka ndende mu chochuluka macromolecule ndi poyerekeza ndi zina njira. Komanso, ngati Mwachitsanzo, counterions ang'onoang'ono zoipa mlandu, zimenezi zimachititsa kuti mbali lamkati la macromolecule ali ndithu mlandu, ndi njira yomweyo pafupi ndi buku la macromolecule wa - negative. Ie kuzungulira ndithu mlandu macroion buku, pali mtundu wa "ion mlengalenga" wa ang'ono potsimikizira-ayoni - zoipa mlandu. Kuchotsa amaayoni m'mlengalenga mlandu kukula amene akupezeka pamene munda electrostatic pakati pa ion buku macroion m'mlengalenga ndi miyeso ikukhudzana mayamwidwe wa counterions yaing'ono. Chifukwa mgwirizano angathe kusiyana pakati pa mlengalenga ndi macroions amaayoni ndi Donnan angathe. Donnan angathe umatchedwanso ngati angathe Kakhungu, chifukwa ndi zinthu zofanana limapezeka pa Kakhungu semipermeable Mwachitsanzo, pamene alekanitsa electrolyte njira yomwe ali ayoni a mitundu iwiri - wangwiro komanso si angathe kudutsa therethrough wa zosungunulira choyera.

Donnan angathe tinganene kuti ngati kuchepetsa vuto la lingathe mayamwidwe, pamene kuyenda kwa mmodzi wa ayoni (mu izi macroion choncho) ndi ziro. Ndiye, molingana [1, p. 535], kutenga woyang'anira kauntala Angafanane ndi:

E D = (RT / F) Ln ( A1 / A2), kumene

Mkonzi - Donnan kuthekera;

R - chilengedwe mpweya nthawi zonse;

T - thermodynamic kutentha;

F - Faraday zonse;

A1, A2 - potsimikizira-ntchito magawo kukhudzana.

Mu membala lino, m'mene Kakhungu alekanitsa poliosnovaniya njira (pH = LG 1 = 14) ndi polyacid (pH = LG 2 = 0), Donnan angathe kudutsa nembanemba ndi firiji (T = 300 0 K) adzakhala:

E D = (RT / F) (LG ndi 1 - LG 2) Ln (10) = (8.3 * 300/96500) * (14 - 0) * Ln (10) = 0.83 Volts

Donnan angathe ukuwonjezeka mogwirizana mwachindunji kutentha. Pakuti mayamwidwe wa electrochemical selo Peltier kutentha ndiye gwero yekha kupanga ntchito zothandiza, n'zosadabwitsa kuti zinthu ngati emf kumawonjezera ndi kuwonjezeka kutentha. Mu mayamwidwe selo kwa kupanga ntchito, Peltier kutentha nthawi anatengedwa kuchokera chilengedwe. Pamene utuluke panopa mwa EDL anapanga Donnan tingati m'njira imodzimodzi ndi malangizo abwino a m'munda wa des (i.e., pamene munda wa des amachita ntchito zabwino), kutentha odzipereka ku malo yopanga pepala ili.

Koma chinthu mayamwidwe ndi mosalekeza ndi unidirectional kusintha mu ndende ion, zomwe mapeto kwa equalization ndende ndi Kuyima imatsogoleredwa mayamwidwe, mosiyana ndi mgwirizano Donnan, momwe, zikakhala kuchucha quasistatic mafunde ion ndende, kamodzi popeza anafika mtengo ena, akhala zikutsatiridwa .

Mkuyu. 2 chimasonyeza chithunzi cha redox Zoyenereza pa zochita za hydrogen ndi mpweya pamene kusintha acidity wa njira. Tchati limasonyeza kuti elekitirodi angathe mpweya mapangidwe anachita, pakalibe OH- ayoni (1.23 volts m'malo Acidic) ndi osiyana lingathe amodzi ndende mkulu (volts 0.4 mu sing'anga ndi zamchere) pa 0,83 volts. Mofananamo, elekitirodi angathe anachita wa hydrogen zomwe zimapezeka pakalibe H + (-0.83 volts mu sing'anga zamchere) ndi osiyana lingathe amodzi ndende mkulu (0 V mu sing'anga ndi acid), komanso pa 0,83 volts [4. 66-67]. Ie zoonekeratu kuti 0,83 volts chofunika kupeza mkulu wa ndende madzi mu ayoni ziwalo. Izi zikutanthauza kuti 0,83 volts chofunika kwa gulu la ndale dissociation la tinthu madzi mu H + ndipo OH- ayoni. Choncho, ngati nembanemba ndi imayendetsedwa mbali cathode malo acidic sing'anga wathu ndi mu anodic zamchere, ndi voteji angafikire ake Del 0,83 volts, amene ali ogwirizana wabwino ndi anapezazo ndi ongolankhula anazipereka. voteji limapereka mkulu madutsidwe danga des Kakhungu ndi dissociation madzi mu ayoni mkati mwake.

Mkuyu. 2. Chithunzi Zoyenereza redox anachita

kuwonongeka kwa madzi, ndi H ayoni + ndipo OH- mu hydrogen ndi oxygen.

NGATI ndi Peltier kutentha (Zakumapeto №2)

"The chifukwa cha Peltier tingati ndi mphamvu avareji onyamula mlandu (kwa ma elekitironi definiteness) nawo madutsidwe magetsi mu ochititsa zosiyanasiyana osiyana ... Mu kusintha kuchokera kondakitala wina mu elekitironi wina kapena kupatsira owonjezera mphamvu gululi kapena yothandiza kupanda mphamvu ndalama zake (malingana ndi malangizo panopa).

Mkuyu. 3. Peltier zotsatira pa zitsulo kukhudzana ndi michenga yopangira zida zamagetsi n-: ԐF - Fermi yofanana; ԐC - pansi pa conduction gulu la michenga yopangira zida zamagetsi ya; ԐV - valence gulu; Ine - zabwino malangizo a panopa; mabwalo mivi wasonyeza schematically ma elekitironi.

Ngati choyamba pafupi oyandikana adzamasulidwa, ndipo chachiwiri - otchedwa odzipereka .. Peltier kutentha. Mwachitsanzo, pa kukhudzana michenga yopangira zida zamagetsi - zitsulo (Chithunzi 3) mphamvu ya ma elekitironi kuti kudali ku N-mtundu michenga yopangira zida zamagetsi ku zitsulo (kumanzere kukhudza) ndi apamwamba kwambiri kuposa Fermi mphamvu ԐF. Chotero, chophwanya mgwirizano matenthedwe mu zitsulo. Mgwirizano abwezeretsedwa chifukwa cha mwansanga, imene thermalized ma elekitironi, kupereka owonjezera mphamvu crystalline. gululi. The michenga yopangira zida zamagetsi zitsulo (kukhudza) angaphunzitse okha ma elekitironi ambiri amphamvu, kuti elekitironi mafuta zitsulo akamazizira. Pa kubwezeretsedwa kwa mgwirizano kufalitsa oscillation mphamvu ankadya latisi "[2, p. 552].

Kulankhula ndi zitsulo / tsa-michenga yopangira zida zamagetsi vuto ndi ofanana. chifukwa tsa-madutsidwe michenga yopangira zida zamagetsi mabowo kupereka valence ake gulu kuti ali pansipa mlingo Fermi, ndiye kukhudzana adzakhala utakhazikika, imene ma elekitironi zichokere P-michenga yopangira zida zamagetsi ku zitsulo. Peltier kutentha anamasulidwa kapena chosakanikirana ndi mgwirizano wa ochititsa awiri, chifukwa yopanga zoipa kapena zabwino za NGATI mkati.

Zina lamanzere kukhudzana kusiyana (mkuyu. 3), limene Peltier kutentha Kugawilidwa kwanthaka, ndi electrolytic selo Mwachitsanzo, amadzimadzi NaOH njira (Chithunzi 4) ndi zitsulo michenga yopangira zida zamagetsi ndipo N-zilekeni mankhwala inert.

Mkuyu. 4. kumanzere kukhudzana N-michenga yopangira zida zamagetsi ndi zitsulo ndi lotseguka ndipo anaikidwa kusiyana kwa njira electrolyte. Mayina ndi amodzi mkuyu. 3.

Chifukwa, pamene utuluke panopa «Ine», ndi michenga yopangira zida zamagetsi wa N-ma elekitironi mu mphamvu apamwamba kufika njira kuposa akutuluka yothetsera mu zitsulo, mphamvu imeneyi muyeso (kutentha kwa Peltier) ayenera kuima mu selo.

Panopa mwa selo kokha nkhani ya kuchucha m'menemo zochita electrochemical. Ngati exothermic anachita muchipindachi, kutentha Peltier adzamasulidwa ku selo, zambiri ali kopita. Ngati zimene selo - endothermic, ndi Peltier kutentha thunthu kapena mwina kukwaniritsa zotsatira endothermic, ie, kupanga mankhwala anachita. Mu chitsanzo ichi okwana khungu anachita: 2H2O → 2H2 ↑ + O2 ↑ - endothermic, kotero kutentha (mphamvu) wa Peltier ndi kulenga mamolekyulu ndi H2 O2, anapanga pa maelekitirodi lapansi. Choncho, timapeza kuti kutentha kwa Peltier anasankha sing'anga ku lamanja N-kukhudzana michenga yopangira zida zamagetsi / zitsulo si imabwereranso mu chilengedwe, ndipo kusungidwa mu mawonekedwe a mphamvu mankhwala hydrogen ndi mpweya mamolekyulu. Mwachionekere, kugwira ntchito kwa anthu wamba voteji chimadyedwa kwa electrolysis wa madzi, mu nkhani iyi adzakhala kakang'ono kuposa mu nkhani ya maelekitirodi zofanana, kuchititsa palibe zosayembekezereka wa Peltier zotsatira ..

Kaya katundu wa maelekitirodi, ndi electrolytic foni lokha akhoza kuyamwa kapena kupanga kutentha pamene kudutsa Peltier panopa thereto. The quasi-malo amodzi zinthu, kusintha angathe maselo Gibbs [4, p. 60]:

Δ G = Δ H - T Δ S, kumene

Δ H - enthalpy kusintha kwa maselo;

T - thermodynamic kutentha;

Δ S - kusintha mu mphamvu zosagwiritsika ntchito selo;

Q = - T Δ S - kutentha kwa Peltier selo.

Kwa haidrojeni-mpweya electrochemical Selo T = 298 (K), kusintha enthalpy ΔHpr = - 284.5 (KJ / mol) [8, p. 120], kusintha Gibbs angathe [4. a. 60]:

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

z - chiwerengero cha ma elekitironi pa molekyulu;

F - Faraday zonse;

E - emf selo.

Choncho

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

mwachitsanzo haidrojeni-mpweya electrochemical selo amapanga kutentha m'malo Peltier, pamene kuwongolera mphamvu zosagwiritsika ntchito yake ndi kutsitsa ake. Kenako mu ndondomeko osiyanitsidwa, ndi electrolysis wa madzi, choncho chitsanzo chathu, Peltier kutentha Q yamakono = - Q Ave = - 47.3 (KJ / mol) wa electrolyte adzakhala odzipereka kwa chilengedwe.

Potanthauza P - Peltier kutentha anatengedwa ku malo lamanja N-kukhudzana michenga yopangira zida zamagetsi / zitsulo. Kutentha P> 0 ayenera kuima mu selo, koma chifukwa kuwonongeka kwa madzi mu selo endothermic anachita (Δ H> 0), ndi Peltier kutentha P azilipira kwa zotsatira matenthedwe zotani:

Δ G arr = (Δ H arr - n) + Q yamakono                                                                        (1)

Yamakono Q zimatengera yekha zikuchokera electrolyte, chifukwa Ndi khalidwe la selo electrolytic ndi maelekitirodi inert, ndipo N amadalira yekha pa zinthu elekitirodi.

Aone kuti pali (1) chimasonyeza kuti kutentha kwa Peltier P ndi Peltier kutenthetsa yamakono Q, ndi kupanga ntchito zothandiza. Ie Peltier kutentha unachotsedwa sing'anga amachepetsa mtengo wa kunja kwa thupi mphamvu zoyendetsera wofunikila electrolysis. Nkhani ina kumene kutentha sing'anga ndi gwero la mphamvu kwa kupanga ntchito zothandiza, ndi khalidwe la mayamwidwe, komanso maselo ambiri electrochemical zitsanzo za zinthu amenewa tikuonera [3, p. 248 - 249].

Zothandizira

1. Gerasimov Ya. I. Inde zimapangidwira thupi. Chitsanzo: Pakuti yunivesite. V 2 T. T.II. - 2 tira .. - M:. Chemistry, Moscow, 1973. - 624 p.
2. Dashevskiy 3. M. Peltier kwenikweni. // thupi Encyclopedia. Mu 5 m. T. III. Magneto - Poynting Lingaliro Lovomerezeka. / Ch. Mkonzi. A. M. Prohorov. Mkonzi. kulengeseka. DM Alekseev, A. M. Baldin, AM Bonch-Bruevich, A. Borovik-Romanov ndi ena - M:.. Great Russian Encyclopedia, 1992. - 672 p. - ISBN 5-85270-019-3 (3 m.); ISBN 5-85270-034-7.
3. Krasnov KS thupi Chemistry. Mu 2 mabuku. Vol. 1. mpangidwe wa chinthu. Yopezeka m'zinthu zachilengedwe: Proc. sukulu yapamwamba; KS Krasnov, N. K. Vorobev, I. neri Al Godnev -. 3 tira .. - M:. Apamwamba. wk, 2001. -. 512. - ISBN 5-06-004025-9.
4. Krasnov KS thupi Chemistry. Mu 2 mabuku. Vol. 2. Electrochemistry. kinetics mankhwala ndi catalysis: Proc. sukulu yapamwamba; KS Krasnov, NK Vorobyov I. N. Godnev neri Al. -3 Mkonzi., Rev. - M:. Apamwamba. wk, 2001. -. 319. - ISBN 5-06-004026-7.
5. Sivukhin nkhanza za m'banja ambiri njira ya sayansi. Chitsanzo: Pakuti yunivesite. Mu 5 m. T.III. Magetsi. - 4 dwa, olakwika .. - M: FIZMATLIT. Kusindikiza nyumba ya MIPT, 2004. - 656 p. - ISBN 5-9221-0227-3 (3 m.); 5-89155-086-5.
6. Tager A. A. thupi kapangidwe ka ma polima. - M:. Chemistry, Moscow, 1968. - 536 p.
7. Vetter K. Electrochemical kinetics, lotembenuzidwa kuchokera m'Chijeremani ndi kusinthidwa la wolemba a kope Russian, lolembedwa ndi Corr. USSR Academy of Sciences prof. Kolotyrkin YM - M:. Chemistry, Moscow, 1967. - 856 p.
8. P. Atkins thupi Chemistry. Mu 2 v. T.I., amachoka mu Chingerezi a dotolo wa sayansi mankhwala Butin kp - M:. Mir, Moscow, 1980. - 580 p.