Amfani Aiki da zafi na muhalli

Part 1. Wasu sharuddan da ma'anar.

A electromotive karfi (emf) ne na game waje karfi filin rabo hada da wani halin yanzu source ... waje karfi aiki a electroplating Kwayoyin a iyakoki tsakanin electrolyte da wayoyin. Sun kuma yi aiki a kan iyaka tsakanin biyu jũna karafa da kuma sanin lamba m bambanci therebetween [5, p. 193, 191]. Adadin tsalle iko a kan duk saman na kewaye sashe ne daidai da m bambanci tsakanin conductors, located a sarkar iyakar, da kuma ake kira da electromotive karfi emf shugaba kewaye ... sarkar kunsha kawai na conductors na farko irin shi ne daidaita da yuwuwar Jump tsakanin na farko da na karshe shugaba a kai tsaye tuntube su (Volta dokar) ... Idan da kewaye ne ya kamata bude, da emf wannan kewaye shi ne sifili. Don gyara bude-kewaye shugaba, wanda ya hada da akalla daya electrolyte, doka volts ... Babu shakka, kawai shugaba kewaye hada da akalla daya shugaba na biyu irin su electrochemical Kwayoyin (ko sarƙoƙi electrochemical abubuwa) [1, p. 490 - 491].

Polyelectrolytes ne polymers iya dissociating cikin ions a cikin bayani, haka a wannan macromolecule, babban yawan maimaituwa zargin ... crosslinked polyelectrolytes (ion exchangers, ion-musayar guduro) bai narke, kawai kumbura, yayin da rikewa da ikon dissociate [6, p. 320 - 321]. Polyelectrolytes dissociate cikin barnatar da cajin macroion da H + ions ake kira polyacids da dissociates cikin gaskiya ma cajin ions da OH- macroion kira poliosnovaniyami.

Donnan ma'auni m ne m bambanci da ya auku a cikin lokaci iyaka tsakanin biyu Wutan idan wannan iyaka ba permeable ga duk ions. Impermeability iyaka ga wasu ions za a iya lalacewa, misali, gaban membranes da sosai kunkuntar pores wanda suke m ga barbashi sama a wasu size. Zababben permeability na dubawa ya auku da kuma idan wani ions haka karfi da nasaba da daya daga cikin bulan cewa bar shi kullum iya ba. Daidai nuna hali ionic ion musayar resins, ko ion-musayar kungiyar gyarawa homopolar bond a cikin kwayoyin raga ko matrix. The bayani, kasancewa cikin irin wannan matrices siffofin tare da shi guda lokaci. bayani, located waje, - na biyu [7. 77].

A lantarki biyu Layer (EDL) tana gudana a ke dubawa na biyu bulan kafa na oppositely cajin yadudduka zubar a wani nesa daga juna [7. 96].

Peltier qaddamar da wannan kadaici ko sha na zafi a lamba na biyu daban-daban conductors dangane kan shugabanci na lantarki sunã gudãna lamba [2, p. 552].

Part 2: Amfani da zafi matsakaici a cikin electrolysis na ruwa.

La'akari da ginshikai na abin da ya faru na kewaye da electrochemical cell (nan kashi), nuna schematically a cikin siffa. 1, mafi emf saboda da ciki lamba m bambancin (PKK) da kuma sakamako na Donnan (taƙaitaccen bayanin jigon da Donnan sakamako, ciki PKK da kuma hade Peltier zafi ne bayar a cikin na uku ɓangare na article).

Siffa 1. Schematic misali na wani electrochemical cell: 1 - da cathode aka tuntube da wani bayani da 3, da electrochemical rage dauki na electrolyte cations faruwa a kan bãyan tẽkun, Ya sanya daga wani chemically inert dauke da doped n-semiconductor. Sashe na daga cikin cathode a haɗa shi zuwa wani waje ƙarfin lantarki source, metallized. 2 - da anode aka tuntube da wani bayani da 4, a kan surface daga gare faruwa electrochemical hadawan abu da iskar shaka dauki na electrolyte anions, Ya sanya daga chemically inert dauke da doped p-semiconductor. Sashe na daga cikin anode a haɗa shi zuwa wani waje ƙarfin lantarki source, metallized. 3 - cathode sarari, polyelectrolyte bayani, dissociating a ruwa a macroion R- barnatar da cajin da gaskiya ma cajin counterions kananan K + (a cikin rãyuwar misali ne hydrogen ion H +). 4 - anode daki polyelectrolyte bayani a ruwa dissociating cikin gaskiya ma cajin macroion R + da barnatar da cajin counterions kananan DUNIYA (a cikin wannan misali da shi hydroxide ions OH-). 5 - da membrane (diaphragm), shi ne impermeable zuwa macromolecules (macroion) polyelectrolytes, amma gaba daya permeable ga kananan counterions K +, â- da ruwa kwayoyin shared sarari 3 da 4. Evnesh - wani waje ƙarfin lantarki Madogararsa.

Emf ta Donnan sakamako

Domin tsabta, da electrolyte na cathode sarari (. 3, Figure 1) da aka zaba mai ruwa-ruwa polyacid bayani (R-H +), da electrolyte da anode daki (4, fig 1.) - mai ruwa-ruwa poliosnovaniya (R + OH-). A sakamakon dissociation polyacids a cathode daki, a kusa da surface na cathode (1, siffa 1), akwai wani ƙara maida hankali H + ions. M cajin bayyana a cikin kusanci da cathode surface an biya diyya barnatar da cajin macroions R-, tun ba za su iya zo kusa da surface na cathode saboda da size da kuma kasancewar wani lallai cajin ionic yanayi (domin cikakkun bayanai ga. Description Donnan sakamako a Annex №1 na uku ɓangare na article). Saboda haka, iyaka Layer da wani bayani kai tsaye a lamba tare da cathode surface yana da wani m cajin. A sakamakon haka, an electrostatic shigar da a kan cathode surface, contiguous tare da bayani, akwai wani mummunan lura da madugu electrons. watau a ke dubawa tsakanin cathode surface da des bayani ya auku. Field na des Firaministan electrons daga cathode - da bayani.

Hakazalika, a kan anode (2, siffa 1), da iyaka Layer na bayani a cikin anode daki (4, siffa 1) kai tsaye a lamba tare da anode surface yana da wani mummunan cajin, da kuma a kan anode surface, contiguous tare da bayani, akwai wani m cajin. watau a ke dubawa tsakanin anode surface da bayani kuma na faruwa des. Field na des Firaministan electrons daga cikin bayani - a anode.

Saboda haka, filin na des a musaya na cathode da anode tare da bayani, da goyan bayan thermal bayani ion yadawa, suna da biyu ciki emf source, mukaddashin a shagali tare da wani waje source, Ina nufin, turawa korau zargin a cikin madauki counterclockwise.

Dissociation poliosnovaniya polyacids da kuma sa thermal yadawa ta hanyar da membrane (5, Figure 1). H + ions daga cathodic sarari - ga anode, kuma OH- ions daga anode daki - a cathode. Macroion R + kuma R- polyelectrolytes ba zai iya motsawa ta cikin membrane, don haka shi daga cathode sarari akwai wani wuce haddi korau cajin, kuma daga anodic sarari - wani wuce haddi tabbatacce cajin, Ina nufin, akwai wani DPP saboda da Donnan sakamako. Saboda haka, membrane ma ya auku a ciki da emf, mukaddashin a shagali tare da wani waje tushen zafi yadawa da kuma kiyaye bayani daga ions.

A cikin misali, da irin ƙarfin lantarki a fadin membrane iya isa 0,83 volts, kamar yadda wannan yayi dace da wani canji a cikin m da misali hydrogen lantarki daga - 0,83 zuwa 0 volts a miƙa mulki daga alkaline matsakaici a cikin anode daki da cathode daki acidic muhalli. Don cikakkun bayanai, gani. A Annex №1 na uku na labarin.

Emf PKK daga cikin

A Sinadarin emf Yana auku, ciki har da a lamba semiconductor anode da cathode to su karfe sassa hidima don haɗa waje ƙarfin lantarki Madogararsa. wannan emf saboda ciki PKK. Ciki IF ba ya yin halitta, da bambanci ga waje filin a cikin sarari kewaye da lamba conductors, Ina nufin Ba ya shafi motsi na cajin barbashi waje da conductors. Construction n-semiconductor / karfe / p-semiconductor aka isasshe da aka sani kuma ake amfani da, misali, wata thermoelectric Peltier koyaushe. The girma na emf irin wannan tsarin a dakin da zazzabi za a iya isa dabi'u na domin na 0.4 - 0.6 karfin wuta [5, p. 459. 2, p. 552]. Fields cikin lambobin sadarwa directed a irin wannan hanyar da suka tura electrons counterclockwise a cikin madauki, Ina nufin yi a shagali tare da waje Madogararsa. A electrons tãyar da makamashi matakin na matsakaici mamaye zafi na Peltier.

Ciki IF tasowa saboda da yadawa na electrons a lamba yankunan da wayoyin da bayani, a akasin haka, Firaministan electrons a kewaye iri na agogo shugabanci a cikin madauki. watau da motsi na electrons a Sinadarin counterclockwise a wadannan lambobi dole ne a kasaftawa Peltier zafi. amma saboda canja wuri na electrons daga cathode a cikin bayani da kuma na bayani a cikin anode ne dole tare da wani endothermic dauki samar da hydrogen da oxygen, da zafi na Peltier ba saki a cikin matsakaici, kuma shi ne don rage endothermic sakamako, Ina nufin kamar "conserved" a cikin enthalpy na samuwar hydrogen da oxygen. Don cikakkun bayanai, gani. A Annex №2 sulusin da labarin.

dako (electrons da ions) matsawa a Sinadarin kewaye ba rufaffiyar hanyõyi, babu cajin a cikin kashi ne ba motsi a cikin rufaffiyar kewaye. Kowane electron anode samu daga cikin bayani (a cikin shakka daga hadawan abu da iskar shaka na OH- ions zuwa oxygen kwayoyin), ya wuce ta wani waje kewaye da cathode, an volatilized tare da hydrogen kwayoyin (a cikin tsari na dawo daga ions H +). Hakazalika ions OH- da H +, ba su motsa a cikin rufaffiyar kewaye, amma kawai ga m lantarki, sa'an nan ƙafe a cikin nau'i na kwayoyin hydrogen da oxygen. watau da ions da electrons kowane motsi a cikin yanayi a accelerating filin na des, kuma ƙarshen hanya, a lokacin da suka isa surface na lantarki ake hada a cikin DNA, tana mayar da dukan adana makamashi - makamashi na wani sinadaran bond, kuma daga cikin madauki!

All na ciki kafofin na emf Sinadarin, rage halin kaka waje tushen ga ruwa electrolysis. Saboda haka, zafi na yanayi mamaye abubuwa a lokacin da aiki don kula da yadawa na des, shi ne don rage kudin na waje source, Ina nufin, Yana qara electrolysis yadda ya dace.

Electrolysis na ruwa ba tare da wani waje Madogararsa.

A bita da matakai abin da ke faruwa a cikin kashi da aka nuna a cikin siffa. 1, wani waje tushen sigogi ba su ɗauke shi zuwa lissafi. Yi tsammani cewa ciki da juriya shi ne daidai rd da kuma wani irin ƙarfin lantarki na 0. Wannan Evnesh Sinadarin wayoyin suna shorted zuwa m kaya (ga siffa 5). A wannan yanayin, da shugabanci da kuma girma na des filayen tasowa a ke dubawa a cikin abubuwa zama guda.

Siffa 5. A maimakon haka Evnesh (siffa 1) ciki har da m kaya RL.

Ƙayyade da yanayin maras wata-wata na yanzu da kwarara a cikin wannan kashi. Canza Gibbs m, bisa ga dabara (1) na Annex №1 na uku na labarin:

Δ G arr = (Δ H arr - n) + Q zamani

Idan P> Δ H + Q zamani na zamani = 284,5 - 47.2 = 237.3 (KJ / mol) = 1.23 (maddî / kwayoyin)

da Δ G arr <0 kuma maras wata-wata tsari ne yiwu.

Za mu tattauna kara da cewa abubuwa hydrogen tsara dauki auku a wani acidic matsakaici (lantarki m of 0 volts), da kuma oxygen a wani alkaline (lantarki yuwuwar na 0.4 volts). Irin wannan lantarki iko samar da wani membrane (5, siffa 5), da irin ƙarfin lantarki a wanda wannan ya zama 0,83 volts. watau da samar da makamashi da ake bukata domin samuwar hydrogen da oxygen an rage ta 0.83 (maddî / kwayoyin). Sa'an nan da yanayin da yiwuwar maras wata-wata tsari zai:

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

Mun samu cewa, makamashi da shãmaki daga cikin hydrogen da oxygen kwayoyin m, kuma ba tare da yin amfani da wani waje ƙarfin lantarki Madogararsa. watau ko a n = 0.4 (maddî / kwayoyin), Ina nufin a lokacin da ciki lantarki HPDC 0.4 volts, kashi zai zama a Jihar tsauri ma'auni, da kuma wani (ko da kananan) canji na auna yanayin zai haifar da da na yanzu a cikin kewaye.

Wani cikas ga halayen a wayoyin ne kunnawa da makamashi, amma shi ne shafe ta da rami sakamako, tasowa saboda da smallness na da rata tsakanin wayoyin da bayani [7, p. 147-149].

Saboda haka, a kan tushen da makamashi sharudda, mu ƙarasa da cewa, maras wata-wata na yanzu a cikin kashi da aka nuna a cikin siffa. 5, yana yiwuwa. Amma abin da jiki dalilai zai iya sa wannan halin yanzu? Wadannan dalilai aka jera a kasa:

1. Yiwuwar mika mulki na electrons daga cathode a cikin bayani ya fi yiwuwar mika mulki daga anode cikin bayani, tun n-semiconductor cathode yana mai yawa free electrons da wani babban makamashi matakin, da kuma p-semiconductor anode - kawai "ramuka", kuma wadannan "ramuka" ne a wani makamashi matakin kasa da cathode electrons.

2. A membrane yana goyan bayan a cathode sarari na wani acidic yanayi, da kuma a cikin anode - alkaline. A cikin hali na inert wayoyin, wannan take kaiwa zuwa gaskiyar cewa a cathode lantarki m zama fi girma fiye da anode. Saboda haka, dole ne electrons motsawa ta wani waje kewaye daga anode ga cathode.

3. A surface lura da polyelectrolyte mafita tasowa saboda da Donnan sakamako, Yãna halitta a cikin lantarki / bayani filin wannan da cewa filin a cathode inganta electron amfanin ƙasa daga cathode a cikin bayani, da kuma filin a anode - electron shigarwa a cikin anode daga cikin bayani;

4. balance gaba da baya halayen a wayoyin (musayar igiyoyin) son zuciya wajen H + ions kai tsaye rage halayen a cathode da hadawan abu da iskar shaka na OH- ions a anode, tun su suna tare da samuwar iskar gas (H2 da O2) iya sauƙi barin dauki zone (Le Chatelier Principle ta).

Gwaje-gwajen.

Domin gwada yawa kimantawa da irin ƙarfin lantarki a fadin kaya da Donnan sakamako, wani gwaji da aka yi a cikin abin da cathode Sinadarin kunshi na kunna carbon tare da matsanancin graphite lantarki da kuma wani anode - cakuda kunna carbon da anion guduro AB-17-8 tare da matsanancin graphite lantarki. Electrolyte - mai ruwa-ruwa NaOH bayani, anode da cathode sarari rabu da wani roba ji. A bude waje wayoyin na wannan kashi da wani irin ƙarfin lantarki na game da 50 MV. Idan aka haɗa zuwa wani kashi na waje load 10 ohm gyarawa halin yanzu na game da 500 microamps. Lokacin da na yanayi zazzabi ƙaruwa daga 20 zuwa 30 0C ƙarfin lantarki zuwa waje lantarki ya karu zuwa 54 MV. Kara ƙarfin lantarki a yanayi zazzabi ya tabbatar cewa tushen emf ne yadawa, Ina nufin thermal motsi na barbashi.

Domin gwada yawa kimantawa da irin ƙarfin lantarki a fadin kaya daga ciki HPDC karfe / semiconductor gwaji da aka gudanar a cikin abin da cell cathode kunshi roba graphite foda tare da matsanancin graphite lantarki da kuma wani anode - wani foda na boron carbide (B4C, p-semiconductor) tare da matsanancin graphite lantarki. Electrolyte - mai ruwa-ruwa NaOH bayani, anode da cathode sarari rabu da wani roba ji. A bude waje wayoyin na kashi ƙarfin lantarki ya game 150 MV. Lokacin da za a haɗa da na waje kaya zuwa kashi 50 kOhm ƙarfin lantarki ya ragu zuwa 35 mv., Irin wannan karfi da irin ƙarfin lantarki drop saboda da low muhimmi boron carbide kuma, a sakamakon, wani babban ciki juriya Sinadarin. Binciken irin ƙarfin lantarki a kan zafin jiki ga wani kashi na irin wannan tsarin ba da za'ayi. Wannan shi ne saboda gaskiyar cewa, a semiconductor, dangane da sinadaran abun da ke ciki, mataki na doping da sauran kaddarorin, da zazzabi canji a hanyoyi daban-daban na iya tasiri ta Fermi matakin. watau zazzabi sakamako a kan emf Sinadarin (karuwa ko raguwa), a cikin wannan yanayin ya dogara da kayan amfani, don haka wannan ba nuni gwaji.

A wannan lokaci shi ci gaba da wani gwaji a wadda cell cathode aka yi da cakuda kunna carbon foda da kuma KU-2-8 tare da matsanancin bakin karfe lantarki da kuma anode daga cakuda kunna carbon foda kuma anion guduro AB-17-8 da waje lantarki daga bakin karfe. Electrolyte - ruwa-ruwa bayani na NaCl, da anode da cathode sarari rabu da wani roba ji. External wayoyin na wannan kashi da Oktoba 2011 ne iya gajarta da'ira da m ammeter. Yanzu wanda ya nuna wani ammeter, game da wani rana bayan bi da bi, ya ragu da 1 Ma - har zuwa 100 mkA (wanda yake a fili saboda da rabuwa da wayoyin), kuma tun sa'an nan fiye da shekara ba ya canja.

A m gwaje-gwajen da aka bayyana a sama dangane da mafi tasiri kayan inaccessibility samu sakamakon ma ƙananan fiye da rubuce zai yiwu. Bugu da kari, sani cewa kashi daga cikin jimlar ciki emf Sinadarin ko da yaushe cinye don rike da lantarki dauki (samar da hydrogen da oxygen) da kuma ba za a iya auna a waje kewaye.

Kammalawa.

Summing up, za mu iya cewa yanayin yale mu mu maida thermal makamashi cikin amfani da makamashi ko aiki, yayin da yin amfani da matsayin "hita" yanayi da kuma ba da ciwon "firiji". Kamar wancan Donnan sakamako da kuma ciki idan tuba thermal makamashi na cajin barbashi a cikin lantarki filin makamashi DEL matsayin endothermic dauki zafi ne tuba a cikin sinadaran makamashi.

Dauke lamba kashi jan zafi daga matsakaici da kuma ruwa, da kuma allocates da wutar lantarki, hydrogen da oxygen! Bugu da ƙari, cikin aiwatar da kuzari da kuma yin amfani da hydrogen a matsayin man fetur, da kuma ruwan ya koma da baya da zafi matsakaici!

Sashe na 3 na Annex.

Wannan bangare ne kara tattauna Donnan ma'auni sakamako, a jamsin na ciki HPDC karfe / semiconductor da Peltier zafi a kan redox halayen da kuma lantarki iko a cikin kashi.

Donnan m (Shafi №1)

La'akari da ginshikai na abin da ya faru na Donnan yiwuwar polyelectrolyte. Bayan dissociation polyelectrolyte counterions fara ta kananan, ta yadawa, barin girma shagaltar da ta macromolecule. Directional yadawa na counterions na karamin girma polyelectrolyte macromolecules a cikin sauran ƙarfi ne saboda ya karu maida hankali a cikin girma da macromolecule kamar yadda idan aka kwatanta da sauran na bayani. Bugu da ari, idan, misali, kananan counterions ana barnatar da caje, wannan results a cikin wannan fili na can ciki rabo daga macromolecule aka gaskiya ma caje, da kuma bayani ne nan da nan dab da ƙara na macromolecule - korau. watau kusa da wani lallai cajin macroion girma, akwai wani irin "ion yanayi" da kananan counter-ions - barnatar da caji. Ƙarshe ionic yanayi cajin girma ya auku a lokacin da electrostatic filin tsakanin ion girma macroion yanayi da kuma ma'aunan da thermal yadawa na kananan counterions. A sakamakon ma'auni m bambanci tsakanin yanayin da ionic macroions ne Donnan m. Donnan m ne ma ake magana a kai a matsayin matattarar m, saboda a irin wannan halin da ake ciki na faruwa a kan wani semipermeable membrane, misali, a lokacin da shi rarrabe electrolyte bayani wanda yana ions na iri biyu - m, kuma ba su iya wucewa therethrough na tsarki da sauran ƙarfi.

Donnan yuwuwar za a iya gani a matsayin wani iyakance hali na yadawa m, a lokacin da motsi na daya daga cikin ions (a cikin wannan harka macroion) ne sifili. Sa'an nan, bisa ga [1, p. 535], shan cajin na counter daidaita daya:

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

Ed - Donnan m.

R - duniya gas m.

T - thermodynamic zazzabi.

F - Faraday m.

A1, A2 - counter-aiki a lamba bulan.

A wannan kungiya, cikinsa da membrane raba poliosnovaniya mafita (PH = LG wani 1 = 14) da kuma polyacid (PH = LG 2 = 0), Donnan m fadin membrane a dakin da zazzabi (T = 300 0 K) zai zama:

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

Donnan m ƙaruwa a kai tsaye gwargwado zuwa da zazzabi. Domin yadawa na electrochemical cell Peltier kadan ne tafin kafa tushen domin samar da amfani aiki, shi ne ba abin mamaki ba cewa irin wannan abubuwa emf ƙara da kara yawan zafin jiki. A yadawa cell domin samar da aiki, Peltier zafi ne ko da yaushe dauka daga yanayi. Lokacin da na yanzu gudana ta hanyar da EDL kafa Donnan sakamako, a wani shugabanci zo daidai da kyau shugabanci na filin na des (Ina nufin, a lokacin da filin na des aikin m aiki), zafi da ake tunawa daga yanayi domin samar da wannan takarda.

Amma da yadawa kashi ne a ci gaba da kuma unidirectional canji a ion taro, wanda kyakkyawan take kaiwa zuwa equalization na maida hankali da kuma tsayawa directed yadawa, sabanin ma'auni Donnan, a cikinta, a cikin wani hali na leaks quasistatic igiyoyin ion taro, da zarar ya kai wani daraja, ya zauna canzawa .

Siffa 2 ya nuna wani zane na redox iko da halayen da hydrogen da oxygen a lokacin da canza acidity na bayani. A ginshiƙi nuna cewa lantarki yuwuwar na oxygen samuwar dauki in babu OH- ions (1.23 volts a wani acidic yanayi) ne daban-daban daga daya yuwuwar a babban taro (0.4 volts a wani alkaline matsakaici) a 0,83 volts. Hakazalika, lantarki yuwuwar na hydrogen-forming dauki in babu H + (-0.83 volts a alkaline matsakaici) ne daban-daban daga daya yuwuwar a babban taro (0 V a wani acid matsakaici), kuma a 0,83 volts [4. 66-67]. watau bayyana a fili cewa 0,83 volts ake bukata domin ya sami wani babban taro na ruwa a cikin Game da ions. Wannan yana nufin cewa 0,83 volts ake bukata domin wani taro na tsaka tsaki dissociation na ruwa kwayoyin a cikin H + kuma OH- ions. Saboda haka, idan membrane yana goyan bayan a cikin Sinadarin cathode sarari acidic matsakaici da kuma a cikin wani alkaline anodic, da irin ƙarfin lantarki iya isa ta DEL 0,83 volts, wanda shi ne a mai kyau yarjejeniya tare da msar tambayar lissafin gabatar a baya. Wannan irin ƙarfin lantarki na samar da wani babban watsin sarari des membrane da ruwa dissociation cikin ions a cikin shi.

Siffa 2. zane redox dauki iko

bazuwar na ruwa, da kuma H + ions da OH- cikin hydrogen da oxygen.

IF da Peltier zafi (Shafi №2)

"A sabili da Peltier sakamako ne cewa talakawan makamashi na cajin yan dako (ga definiteness electrons) da hannu a cikin wutar lantarki watsin a daban-daban conductors na daban-daban ... A mulki daga shugaba a cikin wani electron ko aika da wuce haddi da ikon Grid ko kari a rashin makamashi a da kudi (dangane da halin yanzu shugabanci).

Siffa 3. A Peltier sakamako a kan lamba karfe da kuma semiconductor n-: ԐF - Fermi matakin. ԐC - kasa na madugu band na semiconductor. ԐV - valence band. I - m shugabanci na yanzu. da'irori tare da kibiyoyi nuna schematically electrons.

A cikin farko idan a kusa da lamba da aka saki, da kuma na biyu - da ake kira tunawa .. Peltier zafi. Alal misali, a kan lamba semiconductor - ƙarfe (Figure 3) da makamashi na electrons da cewa wuce daga n-type semiconductor zuwa karfe (bar touch) ne muhimmanci mafi girma fiye da na Fermi makamashi ԐF. Saboda haka, suna cin thermal ma'auni a cikin karfe. Ma'auni ne a mayar a sakamakon collisions, a cikin abin da thermalized electrons, bada haddi makamashi crystalline. Grid. A semiconductor karfe (dama touch) na iya wuce kawai mafi kuzari electrons, don haka da cewa electron gas a karfe cools. A sabuntawa na ma'auni rarraba oscillation makamashi cinye raga "[2, p. 552].

Don tuntube da karfe / p-semiconductor halin da ake ciki shi ne irin wannan. saboda p-watsin semiconductor ramuka samar da valence band cewa shi ne a kasa da Fermi matakin, sa'an nan da lamba za a sanyaya, a cikin abin da electrons daga ƙarƙashinsu daga p-semiconductor zuwa karfe. Peltier zafi saki ko tunawa da lamba biyu conductors, saboda samar da korau ko tabbatacce na ciki IF.

Kunshe a hagu lamba rata (siffa 3), a kan abin da Peltier zafi kasafi, wani electrolytic cell, misali, mai ruwa-ruwa NaOH bayani (Figure 4) da karfe semiconductor kuma n-bari kawai chemically inert.

Siffa 4. The hagu lamba n-semiconductor da karfe ne bude da kuma sanya shi a cikin rata na electrolyte bayani. Zane-zane da suke daidai kamar yadda a cikin siffa. 3.

Domin, a lokacin da na yanzu gudana «Na», da semiconductor na n-electrons a mafi girma makamashi zo bayani fiye da fitowa daga mafita a cikin karfe, wannan wuce haddi da makamashi (zafi na Peltier) dole ne ya tsaya a cikin cell.

A halin yanzu ta cikin cell iya zama kawai wani hali na leaks cikinta electrochemical halayen. Idan exothermic dauki a cikin cell, da Peltier kadan aka saki a cikin cell, kamar yadda mafi tana da babu inda ya tafi. Idan da dauki a cikin cell - endothermic, da Peltier zafi dukansa ko jera rama domin endothermic sakamako, watau, ta samar da wata dauki samfurin. A wannan misali, jimlar cell dauki: 2H2O → 2H2 ↑ + O2 ↑ - endothermic, don haka zafi (makamashi) na Peltier ne don ƙirƙirar kwayoyin da H2 O2, an kafa a kan wayoyin. Saboda haka, da muka samu cewa da zafi na Peltier zaba a matsakaici a dama n-lamba semiconductor / karfe ba a sake dawo a cikin muhalli, kuma an adana a cikin nau'i na guba makamashi na hydrogen da oxygen kwayoyin. Babu shakka, aiki na waje ƙarfin lantarki tushen da aka cinye ga electrolysis na ruwa, a cikin wannan yanayin zai zama karami fiye a cikin hali na m wayoyin, haddasa babu abin da ya faru na Peltier sakamako ..

Ko da kuwa da kaddarorin da wayoyin, da electrolytic cell kanta iya sha ko samar da zafi a lokacin da wucewa ta cikin Peltier halin yanzu, a nan. A kusan-tsaye yanayi, da m canji na Gibbs Kwayoyin [4, p. 60]:

Δ G = Δ H - T Δ S, inda

Δ H - enthalpy canji na cell.

T - thermodynamic zazzabi.

Δ S - canji a cikin entropy na cell.

Q = - T Δ S - zafi na Peltier cell.

Domin a hydrogen-oxygen electrochemical cell a T = 298 (K), da canji a enthalpy ΔHpr = - 284.5 (KJ / mol) [8, p. 120], da canji a cikin Gibbs m [4. wani. 60]:

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

z - yawan electrons da kwayoyin.

F - Faraday m.

E - emf cell.

saboda haka

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

ie hydrogen-oxygen electrochemical cell haifar zafi a cikin Peltier yanayi, yayin da inganta ta entropy da kuma rage ta. Sa'an nan, a cikin kishiya tsari, da electrolysis na ruwa, wanda shi ne yanayin da mu misali, Peltier zafi Q zamani = - Q Ave = - 47.3 (KJ / mol) na electrolyte za a iya tunawa daga yanayi.

Nuna a fakaice P - Peltier zafi dauka daga cikin yanayi a dama n-lamba semiconductor / karfe. A zafi P> 0 dole tsaya a cikin cell, amma saboda bazuwar na ruwa a cikin cell endothermic dauki (Δ H> 0), da Peltier zafi P ne rama domin thermal sakamako na dauki:

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

Mod Q dogara kawai a kan abun da ke ciki na electrolyte, tun Yana da wani halayyar da electrolytic cell da inert wayoyin, kuma n shi ne dogara kawai a kan lantarki da kayayyakin.

Lissafi (1) ya nuna cewa da zafi na Peltier P da kuma Peltier zafi na zamani Q, suna samar da amfani aiki. watau Peltier zafi dauke daga matsakaici rage kudin da na waje ikon tushen da ake bukata domin electrolysis. A halin da ake ciki inda zafi matsakaici ne tushen samar da makamashi domin samar da amfani aiki, shi ne halayyar yadawa, kazalika da yawa electrochemical Kwayoyin, misalai na irin wannan abubuwa suna nuna a [3, p. 248 - 249].

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