Pono keia mau mea hana ma ka wela o ka i nā hana

Part 1. kekahi mau hua'ōlelo a me ka wehewehena i.

Ke electromotive ikaika (emf) mea integral mawaho ikaika kahua hapa ec i kaʻikena kahi ... mawaho ka manehu i ka electroplating keena ma na palena ma waena o ka electrolyte a me na nā uila aʻa lolo. Ka mea i hana ma ka palena ma waena o nā dissimilar ke hooheheeia, a hooholo i ka hui 'Loaʻaʻiaʻana ma therebetween [5, p. 193, 191]. Huina Lele Loaʻaʻia ma luna o nā mea a pau surfaces o ka huakai kaapuni pauku, ua like ia me ka Loaʻaʻia likeʻole ma waena o nā conductors, Aia ma ke kaula wēlau, a ua kapaia ka electromotive ikaika emf alakaʻi mele huakai kaapuni ... kaula iloko olaila wale no na conductors o ka mua ano mea like me ka Loaʻaʻia Lele ma waena o ka mua a me ka hope alakaʻi mele i loko o nā moʻopuna hoʻokaʻaʻike ia (Volta kānāwai) ... Inā ka huakai kaapuni mea pono hamama, ka emf keia huakai kaapuni a ka 'Aʻohe. E hooponopono i ka hamama-kaapuni conductors, a mai nā 'ma ka liʻiliʻi loa hoʻokahi electrolyte, i ke kānāwai' aʻole e pili Volta ... Ua ua maopopo ia wale nō ka huakai kaapuni conductors, a me ma ka liʻiliʻi loa kekahi alakaʻi mele o ka lua o ka ano i electrochemical aeee (paha i puhi ai electrochemical aeee) [1, p. 490 - 491].

Polyelectrolytes i polymers hiki ke dissociating i Ion ma ka pāʻoihana, pela ma ka ia macromolecule, he nui helu o recurring 'āhewa' ana ... crosslinked polyelectrolytes (ion poe kuai moni, ion-mail kēpau) 'aʻole i hoike mai, wale pehu, oiai hoʻokoe iho i ka hiki e dissociate [6, p. 320 - 321]. Polyelectrolytes dissociate i loko o negatively hoopiiia macroion, a ua kapaʻia H + Ion polyacids a dissociates i olelo ikaika mai, papa mai Ion a me OH- macroion kapa poliosnovaniyami.

Donnan equilibrium Loaʻaʻia o ka Loaʻaʻia okoa e ia lŘlŘ ma ka pae palena ma waena o nā electrolytes mau ina keia kali mea ole permeable i nā mea a pau Ion. Impermeability palena no kekahi mau Ion i ke kena ae la, no ka mea hoike, i ka mua o nā membranes me ka loa ololi ili i nā impassable no (particles) ma luna o ka kekahi nui. E wae permeability o ka mau 'ia lŘlŘ a ina kekahi Ion no laila, ikaika ua hoʻopili ai i kekahi o nā kūlana e haʻalele ia ano laulā, e hiki ole. Penei nō hele ionic ion mail kēpau, a ion-mail pae paa homopolar hoopaa i loko o ka puka olu oia i hakakino paha'ōpū mai. Ke kākoʻo pāʻoihana, i loko o ia mau matricesʻano a pu me ia i ka hookahi pae; pāʻoihana, Aia mawaho, - i ka lua [7. 77].

Ka uila papalua, ahu iho (EDL) e hana ma luna o ka mau 'ana o nā kūlana iiiaanoaa o elua oppositely i hoopiiia papa manaʻo ma ka kekahi mamao mai kekahi i kekahi [7. 96].

Peltier ai keia hoʻokaʻawale 'ole omo o ka wela ma ka hui' ana o nā 'okoʻa conductors ke kaumaha ma luna o ke alakaʻiʻana o ka uila pono e kahe ana ma ka leka pepa [2, p. 552].

Part 2: E ho ohana i ka wela meakino i loko o ka electrolysis o ka wai.

E noonoo i keʻano papa hana o ka hanana o ka huakai kaapuni a ka electrochemical aeea (i hoakaka ia hehee ai), hōʻike schematically ma lāʻau. 1, oi emf aie i ka mea maloko hui 'Loaʻaʻia likeʻole (PKK) a me ka hope o Donnan (pōkole ano o ka pā o ka Donnan hookoia, ua hoakaka ia maloko PKK, a pili Peltier wela i loko o ka hapakolu o ka' atikala).

Lāʻau. 1. kiʻikuhi e hoohalike ai o ka electrochemical aeea: 1 - ka cathode ua ua hoʻomaopopo i ka pāʻoihana o ke 3, ka electrochemical ka ho'ēmiʻana naoh o ka electrolyte cations ana ma luna o kona luna, i o ka chemically inertʻelemakule doped N-mea uholo uila. Part o ka cathode ai pili aku ia i ka mawaho anakahi uila kumu, metallized; 2 - ka anode ua ua hoʻomaopopo i ka pāʻoihana o 4, ma ka ili honua ona i hoʻomaka ai electrochemical'okesaside naoh o ka electrolyte anions, i o chemically inertʻelemakule doped P-mea uholo uila. Part o ka anode ai pili aku ia i ka mawaho anakahi uila kumu, metallized; 3 - cathode makahiki, polyelectrolyte pāʻoihana, dissociating i loko o ka wai ma macroion R- negatively i hoopiiia a me ka ikaika kauoha counterions uuku K + (i loko o ka keia kumu hoʻohālike o ka hydrogen ion H +); 4 - anode pahu polyelectrolyte pāʻoihana i ka wai i loko o dissociating olelo ikaika mai, papa mai macroion R + a me ka mea uuku negatively kauoha counterions A- (i loko o kēia hana ia hydroxide Ion OH-); 5 - i kaʻili lahilahi (diaphragm), mea impermeable i macromolecules (macroion) polyelectrolytes, akā, pono permeable i ka poe liilii, counterions K +, A- a me ka wai nā lātoma i kaʻana like makahiki 3 a me ka 4; Evnesh - he mawaho anakahi uila kumu.

Emf ma Donnan kanawai

No ka mōakaaka, ka electrolyte o ka cathode makahiki (. 3, ke Kii 1) ua wae koʻana koko polyacid pāʻoihana (R-H +), ka electrolyte a me ka anode pahu (4, lāʻau 1.) - koʻana koko poliosnovaniya (R + OH-). E like me ka hopena o ka dissociation polyacids i loko o ka cathode pahu, ma ka ili honua o ka cathode (1, lāʻau. 1), he mea ka māhuahua lehulehu o ka H + Ion. Maikaʻi kauoha e hōʻike 'ana ma o ka wahi o ka cathode' ilikai ua ole compensated negatively ia macroions R-, mai (Description Donnan kanawai ma ka hoohui №1 o ka hapakolu o ka 'atikala no lāliʻi ike.) Ka mea hiki ole e hele mai a kokoke i ka ili o ka cathode aie i kona nui, a me ka alo ana o ka ikaika i hoopiiia ionic lewa. Ke'ī mai, i ka mokuna, ahu iho o ka pāʻoihana 'ana ma ka hui' ana me ka cathode 'ilikai i ka maikaʻi kauoha. E like me ka hopena, he electrostatic hoʻokomo ma luna o ka cathode luna, kokoke i ka pāʻoihana, he mea he hopena maikaʻi 'āhewa' ana o ka conduction electrons. Ie ma ka mau 'ma waena o ka cathode' ilikai a me Des pāʻoihana ia lŘlŘ. Field o ka Des pushes electrons mai ka cathode - a hiki i ka pāʻoihana.

Like, ma ka anode (2, lāʻau. 1), i ka mokuna, ahu iho o ka pāʻoihana i loko o ka anode pahu (4, lāʻau. 1) 'ana ma ka hui' ana me ka anode 'ilikai i ka io ka uku ole, a ma ka anode luna, kokoke i ka pāʻoihana, he mea he maikaʻi kauoha. Ie ma ka mau 'ma waena o ka anodeʻili, a me ka pāʻoihana i ia lŘlŘ Des. Field o ka Des pushes electrons mai ka pāʻoihana - he anode.

Ke'ī mai, ke kahua o Des ma na Library o ka cathode a me ka anode me ka pāʻoihana, kākoʻo thermal pāʻoihana ion maholahune, he elua maloko emf kumu, e hana ma ka Concert me ka mawaho kumu, a laila, e hookuke i ka hopena maikaʻi 'āhewa' ana i loko o ka loop counterclockwise.

Dissociation poliosnovaniya polyacids, a me ke kumu no thermal maholahune ma kaʻili lahilahi (5, ke Kii 1) H + Ion, mai ka cathodic hookahi -, a hiki i ka anode, a me OH- Ion, mai ka anode pahu - he cathode. hiki ole Macroion R + a R- polyelectrolytes holo i loko o kaʻili lahilahi, pela no ka mea, mai ka cathode makahiki he mea kekahi i koe io ka uku ole, a mai ka anodic makahiki - he oi maikaʻi ka uku ole, a laila, he mea kekahi DPP aie i ka Donnan kanawai. Penei, o kaʻili lahilahi kekahi ia lŘlŘ i loko o ka emf, e hana ma ka Concert me ka mawaho kumu o ka wela maholahune, a mālama i ka pāʻoihana o Ion.

I ko makou laʻana, ke anakahi uila ma kaʻili lahilahi ke hiki 0,83 volts, e like me keia hoʻopili like i kekahi loli ma ka Loaʻaʻia o ka maʻamau hydrogen'ūholo uila mai - 0,83 a hiki i 0 volts ma ke hoʻololi, mai ka'ākilikai meakino i loko o ka anode pahu ka cathode pahuʻakika 'ia. No ka lāliʻi, ike. I hoohui №1 o ka hapakolu o ka 'atikala.

Emf PKK mai o ka loko

Ka hehee ai emf Ua i, a me loko o ka papa mea uholo uila anode a me ka cathode i kā lākou mea hiki ke hooheheeia wahi lawelawe e hoʻohui i nā mawaho anakahi uila kumu. kēia emf manawa i na PKK. Kūloko, inā 'aʻole e hana, ma ka Akä naÿe i ka mawaho kahua i loko o ka makahiki a puni i ka leka pepa conductors, a laila Ua aʻole e pili mai ka noi o hoopiiia (particles) ma waho o ka conductors. ? Ieoaeunoai N-mea uholo uila / metala / pa-mea uholo uila ua lawa ka ike a me ka ua ia, no ka laʻana, he thermoelectric Peltier Module. I ka nui o ka emf ia i kekahi me nā hale i mehana ke hiki aiee o ka mea o 0,4 - 0,6 Volt [5, p. 459; 2, p. 552]. Mahinaʻai i ka hui 'ana i kuhikuhi ia ma ka ke ala i ka mea, pahu aku ai electrons counterclockwise i loko o ka loop, a laila hana ma Concert me ka mawaho kumu. Nā electrons hoala mai i ka ikehu kiʻekiʻe o ka meakino Komo 'o ia i ka wela o ka Peltier.

Kūloko ina i kupu mai ma muli i ka maholahune o electrons ma ka hui 'mau mea o na nā uila aʻa lolo a me ka pāʻoihana, ma ka mea ku ole, pushes electrons ma ka clockwise ala e hiki aku i loko o ka loop. Ie pono e anao? aou ka noi o electrons i loko o ka hehee ai counterclockwise i loko o kēia hui 'ana Peltier wela. akā, no ka mea, i ka hoolilo ana o electrons mai ka cathode i loko o ka pāʻoihana a me ka o ka pāʻoihana i loko o ka anode ua pono pu ma ka endothermic naoh hoʻomakaʻia hydrogen a me ka oxygen, i ka wela o ka Peltier mai i kuu i loko o ka meakino, a me ka mea e emi ai ka endothermic hopena, a laila e like "conserved" i loko o ka enthalpy o ke kahua o ka hydrogen a me ka oxygen. No ka lāliʻi, ike. I hoohui №2 i ka hapakolu o ka 'atikala.

nā moku halihali mokulele (electrons a me Ion) hoʻoneʻe i hehee ai a puni,ʻaʻole paʻa mau kuamoo, iʻoihana i loko o ka hehee ai ua e hele i loko o ka paʻa kaapuni. Kēlā me kēia huina'ine anode i loaa mai i ka pāʻoihana (i loko o ka papa o ka'okesaside o OH- Ion i ka o oxygen nā lātoma), a ua hele ma kekahi mawaho kaapuni i ka cathode, ua volatilized pu me hydrogen nā lātoma (i loko o ke kaʻina hana o ka hou ana o ka Ion H +). Like me Ion OH- a me H + e ole hoʻoneʻe i loko o ka paʻa kaapuni, akā, wale no ka like'ūholo uila, a laila evaporate i loko o ka palapala o ka hakakino hydrogen a me ka oxygen. Ie a me ka Ion, a electrons kēlā neʻe i loko o kona 'ia i loko o ka accelerating kula o Des, a me ka pau ana o ke alanui, ka wā e hiki i ka ili o ka'ūholo uila e hui ma ka lātoma, hoʻololi' ana i ka mea holoʻokoʻa waiho ikehu - ka ikaika o ka Nine Inch hoopaa, a me ka mai o ka loop!

A pau o ka na kumu o ka emf Hehee ai, emi na koina mawaho kumu no ka wai electrolysis. Ke'ī mai, i ka wela o ka Ambient o ke kemu hehee wale i kona hana, e malama i maholahune o Des, mea e emi i ka lilo o ka mea mawaho kumu, a laila, Ua maoli ka electrolysis ka hoʻokōʻana.

Electrolysis o ka wai me kekahi mawaho kumu.

Ma keʻano o ka hanaʻana no ka hoʻoponopono 'ia i loko o ka hehee ai i hoikeia ma ka lāʻau. 1, he mawaho kumu kiko'î ka mea,ʻaʻole i laweʻia i loko o nui. Ina i ka mea maloko ia'ku mea like e RD a me ke anakahi uila o 0. E Evnesh Hehee ai nā uila aʻa lolo e emi ana malalo iho a hiki i ka OE haawe (e nānā lāʻau. 5). Ma keia hihia, o ke kuhikuhi ana a me ka nui o Des mahinaʻai i kupu mai ma ka mau 'ana ma o ka hehee wale koe i ka ia.

Lāʻau. 5. Aka Evnesh (lāʻau. 1) a me OE e haawe RL.

Ho oholo i ka olelo o ka noho'na makaainana i uluʻikena pele i loko o kēia hehee ai. Hoʻololi i ka Gibbs Loaʻaʻia, e like me ka haʻilula (1) o ka hoohui №1 o ka hapakolu o ka 'atikala:

Δ G arr = (Δ H arr - N) + Q mod

Inā P> Δ H + Q mod mod = 284,5 - 47.2 = 237.3 (kJ / Mol) = 1.23 (eV / lātoma)

ka Δ G arr <0 a me ka noho'na makaainana i ulu kaʻina me ke kūʻokoʻa.

Mākou e noʻonoʻo hou i ka oihana mua hydrogen hanauna naoh ia lŘlŘ i loko o kaʻakika meakino ('ūholo uilaʻia o 0 volts), a me ka oxygen ma loko o ka (Loaʻaʻia'ūholo uila o 0,4 volts) kona'ākilikai. Oia'ūholo uilaʻia e hoʻolako i kaʻili lahilahi (5, lāʻau, 5), ke anakahi uila ma a keia e e 0,83 volts. Ie ka ikehu koi 'ia no ka ho okumu ana o hydrogen a me ka oxygen ma ua hoemi ma 0.83 (eV / lātoma). A laila, i ke ano o ka manawa kūpono o ka noho'na makaainana i ulu kaʻina e:

P> 1,23 - 0.83 = 0.4 (eV / lātoma) = 77.2 (kJ / Mol) (2)

Mākou i loaʻa i ka ikehu ke'ākeʻakeʻa mai o ka hydrogen a me ka oxygen ma nā lātoma avoidable, a me ka hoʻohana 'ana i ka mawaho anakahi uila kumu. Ie a hiki ma N = 0.4 (eV / lātoma), a laila ka wā o ka pahale'ūholo uila HPDC 0,4 volts, hehee ai e ia i loko o ka moku'āina o hōʻeuʻeu equilibrium, a me kekahi (he uuku) loli o ke kaulike kūlana e i ka pono ma ka huakai kaapuni.

Kekahi keʻakeʻa nei i na reactions ma na nā uila aʻa lolo o ka ho'ā hope ikehu, akā, ka mea, ua eliminated ma ka tunnel kanawai, ala ka ai i ka uuku o ka nahā i waena o nā nā uila aʻa lolo a me ka pāʻoihana [7, p. 147-149].

Penei, ma ke kumu o ka ikaika me ka noʻonoʻo, ke manao nei makou noho'na makaainana i ulu pono i loko o ka hehee ai i hoikeia ma ka lāʻau. 5, he mea hiki. Akā, aha physical kumu hiki i keia au i? Mau kumu i ma lalo iho:

1. Ka pahiki o ka hoʻololi o electrons mai ka cathode i loko o ka pāʻoihana ma luna ma mua o ka pahiki o hoʻololi mai ke anode i loko o ka pāʻoihana, mai N-mea uholo uila cathode i ka hailona o noa electrons me ke kiʻekiʻe ikehu pae, a me ka pa-mea uholo uila anode - wale "lua", a me kēia mau "lua" i ma ka ikehu pae ma lalo o ka cathode electrons;

2. kaʻili lahilahi Kākoʻo i loko o kaʻakika 'ia cathode makahiki a me ka anode - kona'ākilikai. Ma ka hihia o inert nā uila aʻa lolo, ua hiki aku i ka mea ana i cathode'ūholo uilaʻia i nui ma mua o ka anode. Nolaila, e neʻe electrons ma kekahi mawaho kaapuni mai ka anode a hiki i ka cathode;

3. kaʻilikai malama o ka polyelectrolyte pāʻoihana i kupu mai ma muli i ka Donnan keia, hana ma ka'ūholo uila / pāʻoihana kahua ia i ke kula ma ka cathode paipai 'ia ka huina'ine hua mai i ka cathode i loko o ka pāʻoihana, a me ke kula ma ka anode - huina'ine e komo i loko o ka anode, mai ka pāʻoihana;

4. kaulike i mua, a ke hoʻololi reactions ma na nā uila aʻa lolo (mail paialewa) biased i H + Ion pololei ka ho'ēmiʻana reactions ma ka cathode a me ka'okesaside o OH- Ion ma ka anode, mai ka mea, i hele pu me ia e ho okumu o ke kinoea (h2 a me O2) hiki no ke puana e waiho naoh ciia (Le Chatelier ka loina hooponopono).

Ho okolohua.

No ka laupaʻi loiloi 'ana o ke anakahi uila ma ka haawe ana ma ka Donnan kanawai, he hoʻokolohua i hanaʻi ma a ka cathode hehee ai oia no ka ho'ā' kalapona me ka pā graphite'ūholo uila a me ka anode - i ka läÿau, o ka ho'ā 'kalapona a me ka anion kēpau AB-17-8 me ka mea mawaho graphite'ūholo uila. Electrolyte - koʻana koko NaOH pāʻoihana, anode a me ka cathode hakahaka i hookaawale ia e ka kemikala ikeia. Ma hamama mawaho nā uila aʻa lolo o keia hehee ai i ke anakahi uila o ma kahi o 50 MV. I ka ai pili aku i ka mawaho e haawe i ka hehee ai 10 ohm haka pono o kahi o 500 microamps. I ka wā o ka Ambient piʻina mai ka 20 a hiki i 30 0C anakahi uila ma luna o ka mea mawaho nā uila aʻa lolo mahuahua i 54 MV. Mahuahua i ke anakahi uila ma ka Ambient ana wela hōʻoia ana i ke kumu o ka emf Ua maholahune, a laila thermal ka noi o na (particles).

No ka laupaʻi loiloi 'ana o ke anakahi uila ma luna o ka haawe ana i ka mea maloko ina metala / mea uholo uila hoʻokolohua i mālama' ia i loko o i ka halepaahao cathode ninoieo o kemikala graphite ka pauka me ka pā graphite'ūholo uila, a me ka anode - boron carbide pauka (B4C, pa-mea uholo uila) me ka mea mawaho graphite'ūholo uila. Electrolyte - koʻana koko NaOH pāʻoihana, anode a me ka cathode hakahaka i hookaawale ia e ka kemikala ikeia. Ma hamama mawaho nā uila aʻa lolo o ka hehee ai anakahi uila ua ma kahi o 150 MV. I ka ai pili aku i ka mawaho e haawe i ka hehee ai 50 kOhm anakahi uila, haule iho i 35 MV., Na ka ikaika anakahi uila e like no me ka haʻahaʻa kūʻiʻoo boron carbide, a, me ka hopena, he kiʻekiʻe maloko e kū'ē'ē mai hehee ai. ua i lawe mai hoʻokolokolo 'anakahi uila kū'ē ana wela no i hehee ai o ia' ole. O ke kumu ho i ka mea e, no ka mea uholo uila, ke kaumaha ma muli kona Nine Inch haku mele 'ana, degere o ka doping a me nā waiwai, ka mahana loli ma ke ano o ke ho ololi i kona Fermiʻilikai. Ie wela kanawai ma emf Hehee ai (mahuahua ana a me ka emi ana), ma keia hihia hilinaʻi nui ma luna o nā mea i hoʻohana, no laila, i kēia mea,ʻaʻole hōʻike hoʻokolohua.

Ma keia wahi e hoomau kekahi hoʻokolohua ma i aeea cathode ua i mai o ka läÿau, o ka ho'ā 'kalapona ka pauka a me KU-2-8 me ka mea ma waho kuhiliʻole kila'ūholo uila, a me ka anode, mai ka läÿau, o ka ho'ā' kalapona ka pauka a me ka anion kēpau AB-17-8 i ka mawaho'ūholo uila mai kuhiliʻole kila. Electrolyte - koʻana koko pāʻoihana a NaCl, ka anode a me ka cathode hakahaka i hookaawale ia e ka kemikala ikeia. Mawaho nā uila aʻa lolo o keia hehee ai me October 2011 e hiki i ka pokole-huakai kaapuni i ka OE ammeter. O kēia i hōʻike he ammeter, e pili ana i ka lā ma hope hoʻi, ua hoʻemi ma 1 Ma - mai i 100 mkA (i mea apparently no a hiki i ka polarization o na nā uila aʻa lolo), a mai laila aku ma mua o ka makahiki 'aʻole e hoʻololi' ana i.

I ka mea hiki ia mea i ho'ākāka 'ia ma luna ma ka pili ana i ka nui ka hoʻokō pono inaccessibility loaa hualoaʻa kūpono kou haʻahaʻa ma mua o theoretically mea hiki. Eia hou, e makaala i ka hapa o ka huina maloko emf Hehee ai mau hoopau no ka malama ana i ka'ūholo uila naoh (ke? Iecaianoaaiiie o ka hydrogen a me ka oxygen), aʻaʻole hiki ke ana i loko o ka mawaho huakai kaapuni.

Panina Manaʻo.

Summing mai, ua hiki ke manao nei makou, ano e leie aku mākou, e hoohuli thermal ikehu i pono keia mau mea ikehu a me ka hana, 'oiai hoʻohana like me ka "iaia? Aaaoaeuiuo" i hoʻolilo' ia a me ka ole i loaa i kekahi "Pahu Hau". Pela Donnan kanawai a me ka na ina hoohuliia thermal ikehu o na (particles) ia i loko o ka uila kahua ikehu Del like me ka endothermic naoh wela ua hoohuliia i loko o Nine Inch ikehu.

Noonoo papa hehee ai i pau ai ka wela mai o ka meakino a me ka wai, a me allocates uila mana, a me ka hydrogen ka oxygen! A, i ke kaʻina hana o ka ikehu hokii, a me ka hoʻohana 'ana o ka hydrogen like me ka wahie, a me ka wai huli hoʻi i ka wela meakino!

Part 3 o ka hoohui aku.

Keia hapa ua hou kamaʻilio nui Donnan equilibrium kanawai, ma ka hookui ana o ka pā HPDC metala / mea uholo uila a me Peltier wela ma luna o redox reactions a me'ūholo uilaʻia i loko o ka hehee ai.

Donnan Loaʻaʻia (i paiiaʻi na №1)

E noonoo i keʻano papa hana o ka hanana o Donnan Loaʻaʻia no ka polyelectrolyte. Ma hope o dissociation polyelectrolyte counterions hoʻomaka kona uuku, ma ka maholahune, waiho i ka buke e ku ma ka macromolecule. Directional maholahune o counterions o ka poe liilii, ka leo polyelectrolyte macromolecules ma ka'ūheheʻe ia lŘlŘ no ka mea, o ka mea mahuahua lehulehu ma ka buke hoʻohālikelike me ka macromolecule koe pāʻoihana. Eia, ina, no kekahi laʻana, uuku counterions i negatively i hoopiiia, keia hualoaʻa ma i ka pahale hapa o ka macromolecule e ikaika i hoopiiia, a me ka pāʻoihana mea koke e pili ana i ka buke o ke macromolecule - io. Ie puni ka ikaika i hoopiiia macroion ka leo, aia no he ano o ka "ion lewa" o ka mea liilii, ee-Ion - negatively i hoopiiia. Hoopau wale ionic lewa kauoha ulu ia lŘlŘ ka wā o ka electrostatic kahua ma waena o ka ion ka leo macroion lewa a me ka mea kaupaona o ka thermal maholahune o liʻiliʻi counterions. Ke kūpono equilibrium Loaʻaʻia likeʻole ma waena o ka lewa, a me ka ionic macroions o Donnan Loaʻaʻia. Donnan Loaʻaʻia ua i haawi ia ia e like me ka ʻili lahilahi Loaʻaʻia, no ka mea, he like kulana home 'ole ia lŘlŘ ma luna o ka semipermeableʻili lahilahi, no kekahi laʻana, ka wā e hoʻokaʻawale i ka electrolyte pāʻoihana i mea Ion o nāʻano - hiki ia oe, aʻaʻole hiki ke hele therethrough o ka'ūheheʻe maemae.

Donnan Loaʻaʻia hiki ke noʻonoʻo me ka ke kaupalenaʻana hihia o ka maholahune Loaʻaʻia, i ka wa a ka ka hoʻoneʻe o kekahi o na Ion (i loko o keia hihia macroion) He 'Aʻohe. A laila, e like me [1, p. 535], lawe kauoha o ka loan like i kekahi:

E b = (RT / F) Ln ( A1 / A2), kahi

Ed - Donnan Loaʻaʻia;

R - ao kinoea a eia i;

T - thermodynamic wela;

F - Faraday a eia i;

A1, A2 - ee-hanana hulina i loko o ka leka pepa kūlana.

Ma keia lala, ai kaʻili lahilahi hoʻokaʻawale poliosnovaniya pāʻoihana (pH = Lg he 1 = 14) a me ka polyacid (pH = Lg he 2 = 0), Donnan Loaʻaʻia ma kaʻili lahilahi i mehana ea (T = 300 0 K) makemake e:

E b = (RT / F) (Lg he 1 - Lg he 2) Ln (10) = (8,3 * 300/96500 ) * (14 - 0) * Ln (10) = 0.83 Volts

Donnan Loaʻaʻia kēia piʻina ma ka pololei e like me ke ana wela. No ka maholahune o ka mea electrochemical aeea Peltier wela o ka poli kumu no ka? Iecaianoaaiiie o ka pono keia mau mea hana, ia mea e kahaha ko oukou naau i na oihana mua emf maoli he me e māhuahua ana wela. I maholahune aeea no ka? Iecaianoaaiiie o ka hana, Peltier wela ua mau ia mai ke kaiapuni. I ka papa lua i pele ma ka EDL hanaia Donnan hookoia, i loko o ke kuhikuhi ana coinciding me ka maikaʻi ma amau o ka mahinaʻai o ke Des (a laila, i ka wa a ka mahinaʻai o Des hanaʻia maikaʻi hana), wela ke kemu, mai ka papa no ka mea? Iecaianoaaiiie o keia pepa.

Akā, i loko o ka maholahune hehee ai o ke ana, a unidirectional loli i loko o ka lehulehu o ka Ion, a ultimately hele aku ai i equalization o ka lehulehu, a ana kuhikuhi maholahune, e like equilibrium Donnan, ma ka a, ma ka hihia o ka hanana o quasi-kūpaʻaʻikena, ion lehulehu, i kekahi manawa, hiki ole i kekahi waiwai, koe kŰlń .

Lāʻau. 2 hōʻike he kiʻikuhi o ka redox Loaʻaʻia o nā reactions o ka hydrogen a me ka oxygen ma ka wā hoʻololi i kaʻakika o ka pāʻoihana. Ka pakuhi hōʻike i ka'ūholo uilaʻia o ka oxygen ma ho okumu naoh i loko o ka wa e kaawale aku o OH- Ion (1.23 volts i loko o kaʻakika 'ia) mea okoa ka ia Loaʻaʻia ma kiʻekiʻe lehulehu (0.4 volts i loko o ka'ākilikai meakino) ma 0,83 volts mai. Like me, o ka'ūholo uilaʻia o ka hydrogen-ho okumu i naoh i loko o ka wa e kaawale aku o H + (-0.83 volts i loko o kona'ākilikai meakino) okoa ka ia Loaʻaʻia ma kiʻekiʻe lehulehu (0 V ma kaʻakika meakino) mai, no hoi ma 0,83 volts [4. 66-67]. Ie akaka i 0,83 volts ua koi 'ia ma ka mea i loaa i ka kiʻekiʻe lehulehu o ka wai i loko o ka lakou mau Ion. Kēia 'o ia hoʻi i 0,83 volts ua koi' ia no ka nui o'ākilikai dissociation o ka wai nā lātoma i loko o H +, a OH- Ion. Penei, ina o kaʻili lahilahi ua kākoʻo i loko o mākou hehee ai cathode makahikiʻakika meakino, a ma ka'ākilikai anodic, ke anakahi uila hiki a hiki i kona Del 0,83 volts, i mea i maikai like me ka meaʻimi naʻauao omaulia hōʻike mamua. Kēia anakahi uila hoʻolako He kiʻekiʻe conductivity pokole Desʻili lahilahi ma ka wai dissociation i loko o Ion loko ia.

Lāʻau. 2. kiʻikuhi redox naoh Loaʻaʻia

decomposition o ka wai, a me ka H + Ion a me OH- i hydrogen a me ka oxygen.

Ina a me Peltier wela (i paiiaʻi na №2)

"O ke kumu o ka Peltier hookoia mea i kaʻawelike ikehu o ka uku ole nā moku halihali mokulele (no ka definiteness electrons) komo i loko o ka uila conductivity i loko o kekahi mau conductors o okoa ... I ka hoʻololi mai kekahi alakaʻi mele i loko o kekahi huina'ine a ke hoʻouna i oi aku ka mana maka aha a hu nui ae la ka nele o ka ikaika i kona uku (ke kaumaha ma muliʻikena ao ao).

Lāʻau. 3. Na Peltier kanawai ma ka papa metala, a me ka mea uholo uila n-: ԐF - Fermi ilikai; ԐC - i ka lalo o ka conduction bana o ka mea uholo uila; ԐV - valence ciia; I - maikaʻi ma amau o ka papa; koʻikoʻi a hanohano me nā pua hoikeia schematically electrons.

Ma ka mea mua Ina kokoke ka leka pepa ua hookuu, a me ka lua - ka ai-i kapaia o ke kemu .. Peltier wela. No ka laʻana, ma ka papa mea uholo uila - metala (ke Kii 3) i ka ikaika o na electrons e hele mai i ka N-ʻano mea uholo uila i ka mea hiki ke hooheheeia (haʻalele nano) mea me ka nui loa ma luna ma mua o ka Fermi ka ikehu ԐF. No laila, ka mea, e 'aʻe i ka thermal equilibrium i loko o ka mea hiki ke hooheheeia. Equilibrium ua hoihoi hou ia i ka hopena o ka hookui hookahe koko ana, ma i thermalized electrons, e haawi ana ka liki ole ikehu mea pōaka. maka aha. Ka mea uholo uila metala (pono nano) hiki ke hele wale i ka loa mikiʻala electrons, no laila, ua huina'ine kinoea i loko o ka metala anuanu. Ma hoihoi hou ia ana mai o ka equilibrium hoi o ka makana o ka oscillation ikehu ka lukuʻia puka olu oia "[2, p. 552].

E kelepona i ka mea hiki ke hooheheeia / P-mea uholo uila kulana mea ano like. no ka mea, pa-conductivity mea uholo uila lua i kona valence koa i ka mea ma lalo o ka 'ilikai Fermi, alaila, no ka hui' e e ho'ēmi, ma i electrons kahe mai ka P-mea uholo uila i ka mea hiki ke hooheheeia. Peltier wela oku u paha ke kemu ma ka hui 'ana o nā conductors, aie a hiki i ka? Iecaianoaaiiie o ka hopena maikaʻi' ole maikaʻi o ka mea maloko ina.

Hookomoia ma ka hema hui 'nahā i (lāʻau. 3), ma a ka Peltier wela e auaaeaiea, he electrolytic halepaahao, no kekahi laʻana, koʻana koko NaOH pāʻoihana (ke Kii 4) a me ka mea hiki ke hooheheeia mea uholo uila a me N-e ia e chemically inert.

Lāʻau. 4. ka hema hui 'N-mea uholo uila, a me ka mea hiki ke hooheheeia mea hamama, a hoonoho iho la ma ka nahā o ka electrolyte pāʻoihana. Designations i ka mea like me ia ma lāʻau. 3.

No ka mea, i ka waʻikena lua i pele «au», ka mea uholo uila o ka n-electrons ma ka ikehu kiekie ae hiki pāʻoihana ma mua o hele mai mai o pāʻoihana ma ka mea hiki ke hooheheeia, e kū i kēia oi ikehu (wela o Peltier) i loko o ka halepaahao.

I ka pono ma ka halepaahao i e wale i ka hihia o ka liu i loko electrochemical reactions. Inā ka exothermic naoh i loko o ka halepaahao, me ka Peltier wela ua hoʻokuʻuʻia i loko o ka halepaahao, e like me hou, he wahi e hele ai. Inā ka naoh i loko o ka halepaahao - endothermic, ka Peltier wela ka loa a me ka hapa, e compensate no ka mea endothermic hookoia, 'o ia hoʻi, e hana i kekahi naoh huahana. Ma keia hana, i ka huina o na halepaahao naoh: 2H2O → 2H2 ↑ + O2 ↑ - endothermic, no laila, i ka wela (ikehu) o ka Peltier mea e ho okumu ana i nā lātoma a me h2 O2, e hanaʻia ma luna o nā nā uila aʻa lolo. Pela, ua loaa i ua ole, kuu hoʻi i loko o ka papa o ka wela o ka Peltier koho ma ka meakino i loko o ka akau N-E leka pepa mea uholo uila / mea hiki ke hooheheeia, a ua waiho ia ma ka palapala o Nine Inch ikaika o ka hydrogen a me ka oxygen nā lātoma. ʻae nō hoʻi, ka hana o ka mea mawaho anakahi uila kumu ua hoopauia no ka electrolysis o ka wai, i loko o keia hihia, e e ka li ili ma mua i loko o ka hihia o'ālike nā uila aʻa lolo, ka hoʻomake 'ole hanana o ka Peltier kanawai ..

Ka nānā 'ana i ka waiwai o na nā uila aʻa lolo, ka electrolytic halepaahao iho hiki ka hoʻokemu ole paha wela ka wā maalo ae la oia ma ka Peltierʻikena ana. Ke quasi-kūpaʻa rula, me ka Loaʻaʻia loli o ka Gibbs keena [4, p. 60]:

Δ G = Δ H - T Δ S, kahi

Δ H - enthalpy loli o ka halepaahao;

T - thermodynamic wela;

Δ S - loli i loko o ka entropy o ka halepaahao;

Q = - T Δ S - wela o ka Peltier halepaahao.

No ka hydrogen-oxygen ma electrochemical aeea ma T = 298 (K), i ka loli ma enthalpy ΔHpr = - 284.5 (kJ / Mol) [8, p. 120], o ka loli ma Gibbs Loaʻaʻia [4. i kekahi. 60]

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

Z - helu o electrons no lātoma;

F - Faraday a eia i;

E - emf aeea.

nolaila

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

'o ia hoʻi hydrogen-oxygen ma electrochemical aeea paha ke wela i loko o ka Peltier kaiapuni, oiai ka hoʻomaikaʻi kona entropy a hakumakuma kona. A laila, ma ka inverse kaʻina hana, ka electrolysis o ka wai, i mea no ka hihia i loko o mākou laʻana, Peltier wela Q mod = - Q Ave = - 47.3 (kJ / Mol) o ka electrolyte e e ke kemu, mai ke kaiapuni.

Kû ke P - Peltier wela ia mai ka 'ia i loko o ka akau N-E leka pepa mea uholo uila / mea hiki ke hooheheeia. pono ku i ka wela P> 0 loko o ka halepaahao, akā, no ka mea, decomposition o ka wai i loko o ka halepaahao endothermic naoh (Δ H> 0), ka Peltier wela P mea e compensate no ka thermal hopena o ka naoh:

Δ G arr = (Δ H arr - N) + Q mod                                                                        (1)

Mod Q hilinaʻi nui wale ma luna o ka haku mele 'ana o ka electrolyte, mai He He ano no ka electrolytic halepaahao me ka inert nā uila aʻa lolo a me ka hilinaʻi nui wale ma luna o ka P'ūholo uila pono hana.

Helu kaulike (1) hōʻike i ka wela o ka Peltier P a me Peltier hoʻa'ā i mod Q, nō ka? Iecaianoaaiiie o maikaʻi kēia hana. Ie Peltier wela laweʻia aku ai mai ka meakino ho'ēmi i kā ka lilo ana o ka mawaho mana kumu koi 'ia no ka electrolysis. A kahua kahi o ka wela meakino mea he kumu o ka ikaika no ka? Iecaianoaaiiie o ka pono keia mau mea hana, mea ano o ka maholahune, e like me ka nui electrochemical keena, examples o na oihana mua i hōʻike 'ia i loko o [3, p. 248 - 249].

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