Bara uru Work okpomọkụ nke Environment

Part 1. Ụfọdụ okwu na nkọwa.

The electromotive ike (emf) bụ integral mpụga ike ubi òkè gụnyere a ugbu a isi iyi ... mpụga ike eme ihe electroplating mkpụrụ ndụ na ókè n'etiti electrolyte na electrodes. Ha na-arụ ọrụ na ókè-ala n'etiti abụọ dissimilar ọla na chọpụta kọntaktị nwere ihe dị iche therebetween [5, p. 193, 191]. Ọnụ ego jumps potentials na niile na-ebupụta nke circuit ngalaba bụ hà nwere ihe dị iche n'etiti-eduzi, emi odude ke yinye nsọtụ, na a na-akpọ electromotive ike emf eduzi circuit ... yinye esịnede naanị nke na-eduzi nke mbụ ụdị bụ hà nwere na-awụlikwa elu n'etiti ndị mbụ na ndị ikpeazụ eduzi kpọmkwem kpọtụrụ ha (Volta iwu) ... Ọ bụrụ na sekit bụ n'ụzọ kwesịrị ekwesị, ndị emf a circuit bụ efu. Iji gbazie na-emeghe-circuit eduzi, nke na-agụnye ọ dịkarịa ala otu electrolyte, ọdabara iwu volts ... O doro anya na naanị eduzi circuit gụnyere ọ dịkarịa ala otu eduzi nke abụọ ụdị bụ electrochemical sel (ma ọ bụ ụdọ ígwè electrochemical ọcha) [1, p. 490 - 491].

Polyelectrolytes bụ Polymers ike dissociating n'ime ion na ngwọta, si otú ahụ n'otu macromolecule, a ọnụ ọgụgụ buru ibu nke ugboro ugboro ebubo ... crosslinked polyelectrolytes (ion exchangers, ion-exchange resin) anaghị igbari, naanị zaa, mgbe retaining ike dissociate [6, p. 320 - 321]. Polyelectrolytes dissociate n'ime ezighị ebubo macroion na H + ion na-akpọ polyacids na dissociates n'ime ghaghị ebubo ion na OH- macroion akpọ poliosnovaniyami.

Donnan ịha nwere bụ ndị nwere ihe dị iche na pụtara na-adọ ókè n'etiti abụọ electrolytes ma ọ bụrụ na a ịgba bụghị permeable niile ion. Impermeability ókè ụfọdụ ion nwere ike mere ka ihe atụ, ọnụnọ nke membranes na dị nnọọ warara pores nke bụ agaghi aga maka ahụ n'elu a na-size. Nhọrọ permeability nke interface pụtara na ọ bụrụ na ọ bụla ion otú ike jikọrọ otu n'ime n'ụzọ na-ahapụ ya n'ozuzu ike. Kpọmkwem na-akpa àgwà ionic ion mgbanwe resins, ma ọ bụ ion-exchange otu ofu homopolar nkekọ na molekụla lattice ma ọ bụ matriks. The ngwọta, ịbụ n'ime ndị dị otú ahụ matrices forms ọnụ na ya otu na-adọ; ngwọta, emi odude n'èzí, - nke abụọ [7. 77].

The electric abụọ oyi akwa (EDL) na-na-ewere ọnọdụ na interface nke abụọ n'ụzọ ka nke oppositely ebubo n'ígwé ewekarị na ụfọdụ anya onye ọ bụla ọzọ [7. 96].

Peltier mmadụ a iche ma ọ bụ absorption nke okpomọkụ na kọntaktị nke abụọ dị iche iche na-eduzi dabere n'elu ntụziaka nke eletrik eru site na kọntaktị [2, p. 552].

Part 2: Iji okpomọkụ na-ajụ na electrolysis mmiri.

Tụlee usoro nke omume nke circuit nke electrochemical cell (dịrị gaba n'ime ebe mmewere), gosiri schematically na Fig. 1, ọzọ emf ruru ka esịtidem kọntaktị nwere ihe dị iche (PKK) na mmetụta nke Donnan (nkenke nkọwa nke kachasi mkpa nke Donnan mmetụta, esịtidem PKK na metụtara Peltier okpomọkụ na-nyere na nke atọ akụkụ nke isiokwu).

Fig. 1. schematic nnọchiteanya nke ihe electrochemical cell: 1 - na cathode na-kpọtụụrụ na a ngwọta nke 3, electrochemical Mbelata mmeghachi omume nke electrolyte cations erukwa na ya elu, mere nke a na ya inert kpamkpam doped n-okporo ọkụ. Part nke cathode ejikọta ya na mpụga voltaji iyi, metallized; 2 - na anode na-kpọtụụrụ na a ngwọta nke 4, n'elu ya ime electrochemical ọxịdashọn mmeghachi omume nke electrolyte anions, mere nke na ya inert kpamkpam doped p-okporo ọkụ. Part nke anode ejikọta ya na mpụga voltaji iyi, metallized; 3 - cathode ohere, polyelectrolyte solution, dissociating na mmiri na macroion R- ezighị ebubo na ghaghị ebubo counterions obere K + (na ugbu ihe atụ bụ hydrogen ion H +); 4 - anode ogige polyelectrolyte ngwọta na mmiri dissociating n'ime ghaghị ebubo macroion R + na-ezighị ezi na ebubo counterions obere A- (a ka ihe atụ ya hydroxide ion OH-); 5 - akpụkpọ (diaphragm), bụ impermeable ka macromolecules (macroion) polyelectrolytes, ma kpamkpam permeable ka obere counterions K +, A- na mmiri na ụmụ irighiri ihe na-akọrọ ohere 3 na 4; Evnesh - mpụga voltaji isi iyi.

Emf site Donnan mmetụta

N'ihi na ihe doo anya, ndị electrolyte nke cathode ohere (. 3, Ọgụgụ 1) họrọ okenye polyacid ngwọta (R-H +), na electrolyte na anode ogige (4, fig 1.) - okenye poliosnovaniya (R + OH-). Dị ka a n'ihi nke dissociation polyacids na cathode ogige, nso elu nke cathode (1, Fig. 1), na e nwere onye na ụba ịta nke H + ion. Positive ụgwọ pụtara na gburugburu nke cathode n'elu na-adịghị ụgwọ atụrụ ezighị ebubo macroions R-, ebe ha nwere ike ghara-abịa nso n'elu nke cathode ruru ya size na ọnụnọ nke a ghaghị ebubo ionic ikuku (maka nkọwa ahụ. Description Donnan mmetụta na Mgbakwunye №1 nke atọ akụkụ nke isiokwu). N'ihi ya, ókè oyi akwa nke a ngwọta na-na kọntaktị na cathode n'elu nwere a mma ego. N'ihi ya, ihe electrostatic itinye n'ọkwa na cathode elu, contiguous na ngwọta, e nwere a na-adịghị mma-elekọta conduction electrons. ntụgharị na interface n'etiti cathode elu ma des ngwọta emee. Ubi nke des agabiga electrons si cathode - na ngwọta.

N'otu aka ahụ, na anode (2, Fig. 1), ókè oyi akwa nke ihe ngwọta na anode ogige (4, Fig. 1) na na kọntaktị na anode n'elu nwere a na-adịghị mma ụgwọ, na na anode elu, contiguous na ngwọta, e nwere a mma ego. ntụgharị na interface n'etiti anode elu na ngwọta Oputakwara des. Ubi nke des agabiga electrons si ngwọta - a anode.

N'ihi ya, na ubi nke des na ihu nke cathode na anode na ngwọta, na-akwado thermal ngwọta ion mgbasa, abụọ esịtidem emf iyi, na-eme ya na mpụga iyi, i.e., ịkwa ọjọọ ebubo na akaghị counterclockwise.

Dissociation poliosnovaniya polyacids na-emekwa thermal mgbasa site akpụkpọ ahụ (5, Ọgụgụ 1). H + ion si cathodic ohere - na anode, na OH- ion si anode ogige - a cathode. Macroion R + na R- polyelectrolytes-enweghị ike ime site na akpụkpọ ahụ, n'ihi ya, ọ si cathode ohere e bụ ngafe ọjọọ ụgwọ, na si anodic ohere - ihe ngafe mma ụgwọ, i.e., ọ dị ihe ọzọ DPP ruru ka Donnan mmetụta. N'ihi ya, akpụkpọ ahụ Oputakwara n'ime emf, na-eme ya na mpụga isi iyi nke okpomọkụ mgbasa na nọgidere na-enwe ihe ngwọta nke ion.

Anyị ihe atụ, voltaji gafee akpụkpọ ahụ nwere ike iru 0,83 volts, dị ka a kwekọrọ na a mgbanwe nwere nke ọkọlọtọ hydrogen electrode si - 0,83 ka 0 volts na mgbanwe site na alkaline ajụ na anode ogige ndị cathode ogige acidic gburugburu ebe obibi. Maka nkọwa, lee. Na Mgbakwunye №1 nke atọ akụkụ nke isiokwu.

Emf PKK si n'ime

The mmewere emf Ọ na-adị, gụnyere ke kọntaktị okporo ọkụ anode na cathode ha metal akụkụ-eje ozi jikọọ mpụga voltaji isi iyi. Nke a emf n'ihi esịtidem PKK. Esịtidem Ọ BỤRỤ na-adịghị ike, na iche mpụga ubi na ohere gburugburu na kọntaktị na-eduzi, i.e. Ọ na-adịghị emetụta ngagharị nke ebubo ahụ n'èzí na-eduzi. Construction n-okporo ọkụ / metal / p-okporo ọkụ na-zuru ezu mara na a na-eji ihe atụ, a thermoelectric Peltier modul. The ịdị ukwuu nke emf ndị dị otú ahụ a Ọdịdị na ụlọ okpomọkụ nwere ike iru ụkpụrụ nke iji nke 0.4 - 0,6 volt [5, p. 459; 2, p. 552]. Fields na kọntaktị na-eduzi ndị dị otú ahụ n'ụzọ ha na-asọ electrons counterclockwise na akaghị, i.e. eme ya na mpụga isi iyi. The electrons bulie ike larịị nke na-ajụ-adọrọ okpomọkụ nke Peltier.

Esịtidem Ọ BỤRỤ na ịda n'ihi na mgbasa nke electrons na kọntaktị ebe nke electrodes na ngwọta, na Kama nke ahụ, agabiga electrons na malite direction na akaghị. ntụgharị ukporo nke electrons na mmewere counterclockwise na ndị a na kọntaktị ga-ekenyela Peltier okpomọkụ. ma n'ihi nyefe nke electrons si cathode n'ime ihe ngwọta na nke ihe ngwọta na anode na-bụchaghị esonyere ihe endothermic mmeghachi omume na-amụba hydrogen na oxygen, okpomọkụ nke Peltier na-adịghị tọhapụrụ n'ime ọkara, na bụ iji belata endothermic mmetụta, i.e. dị ka "ichekwa" na enthalpy nke guzobere hydrogen na oxygen. Maka nkọwa, lee. Na Mgbakwunye №2 nke atọ akụkụ nke isiokwu.

ebu (electrons na ion) ịkpali na mmewere circuit bụghị mechiri emechi ụzọ, nweghị ebubo na mmewere na-adịghị akpụ akpụ na a mechiri emechi circuit. Onye ọ bụla elektrọn anode enwetara site na ngwọta (na N'ezie nke ọxịdashọn nke OH- ion ka oxygen ụmụ irighiri), gabiga mpụga circuit na cathode, na-volatilized ọnụ na hydrogen ụmụ irighiri (na usoro nke na mgbake nke ion H +). N'otu aka ahụ ion OH- na H + adịghị akpali na a mechiri emechi circuit, ma naanị na kwekọrọ ekwekọ electrode, wee ikusi n'ụdị molekụla hydrogen na oxygen. ntụgharị na ion na electrons ọ bụla na-akpụ akpụ na ya gburugburu ebe obibi na ngwa ngwa ubi nke des, na ọgwụgwụ nke ụzọ, mgbe ha ruru elu nke electrode na-jikọtara na molekul, n'ịtụgharị dum echekwara ike - ume nke a chemical nkekọ, na nke loop!

All nke esịtidem isi mmalite nke emf Mmewere, belata efu mpụga isi iyi nke mmiri electrolysis. N'ihi ya, oké okpomọkụ nke ihere na-adọrọ ọcha n'oge ya ọrụ ịnọgide na-enwe mgbasa nke des, bụ iji belata na-eri nke mpụga iyi, i.e., Ọ enwekwu electrolysis arụmọrụ.

Electrolysis nke mmiri na-enweghị ọ bụla mpụga isi iyi.

Na akafiakde na Filiks aa na mmewere e gosiri na Fig. 1, mpụga iyi parameters na-adịghị sonye na akaụntụ. E were ya na esịtidem eguzogide bụ hà Rd na a voltaji nke 0. Nke Evnesh Mmewere electrodes na-shorted ka a n'ezinụlọ ibu (lee Fig. 5). Na nke a, ndị nduzi na ịdị ukwuu nke des ubi ịda na interface na ndị ọcha-anọgide na otu.

Fig. 5. Kama Evnesh (Fig. 1) gụnyere n'ezinụlọ ibu RL.

Kpebisie ike na ọnọdụ nke n'amaghi ugbu a eruba na a mmewere. Na-agbanwe agbanwe Gibbs nwere, dị ka usoro (1) nke Mgbakwunye №1 nke atọ akụkụ nke isiokwu:

Δ G arr = (Δ H arr - n) + Q mod

Ọ bụrụ na P> Δ H + Q mod mod = 284,5 - 47.2 = 237.3 (King James Version / mol) = 1.23 (eV / molekul)

na Δ G arr <0 na n'amaghi usoro-ekwe omume.

Anyị ga-atụle n'ihu na ọcha hydrogen ọgbọ mmeghachi omume na-adị na ihe acidic ajụ (electrode nwere nke 0 volts), na oxygen na-alkaline (electrode nwere nke 0.4 volts). Dị otú ahụ electrode potentials na-enye a akpụkpọ ahụ (5, Fig. 5), na voltaji na nke a kwesịrị 0,83 volts. ntụgharị ike a chọrọ maka guzobe hydrogen na oxygen na-belata 0.83 (eV / molekul). Mgbe ahụ bụ ọnọdụ ndị nwere ike nke n'amaghi usoro ga:

P> 1,23 - 0.83 = 0.4 (eV / molekul) = 77.2 (King James Version / mol) (2)

Anyị na-ahụ na ike mgbochi nke hydrogen na oxygen ụmụ irighiri kemgbochi na-enweghị iji mpụga voltaji isi iyi. ntụgharị ọbụna na n = 0.4 (eV / molekul), i.e. mgbe n'ime electrode HPDC 0.4 volts, mmewere ga-a obodo nke ike ịha, na ihe ọ bụla (ọbụna obere) mgbanwe nke itule ọnọdụ ga-eme ka nke ugbu a na circuit.

Ọzọ na-egbochi ndị Jeremaya mere na electrodes bụ ebighị ike, ma ọ na-tutu amama site ọwara mmetụta, ịda ruru ka smallness nke ọdịiche n'etiti electrodes na ngwọta [7, p. 147-149].

N'ihi ya, na-adabere na nke ike, anyị na-ekwubi na n'amaghi ugbu a na mmewere e gosiri na Fig. 5, ọ bụ omume. Ma ihe ahụ ihe nwere ike ime ka nke a ugbu a? Ihe ndị a na-depụtara n'okpuru:

1. The puru nke mgbanwe nke electrons si cathode n'ime ihe ngwọta elu karịa puru mgbanwe si anode n'ime ihe ngwọta, ebe n-okporo ọkụ cathode nwere otutu free electrons na a elu ume larịị, na p-okporo ọkụ anode - na "n'olulu", na ndị a "n'olulu" bụ na onye ike larịị n'okpuru cathode electrons;

2. The akpụkpọ ahụ a na-akwado na cathode ohere nke ihe acidic na gburugburu ebe obibi, na anode - alkaline. N'ihe banyere inert electrodes, a na-eduga ná eziokwu na a cathode electrode nwere na-aghọ ibu karịa anode. N'ihi ya, electrons ga-akpali site na mpụga circuit si anode na cathode;

3. The n'elu-ndebe nke polyelectrolyte ngwọta ịda ruru ka Donnan mmetụta, na-emepụta na electrode / ngwọta ubi ndị dị otú ahụ na n'ọhia na cathode akwalite elektrọn mkpụrụ si cathode n'ime ihe ngwọta, na n'ọhia na anode - elektrọn abanye anode si ngwọta;

4. itule na-atụ ma laa azu Jeremaya mere na electrodes (exchange okwukwo) abụchaghị eziokwu n'ebe H + ion kpọmkwem Mbelata Jeremaya mere na cathode na ọxịdashọn nke OH- ion na anode, ebe ha na-ebu guzobere gas (H2 na O2) ike nke na-adị mfe na-ahapụ mmeghachi omume mpaghara (Le Chatelier si ụkpụrụ).

Nwere.

N'ihi na quantitative nwale nke voltaji gafee ibu site Donnan mmetụta, nnwale e rụrụ nke cathode mmewere ẹkewetde nke ọrụ carbon na elu graphite electrode na ihe anode - a ngwakọta nke na-arụ ọrụ carbon na anion resin AB-17-8 na elu graphite electrode. Electrolyte - okenye NaOH solution, anode na cathode oghere na-iche site a sịntetik chere. On oghe mpụga electrodes a mmewere nwere a voltaji nke banyere 50 MV. Mgbe ejikọrọ ihe mmewere nke mpụga ibu 10 ohm ofu ugbu a nke banyere 500 microamps. Mgbe ihere okpomọkụ na-abawanye site 20 ruo 30 0C voltaji na mpụga electrode mụbara 54 MV. Amụba voltaji na ihere okpomọkụ na-egosi na isi iyi nke emf bụ mgbasa, i.e. thermal ngagharị nke ahụ.

N'ihi na quantitative nwale nke voltaji gafee ibu site n'ime HPDC metal / okporo ọkụ nnwale E duziri nke cell cathode mejupụtara sịntetik graphite powder na elu graphite electrode na ihe anode - a ntụ ntụ nke boron carbide (B4C, p-okporo ọkụ) na elu graphite electrode. Electrolyte - okenye NaOH solution, anode na cathode oghere na-iche site a sịntetik chere. On oghe mpụga electrodes nke mmewere voltaji bụ banyere 150 MV. Mgbe ejikọta mpụga ibu mmewere 50 kOhm voltaji ama esịn 35 MV., Dị otú ahụ a siri ike voltaji dobe n'ihi na ala intrinsic boron carbide na, dị ka a N'ihi ya, a elu esịtidem eguzogide mmewere. Nchọpụta voltaji vesos okpomọkụ ihe mmewere nke ndị dị otú Ọdịdị na-adịghị rụrụ. Nke a bụ n'ihi na eziokwu na, n'ihi na a okporo ọkụ, dabere na ya chemical mejupụtara, ogo doping na ndị ọzọ na Njirimara, okpomọkụ mgbanwe ụzọ dị iche iche nwere ike ime ya Fermi larịị. ntụgharị okpomọkụ mmetụta emf Mmewere (abawanye ma ọ bụ ọnụ), na nke a na-adabere na ihe eji, otú a bụ bụghị indicative nnwale.

Na n'ọnọdụ a ọ nọgidere ọzọ nnwale nke cell cathode ka nke a ngwakọta nke na-arụ ọrụ carbon ntụ ntụ na Ku-2-8 na elu igwe anaghị agba nchara electrode na anode si a ngwakọta nke na-arụ ọrụ carbon ntụ ntụ na anion resin AB-17-8 na mpụga electrode si igwe anaghị agba nchara. Electrolyte - okenye ihe ngwọta nke NaCl, na anode na cathode oghere na-iche site a sịntetik chere. Mpụga electrodes a mmewere na October 2011 na-enwe ike Egbubikwala n'ezinụlọ ammeter. Ugbu nke na-egosi ihe ammeter, banyere a ụbọchị mgbe n'aka, mgbada n'usoro site na 1 MA - ruo 100 mkA (nke bụ o doro anya na n'ihi na polarization nke electrodes), ọ bụkwa mgbe ahụ ihe karịrị otu afọ na-adịghị agbanwe agbanwe.

Na bara nwere kọwara n'elu na njikọ na ndị ọzọ dị irè ihe inaccessibility nwetara ihe n'ụzọ ala karịa madu puru. Ke adianade do, mara na akụkụ nke ngụkọta esịtidem emf Mmewere mgbe iwesa maka ịnọgide na electrode mmeghachi omume (mmepụta nke hydrogen na oxygen) na-apụghị tụrụ na mpụga circuit.

Mmechi.

N'ịchịkọta, anyị nwere ike ikwubi na ọdịdị-enye anyị ohere tọghata thermal ume bara uru ike ma ọ bụ na-arụ ọrụ, na-eji dị ka a "okpomọkụ" gburugburu ebe obibi na-enweghị a "friji". N'ihi ya Donnan mmetụta na esịtidem Ọ BỤRỤ na tọghatara thermal ike nke ebubo ahụ na electric ubi ume del ka endothermic mmeghachi omume okpomọkụ na converted n'ime chemical ike.

Weere kọntaktị mmewere erepịakwa okpomọkụ si ọkara na mmiri, na allocates electric ike, hydrogen na oxygen! Ọzọkwa, na usoro nke oriri ike na ojiji nke hydrogen ka a mmanụ ụgbọala, na mmiri na-alaghachi azụ okpomọkụ na-ajụ!

Part 3 nke Mgbakwunye.

Nke a na akụkụ bụ n'ihu tụlere Donnan ịha mmetụta, na nkwụsị nke dị n'ime HPDC metal / okporo ọkụ na Peltier okpomọkụ redox Jeremaya mere na electrode potentials na mmewere.

Donnan nwere (Odide Ntụkwasị №1)

Tụlee usoro nke omume nke Donnan ike polyelectrolyte. Mgbe dissociation polyelectrolyte counterions amalite obere, site mgbasa, na-ahapụ olu nwere site na macromolecule. Directional mgbasa nke counterions nke obere olu polyelectrolyte macromolecules na mgbaze bụ n'ihi na ụba ịta na nnukwu nke macromolecule dị ka e jiri ya tụnyere ndị ọzọ nke ihe ngwọta. Ọzọkwa, ọ bụrụ na ihe atụ, obere counterions na-ezighị-ebubo, nke a na-na n'ime akụkụ nke macromolecule na-ghaghị ebubo, na ngwọta bụ ozugbo n'akụkụ ka olu nke macromolecule - adịghị mma. ntụgharị gburugburu a ghaghị ebubo macroion olu, e bụ ụdị "ion ikuku" nke obere counter-ion - ezighị ebubo. Nchupu ionic ikuku ụgwọ uto pụtara mgbe electrostatic ubi n'etiti ion olu macroion ikuku na-ọtùtù kwes mgbasa nke obere counterions. Ihe ịha nwere ihe dị iche n'etiti ikuku na ionic macroions bụ Donnan nwere. Donnan nwere na-ezo dị ka akpụkpọ ahụ nwere, n'ihi na a ọnọdụ yiri nke ahụ emee on a semipermeable akpụkpọ ahụ, n'ihi na ihe atụ, mgbe ọ na-ekewapụ electrolyte ngwọta nke nwere ion nke abụọ - ike na-adịghị ike nke na-agafe therethrough nke dị ọcha mgbaze.

Donnan nwere ike ga-atụle ka a na ịmachi ikpe nke mgbasa nwere, mgbe agagharị nke otu n'ime ion (na nke a macroion) bụ efu. Mgbe ahụ, dị ka [1, p. 535], na-ewere ụgwọ nke counter hà otu:

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

Ed - Donnan nwere;

R - eluigwe na ala gas mgbe nile;

T - thermodynamic okpomọkụ;

F - Faraday mgbe nile;

A1, A2 - counter-ọrụ na kọntaktị n'ụzọ.

Na nke a otu, nke akpụkpọ ekewapụ poliosnovaniya ngwọta (onye Onyenwe anyị + = LG a 1 = 14) na polyacid (onye Onyenwe anyị + = LG a 2 = 0), Donnan nwere gafee akpụkpọ ahụ na ụlọ okpomọkụ (T = 300 0 K) ga-abụ:

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

Donnan nwere abawanye kpọmkwem hà okpomọkụ. Maka mgbasa nke electrochemical cell Peltier okpomọkụ bụ naanị iyi n'ihi na mmepụta nke bara uru na-arụ ọrụ, ọ bụghị ihe ijuanya na ndị dị otú ọcha emf enwekwu na-amụba okpomọkụ. Na mgbasa cell maka mmepụta nke-arụ ọrụ, Peltier okpomọkụ na-mgbe na-e si na gburugburu ebe obibi. Mgbe ugbu a aga site EDL kpụrụ Donnan mmetụta, na a direction coinciding na nti direction nke ubi nke des (i.e., mgbe ubi nke des anamde nti ọrụ), okpomọkụ na-etinye obi gị dum site na gburugburu ebe obibi n'ihi na mmepụta nke a akwụkwọ.

Ma mgbasa mmewere bụ a na-aga n'ihu na unidirectional mgbanwe ion ịta, nke n'ikpeazụ na-eduga ná equalization nke ịta na ịkwụsị eduzi mgbasa, n'adịghị ịha Donnan, nke, na a bụrụ na nke leaks quasistatic okwukwo ion ịta, ozugbo ọ ruru ụfọdụ uru, na-anọgide na-agbanweghi agbanwe .

Fig. 2 na-egosi na a esereese nke redox potentials nke Jeremaya mere, nke hydrogen na oxygen mgbe na-agbanwe agbanwe acidity nke ngwọta. The chaatị na-egosi na electrode nwere nke oxygen guzobere mmeghachi omume na-anọghị nke OH- ion (1.23 volts na acidic gburugburu) bụ dị iche iche si na otu nwere na elu ịta (0.4 volts na alkaline ajụ) at 0,83 volts. N'otu aka ahụ, electrode nwere nke hydrogen na-akpụ mmeghachi omume na-anọghị nke H + (-0.83 volts na alkaline ajụ) bụ dị iche iche si na otu nwere na elu ịta (0 V na acid-ajụ), nakwa na 0,83 volts [4. 66-67]. ntụgharị doro anya na 0,83 volts a chọrọ iji nweta a akwa ịta mmiri na nwoke ion. Nke a pụtara na 0,83 volts a chọrọ maka a uka nke na-anọpụ iche dissociation nke mmiri ụmụ irighiri n'ime H + na OH- ion. N'ihi ya, ọ bụrụ na akpụkpọ ahụ a na-akwado na anyị mmewere cathode ohere acidic ọkara na na alkaline anodic, na voltaji nwere ike iru ya del 0,83 volts, nke bụ na ezi nkwekọrịta na usoro iwu mgbawa ọkọnọ mbụ. Nke a voltaji enye a elu conductivity ohere des akpụkpọ ahụ site mmiri dissociation n'ime ion n'ime ya.

Fig. 2. Osise redox mmeghachi omume potentials

decomposition nke mmiri, na H + ion na OH- n'ime hydrogen na oxygen.

Ọ BỤRỤ na Peltier okpomọkụ (Odide Ntụkwasị №2)

"The kpatara nke Peltier mmetụta dị na nkezi ike nke ihe-ndebe-ebu (maka definiteness electrons) abuana ke electric conductivity dị iche iche na-eduzi nke dị iche iche ... Na mgbanwe site onye na-eduzi ya n'ime ọzọ elektrọn ma ọ bụ na-ebunye ngafe ike okporo ma ọ bụ ịgbakwunye a enweghị ike na ya ga-efu (dabere na ugbu a direction).

Fig. 3. The Peltier utịp ke kọntaktị metal na okporo ọkụ n-: ԐF - Fermi larịị; ԐC - ala nke conduction gbalaga nke okporo ọkụ; ԐV - valence gbalaga; M - mma direction nke ugbu a; okirikiri na akụ gosiri schematically electrons.

Ke akpa idaha nso na kọntaktị na-tọhapụrụ, na nke abụọ - na-akpọ etinye obi gị dum .. Peltier okpomọkụ. Ka ihe atụ, na kọntaktị okporo ọkụ - metal (Ọgụgụ 3) ume nke electrons na-agafe si n-ụdị okporo ọkụ ka metal (ekpe aka) bụ budata elu karịa Fermi ume ԐF. Ya mere, ha na-emebi thermal ịha na metal. Ịha e weghachiri dị ka a n'ihi nke collisions, nke thermalized electrons, na-enye ngafe ume crystalline. okporo. The okporo ọkụ metal (nri aka) nwere ike gafee naanị ndị kasị energetic electrons, ka elektrọn gas na metal cools. On mweghachi nke ịha nkesa nke oscillation ọkụ eletrik lattice "[2, p. 552].

Iji kpọtụrụ metal / p-okporo ọkụ ọnọdụ yiri nke ahụ. n'ihi na p-conductivity okporo ọkụ oghere enye ya valence gbalaga nke bụ n'okpuru Fermi larịị, mgbe ahụ, na kọntaktị ga-mma, na nke electrons igba si p-okporo ọkụ na metal. Peltier okpomọkụ tọhapụrụ ma ọ bụ etinye obi gị dum site na kọntaktị nke abụọ na-eduzi, n'ihi na mmepụta nke na-adịghị mma ma ọ bụ mma nke esịtidem Ọ BỤRỤ.

Esịne ke ekpe kọntaktị ọdịiche (Fig. 3), nke Peltier okpomọkụ oke, ihe electrolytic cell, n'ihi na ihe atụ, okenye NaOH ngwọta (Ọgụgụ 4) na metal okporo ọkụ na n-ka ọ bụrụ na ya inert.

Fig. 4. The ekpe kọntaktị n-okporo ọkụ na metal bụ na-emeghe ma dọba ke ọdịiche nke electrolyte ngwọta. Designations bụ otu dị Fig. 3.

N'ihi na, mgbe ugbu a aga «m», na okporo ọkụ nke n-electrons na elu ike na-abata ngwọta karịa apụta nke ngwọta na metal, a ngafe ume (okpomọkụ nke Peltier) ga na-eguzo cell.

The ugbu a site na cell nwere ike ịbụ naanị a bụrụ na nke leaks nime ya electrochemical Jeremaya mere. Ọ bụrụ na ndị exothermic mmeghachi omume na cell, nke Peltier okpomọkụ a tọhapụrụ na cell, dị ka ihe ọ enweghị ebe ọ ga-aga. Ọ bụrụ na mmeghachi omume na cell - endothermic, na Peltier okpomọkụ ya kpam kpam ma ọ bụ obere iji chefuo endothermic mmetụta, ie, na-etolite a mmeghachi omume ngwaahịa. Na nke a atụ, ngụkọta cell mmeghachi omume: 2H2O → 2H2 ↑ + O2 ↑ - endothermic, otú okpomọkụ (ike) nke Peltier bụ ike ụmụ irighiri na H2 O2, na-guzobere na electrodes. N'ihi ya, anyị na-enweta na okpomọkụ nke Peltier họrọ na-ajụ na nri n-kọntaktị okporo ọkụ / metal na-adịghị tọhapụrụ azụ n'ime gburugburu ebe obibi, na-echekwara na n'ụdị chemical ike nke hydrogen na oxygen ụmụ irighiri. N'ụzọ doro anya, ọrụ nke mpụga voltaji isi iyi na-iwesa maka electrolysis mmiri, na nke a ga-nta karịa na ikpe nke yiri electrodes, na-eme adịghị omume nke Peltier mmetụta ..

N'agbanyeghị nke Njirimara nke electrodes, na electrolytic cell onwe ya nwere ike banye ma ọ bụ n'ịwa okpomọkụ mgbe agafe Peltier ugbu thereto. The-azọrọ-static ọnọdụ, ndị nwere mgbanwe nke Gibbs mkpụrụ ndụ [4, p. 60]:

Δ G = Δ H - T Δ S, ebe

Δ H - enthalpy mgbanwe nke cell;

T - thermodynamic okpomọkụ;

Δ S - mgbanwe ke entropy nke cell;

Q = - T Δ S - okpomọkụ nke Peltier cell.

N'ihi na a hydrogen-oxygen electrochemical cell na T = 298 (K), mgbanwe enthalpy ΔHpr = - 284.5 (King James Version / mol) [8, p. 120], mgbanwe na Gibbs nwere [4. a. 60]:

ΔGpr = - zFE = 2 * 96485 * 1.23 = - 237.3 (King James Version / mol), ebe

z - ọnụ ọgụgụ nke electrons kwa molekul;

F - Faraday mgbe nile;

E - emf cell.

Ya mere

Q Ekele = - T Δ S Ekele = Δ G wdg - Δ H wdg = - 237,3 + 47,2 = 284,5 (King James Version / mol)> 0,

ie hydrogen-oxygen electrochemical cell site na okpomọkụ na Peltier gburugburu ebe obibi, mgbe rụọ ọrụ ya entropy na ẹsụhọde ya. Mgbe ahụ, na inverse usoro, electrolysis nke mmiri, nke bụ ikpe anyị atụ, Peltier okpomọkụ Q mod = - Q Ekele = - 47.3 (King James Version / mol) nke electrolyte ga-etinye obi gị dum site na gburugburu ebe obibi.

Ịpụta P - Peltier okpomọkụ e si na gburugburu ebe obibi na-nri n-kọntaktị okporo ọkụ / metal. The okpomọkụ P> 0 ga-eguzo cell, ma n'ihi decomposition nke mmiri na cell endothermic mmeghachi omume (Δ H> 0), na Peltier okpomọkụ P bụ iji chefuo thermal mmetụta nke mmeghachi omume:

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

Mod Q adabere naanị na ihe ndị mejupụtara nke electrolyte, ebe Ọ bụ ihe e ji mara nke electrolytic cell na inert electrodes, na n bụ dabere naanị na electrode ihe.

Akụkụ (1) na-egosi na okpomọkụ nke Peltier P na Peltier ikpo mod Q, bụ mmepụta nke bara uru ọrụ. ntụgharị Peltier okpomọkụ wepụwo na-ajụ na-ebelata-eri nke mpụga ike isi iyi chọrọ maka electrolysis. A ọnọdụ ebe okpomọkụ na-ajụ bụ isi iyi nke ike n'ihi na mmepụta nke bara uru na-arụ ọrụ, bụ ndị e ji amata mgbasa, nakwa dị ka ọtụtụ electrochemical mkpụrụ ndụ, ihe atụ nke ndị dị otú ahụ ihe na-egosi na [3, p. 248 - 249].

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