Fisicoquimica

 

E.Ektrbluhhebk Ic hbapcrcheøk lf ic hekåhc fxpfreafktci hbk ics fhuchebkfs lf vfibhelcl prbpufstcs puflf iifvcrsf c hcdb lf lbs ackfrcs= 3. Fi aåtblb aåtblb lf ektfgrc ektfgrcheø heøk, k, quf hbkse hbksestf stf fk hbapc hbapcrcr rcr ics hbkhfk hbkhfktrc trcheb hebkfs kfs bdsfrvc bdsfrvclc lc y fsaclc fk nukheøk lfi fapb. Ci uscr fstf aåtblb fs kfhfscreb ektfgrcr ic fhucheøk lf vfibhelcl pcrc prflfher ic rficheøk lf He fk nukheøk lf t. Fk ics seguefktfs sfhhebkfs sf rfsuafk rfsu afk fstcs ektfgrcheb ektfgrchebkfs kfs pcrc rfchhebk rfchhebkfs fs errfvfrse errfvfrsedifs difs,, rfvfrsedi rfvfrsedifs fs y hbapifmc hbapifmcs. s. 4. Fi aåtblb aåtblb lenfrfkhec lenfrfkhecii rfquefrf rfquefrf ukc lenfrfkh lenfrfkheche echeøk øk lf ibs lctbs fxpfre fxpfreafktc afktcifs ifs lf He fk nukheøk lf t, pcrc bdtfkfr ukc vfibhelcl fxpfreafktci. Ic vfibhelcl sf hbapcrc fktbkhfs hbk ic bdtfkelc fk dcsf c ic fhucheøk lf vfibhelcl prbpufstc. prbpufstc.

Tfchhebkfs rfvfrsedifs Ics rfchhebkfs rfvfrsedifs u bpufstcs sbk cquåiics fk quf ibs prbluhtbs lf ic rfchheøk ekeheci puflfk prbhflfr pcrc nbracr kufvcafktf ic sustckhec bregekci. 

Fhuchebkfs hbkhfktrcheøk-fapb hbkhfktrcheøk-fapb pcrc rfchhebkfs rfvfrsedifs

Zreafr brlfk. brlfk. Xe `3 y `¼3 sbk ics hbkstcktfs lf vfibhelcl lerfhtc f ekvfrsc pcrc fi prbhfsb fifafktci C

D

fktbkhfs

∔l H    1 `  H  ∔`   C

lt 

3

 C

3

H D ( 4∔6> )

Ic hbkhfktrcheøk lf D puflf fxprfscrsf fk tåraekbs lf HC pbr afleb lf uk seapif dcickhf lf acscs. C lfkselcl hbkstcktf, y pufstb quf fi kýafrb lf abifs fs hbkstcktf, ic hbkhfktrcheøk lf D fs su hbkhfktrcheøk ekeheci (HD): a?s ic hbkhfktrcheøk lf C quf oc rfchhebkclb0 fs lfher, H c1( H c ): + H  C  :∔H  C ( 4 ∔67 )  C : Hbadekcklb fstf rfsuitclb hbk ic Fh. (4-6>) sf bdfkf

∔l H  C   1( ` 3 + ` ¼ 3 ) H  C ∔ ` 3 ² lt 

Fk fi fqueiedreb, ics vfibhelclfs lf rfchheøk lerfhtc f ekvfrsc sbk egucifs, y ic Fh. (4-6>) sf trcksnbrac fk ` 3 ²

 

²²² lbklf @ fs ic hbkstcktf lf fqueiedreb. Fieaekcklb `―, lf ic Fh. (4-6?) pbr afleb lfi usb lf ic Fh. (467), sf bdfkf

∔l H  C   1 ` 3 ² lt 

Fktbkhfs, Fktbkh fs, cpieh cpiehckl cklb b ic Fh. Fh. (4(4-67) 67) fk hbkleh hbklehebk ebkfs fs lf fq fquei ueiedr edreb eb pcrc pcrc lftfra lftfraek ekcr cr (H D)fq  y sustuyfklb fstf rfsuitclb fk ic Fh. (4-65), tfkfabs quf  @ 1 ² ²²

( H ²² D )+ )+²² ² ² Hbk fstf vcibr lf (H D) + (HC): pblfabs fxprfscr ic Fh. (4->: fk tåraekbs lf (H C)fq

∔l H  C ` + 3   1 ` 3   ² lt 

` 

b H ¼   C 1 `   TT H ¼   CC ( 4 ∔>4) ∔llt  Lbklf `  T 1

` 3( @ +3)   (4∔>8 )  @ 

U H ¼  C1H  C ∔² ²

Ic Fh. (4->4) fs seaeicr c ic Fh. (4-4) sf rffrf c ic hbkhfktrcheøk lf brtb-oelrøgfkb. Xupbkefklb quf fi oelrøgfkb sfc uk gcs elfci c ics hbklehebkfs lf ic rfchheøk y quf Z sfc ic prfseøk tbtci, sf bdfkf quf H  C1

 Z  Z   U :1  ( 3 ∔U  T ) (D )  T g \   T g \ 

Clfaãs,

²²

Xustuyfklb fstbs rfsuitclbs fk ic Fh. (4->4) y uscklb ics Fhs. (4->8) y (4->> ) lt   @ 

P

Q

cbklf @ fs ic hbkstcktf lf fqueiedreb. Zcrc fxprfscr tblcs ics hbkhfktrchebkfs fk tåraekbs lf ukc vcrecdif, pblrácabs uscr fi grclb lf vfrehcheøk lf ic rfchheøk, t, hbab ib oeheabs fk ic Xfh. 4-5. Zcrc uk sestfac lf vbiuafk hbkstcktf rfsuitc aãs seapif uscr ukc hbkhfktrcheøk hbab vcrecdif. Xupøkgcsf quf ekeheciafktf søib fstãk prfsfktfs C y D fk hbkhfktrchebkfs lf (H C):  y (HD):  Xf sfifhhebkc ic vcrecdif HH . Ics btrcs hbkhfktrchebkfs fk tåraekbs lf Hh sbk H  C1² ² H D1 ² ²

 

H  L 1H h

Xustuyfklb fstcs fhuchebkfs lf hbkhfktrcheøk fk ic Fh. (4->>) sf bdfkf l H h

3

` 4 lt 

  1²

Suf puflf fshredersf hbab l H h

3

4

  1γ + δ H h + θ H h ( 4∔>? )

` 4 lt 

Lbklf γ 1² ²  δ 1∔ 1∔²²

θ 13 ∔

3 ` 

Ic rfsbiuheøk lf ic Fh. (4->?) hbk Hh 1 : hucklb t 1 :, fs 4 θ H h 3

q

3 4

3 4

ik

 δ ∔q 4 θ H h  δ + q

3 4

+3 1` 4 t ( 4 ∔7: ) +3

Lbklf 4

q 1 δ ∔ < γθ ( 4∔73 ) Hucklb sf hbkbhfk ics hbkhfktrc Hucklb hbkhfktrchebk hebkfs fs ekehecifs ekehecifs y ic hbkstcktf lf fqueiedr fqueiedreb, eb, γ , δ y θ   puflfk fvciucrsf sek prbdifacs. Fktbkhfs, ibs lctbs fxpfreafktcifs lf hbkhfktrcheøk-fapb. Xe ic fhucheøk lf vfibhelcl lf sfguklb brlfk fs scsnchtbrec, sf bdtfklrã ukc iákfc rfhtc hbk ukc pfklefktf eguci c `4. Zcrc btrcs nbracs lf fhuchebkfs lf vfibhelcl y lenfrfktfs hbklehebkfs ekehecifs, fi prbhfleaefktb lf ektfgrcheøk puflf sfr aãs lehei. Fi lfscrrbiib pcrc rfchhebkfs rfvfrsedifs hbrrfspbklf c ftcpcs fifafktcifs, pufs sf usc ic rficheøk @ 1 `/`― `/`― pcrc pcrc fieae fieaekcr kcr ic hbkstc hbkstcktf ktf lf vfibhe vfibhelcl lcl fk ler lerfh fhheø heøk k ekvfrs ekvfrsc. c. Zcrc Zcrc rfchhe rfchhebkf bkfss kb fifafktcifs, fstc rficheøk søib fs vãielc hucklb ibs lctbs fxpfreafktcifs sbk lf kcturcifzc tci quf fxestfk hbklehebkfs auy hfrhckcs ci fqueiedreb pcrc tblcs ics ftcpcs eklevelucifs. eklevelucifs.

Fmfapib. Ic rfchheøk fktrf fi yblurb lf afib y ic leafi-p-tbiuelekc nbrac fk sbiuheøk lf ketrb ketrbdf dfkh khfk fkb b uk ukcc sci sci huct huctfr frkc kcre recc lf cabk cabkeb eb eb ebke kezc zclc lc.. Fs Fstc tc rfch rfchhe heøk øk pu pufl flff fs fstu tule lecr crsf sf hekåhcafktf fk ic aesac nbrac quf ic rfchheøk lf ic treaficaekc. Ibs lctbs sf bdtuvefrbk fapfzcklb hbk hbkhfktrcheøk lfukc :.:6sbiuheøk abi g/I. ekeheci quf hbkfkf yblurb lf afib y leafi-p-tbiuelekc c ukc

 

supbkefklb quf ic hbkstcktf lf fqueiedreb pcrc fstc rfchheøk fs 3.>) fs cpiehcdif. Fxprfscklb ic vfibhelcl fk tåraekbs lf ic hbkhfktrcheøk hbkhfktrcheøk lf yblurb sf bdfkf l H  E 

  1 ` 4 H  A H \ ∔ ` ¼ 4 H  E  H  K ( C )

lt 

Ics hbkhfktrchebkfs ekehecifs lf ibs rfchtcktfs sbk egucifs y ic lf ibs prbluhtbs sbk hfrb. XE sf hbkselfrc quf H, fs ic hbkhfktrcheøk lf yblurb y quf H A fs ic hbkhfktrcheøk lf huciquefrc lf ibs rfchtcktfs, ic Fh. (4->7) sf trcksnbrac fk 3

l H 3

` 4 lt 

  1² ²

Aåtblb lf ektfgrcheøk. Ic sbiuheøk lf ic Fh. (D) fstã lclc pbr ics Fhs. (4-7:) y (4-73), lbklf Hh 1 H, y γ 1²  δ 1∔4 ² ² θ 1

` ∔3 `