ऊष्मारसायन

ushmarasayan ke aantargat rasayanik kriyaoan mean kshepit ya shoshit oorja ka adhyayan kiya jata hai. pratyek mean ek vishisht aantarnihit (iantrianzik) oorja hoti hai. udaharan ke lie yadi kriya

k + kh ® g + gh

mean bhag lenevale padarthoan k, kh, g tatha gh ko aantarnihit oorja kramanusar ka, kha, ga tatha gha dvara vyakt ki jae, to in oorjaoan ke nimnalikhit sanbandh sanbhav haian :

(ka + kha) = (ga + gha);

(ka +kha) < (ga + gha);

(ka + kha) > (ga + gha).

pratham avastha mean pratikarakoan ki oorja ka yogaphal kriyaphaloan ki oorja ke yogaphal ke barabar hai, atev pratikriya mean n to ushma ka kshepan hoga, n shoshan. parantu vastut: bahut kam kriyaoan mean aisa hota hai. dvitiy avastha mean pratikarakoan ki kul oorja, (ka +kha), kriyaphaloan ki kul oorja, (ga + gha), se adhik hai, atev oorjanityatv (k aaunazarveshan aauv enarji) sanbandhi niyam ke anusar is pratikriya mean (ka + kha) - (ga + gha) ke barabar ushma kshepit hogi. isi prakar tritiy avastha mean (ka + kha) - (ga + gha) ke barabar oorja shoshit hogi. jin kriyaoan mean ushma ka kshepan hota hai, ve ushmakshepak (eksotharmik) kahalati haian aur jinamean ushma ka shoshan hota hai, un pratikriyaoan ko ushmashoshak (eandotharmik) kahate haian.

ushmarasayanik samikaran-sadharanataya kisi pratikriya mean kshepit ya shoshit ushma ko usake samikaran dvara vyakt kar dete haian. udaharan ke lie :

H2 (gais) + Cl2 = 2HCl (gais) + 44,000 k0

dvara pakat hota hai ki 1 gram-anu (2 gram) haidrojan gais tatha 1 gram-anu (71 gram) klorin gais se sanyojan se jab 2 gram-anu (73 gram) haidroklorik aml gais banati hai, to 44, 000 kailari ushma kshepit hoti hai. isi prakar nimnaankit samikaran dekhie :

H2 (gais) + I2 = 2HCl (gais) - 11,860 k0

dvara yah prakat hota hai ki yadi 2 gram haidrojan tatha 254 gram ayodin gais ke sanyojan se 256 gram haidrojan ayodaid gais banaee jae to is pratikriya mean 11,860 kailari ushma shoshit hogi.

yah to spasht hai ki kisi bhi kriya mean kshepit ushma ki matra usamean bhag lenevale padarthoan ki bhautik avastha par nirbhar rahegi; isilie bhi likh jati hai. bhautik avastha ka jo prabhav pratikriya-ushma par p data hai vah nimnaankit udaharan se spasht ho jaega :

H2 (gais) + O 2 = H2O (bhap) + 58,000 k0

tatha H2 (gais) + O 2 = H2O (drav) + 68,000 k0

dvitiy samikaran mean ushma ki kshepit matra pratham samikaranoan ki apeksha adhik hai kyoanki isamean 18 gram bhap ke dravit hone mean kshepit ushma ki matra sammilit hai.

jin pratikriyaoan mean pratikarakoan ke ayatan mean bhi parivartan hota hai, unake lie pratikriya-ushma is bat par bhi nirbhar hogi ki pratikriya sthir ayatan par ki gee hai athava sthir dab par. yadi pratikriya karate samay ayatan sthir rakha jae, to mandal (sistam) ko bahy dab ke viruddh kuchh kary nahian karana p data. atev sthir ayatan par pratikriya ki yatharth oorja kshepit ya shoshit hoti hai. parantu yadi kriya karate samay dab ko sthir rakhate hue ayatan ko badhane ya ghatane diya jae, to pratikriya-ushma ka yatharth man jnat nahian hoga. udaharan ke lie; ayatan badhane mean mandal bahy dab ke viruddh kary karata hai, jisamean oorja vyay hogi; atev yadi pratikriya ushmakshepak hai to is avastha mean kshepit ki matra kam ho jaegi. sadharanat: pratikriyaoan ki ushma sthir ayatan par hi napi jati hai.

ushmarasayan ke drishtikon se pratikriyaoan ko pray: kee vargoan mean baant lete haian aur pratikriya svabhav ke anukool pratikriya-ushma ko nam de diya jata hai-jaise vilayan-ushma (hit aauv solyushan), tanukaran-ushma (hita aauv dailyooshan), utpadan-ushma (hit aauv f aaurmeshan), dahan-ushma (hit aauv kanbashchan) tatha shithilikaran-ushma (hita aauv nyootrailaizeshan).

vilayan-ushma-kisi vilaye ko vilayak mean gholane par pray: ushma ka kshepan hota hai. jo lavan jal se kriya karake jalayojit (haidreted) lavan banate haian unake ghulane par adhikatar ushma ka kshepan hota hai. any lavanoan ke ghulane mean kshepit ushma ki matra bahut kam hai. kisi padarth ke ek gram-anu ko vilayak mean gholane par kshepit ya shoshit oorja ki matra ko vilayan-ushma kahate haian.

isake atirikt saandr vilayan ko tanu karane mean bhi ushma mean parivartan hota hai aur ise vilayan ki tanukaran-ushma kahate haian. tanukaran-ushma ki matra vilayanoan ki tanuta ke sath kam hati jati hai aur adhik tanu vilayanoan ke lie ise shoony mana ja sakata hai. aise tanu vilayanoan ki ushmarasayan mean 'jaliy' kahate haian. udaharan ke lie; potaishiyam naitret jal mean vilin hokar ati banu vilayan banata hais, to usaki vilayan ushma 8,500 kailari hoti hai. is tathy ko nimnalikhit samikaran dvara vyakt kar sakate haian :

KNO3 + (jal) = KNO3 (jaliy) - 85,00 k0

utpadan-ushma-avayav tatvoan ke sanyog se kisi yaugik ke ek gram-anu banane mean jitani ushma shoshit ya kshepit hoti hai, use us yogik ki utpadan-ushma kaha jata hai. udaharan ke lie nimnaankit samikaranoan dvara spasht hai ki karban daiaauksaid (CO2) , methen (CH4), tatha naitrik aml (HNO3) ki utpadan-ushma kramanusar 94.4, 18.8 tatha 42.4 kailari hai :

C + O2 = CO2 + 94.4 k0

C + 2H2 = CH4 + 18.8 k0

H2 + N2 = O2 = HNO3 + 42.4 k0

utpadan ushma rrinatmak bhi ho sakati hai, jaise :

C + O2 = C S2 - 22,000 k0

avayav tatvoan se jin yaugikoan ke banane mean ushma kshepit hoti hai unhean ushmakshepak yaugik kahate haian aur jin yaugikoan ke banane mean ushma shoshit hoti hai unhean ushmashoshak yogik kahate haian. adhikatar yaugik ushmakshepak hote haian, jaise haidrojan, kloraid, jal, haidrojan salafaid, salaphar daiaauksaid, karban daiaauksaid, led kloraid adi sab ushmakshepak yaugik haian. ushmashoshak yaugikoan ke udaharan haidrojan ayodaid, karban daisalaphaid, aisetilin, ozon adi die ja sakate haian.

ushmashoshak yaugik ushmakshepak yaugikoan ki apeksha bahut kam sthayi hote haian aur sugamata se apane avayaviy tatvoan mean vichchhedit ho jate haian. ushmakshepak aur ushmashoshak yaugikoan ke sthayitv ka uparyukt bhed unamean aantarnihit oorja ke aantar ke karan hota hai. udaharan ke lie; 1 gram-anu karban tatha 1 gram-anu aksijan ke sanyog se jab 1 gram-anu karban daiaauksaid banata hai, to 94,300 kailari ushma kshepit hoti hai. spasht hai ki apane avayav tatvoan ki apeksha 1 gram-anu karban daiaauksaid mean 94,300 kailari oorja kam hogi. isi prakar karban daisalphaid jaise ushmashoshak yaugik mean apen avayav tatvoan ki apeksha 22,000 kailari oorja adhik hogi. yadi samast tatvoan ki aantarnihit oorja ko shoony man liya jae, to upayukt vivechan se spasht hai ki yaugikoan ki aantarrihit oorja unaki utpadan ushma ke barabar hogi; parantu yadi utpadan oorja rrinatmak hai to aantarnihit oorja dhanatmak hogi aur isake viparit yadi utpadan ushma dhanatmak ho, to aantarnihit oorja rrinatmak hogi. udaharanat: karban daiaauksaid tatha karban daisalaphaid ki aantarnihit oorjaean kramanusar -94,300 tatha +22,000 kailari ke barabar hoangi.

dahan-ushma-kisi tatv yo yaugik ki 1 gram-anu matra ko aauksijan mean sthir ayatan par poornataya jalane se ushma ki jo matra kshepit hoti hai, use us tatv ya yaugik ki dahan-ushma kahate haian.

udaharan ke lie nimnalikhit samikaran se spasht hai ki methen ki dahan-ushma 2,12,800 kailari hai :

CH2 + 2 O2 = C O2 + 2H2 O + 2,12,800 k0

karban ko aauksijan mean jalane par do yaugikoan ka banana sanbhav hai-

C + O2 = C O2 + 49,900 k0

C + O2 = C O + 26,000 k0

yah bat dhyan dene yogy hai ki karban ki dahan-ushma 94,300 kailari hai, 26,000 kailari nahian, kyoanki pratham kriya mean hi karban poornataya jalata ya aksikrit hota hai. doosari kriya mean karban, karban monoksaid mean parivartit ho gaya hai, parantu abhi usaka dahan poorn nahian hua kyoanki karban monoksaid ka aur dahan karake use karban daiaauksaid mean aksikrit kiya ja sakata hai.

dahan-ushma jnat karane ke lie ek vishesh prakar ke kalarimapak ka upayog kiya jata hai jise bam-kalarimapak (b aaumb kailorimitar) kahate haian. vaijnanik baratheloan ne ise sarvapratham 1881 mean banaya tha. yah ganametal ispat ka bana rahata hai aur belan ke akar ka hota hai. isake aantarik tal par ek vishesh prakar ka inaimal chadha rahata hai, jisase usapar aauksijan ki koee kriya nahian hoti. dhakkan dh ko dridhata se band karane ke lie isamean majaboot peanch lage rahate haian. jis padarth ki dahan-ushma nikalana ho usaki ek nishchit matra plaitinam ki pyali 'p' mean le li jati hai aur bam mean lagabhag 20-25 vayumandaliy dab par aauksijan bhar lete haian. isake bad vam ko dridhata se band karake use sadharan kalarimapak mean rakhate haian. sadharan kalarimapak mean jal ki ek nishchit matra le li jati aur prayog dvara pahale hi yah nirdharit kar liya jata hai ki is kalarimapak mean jal ke tap ko 1° seantigred badhane ke lie kitani ushma ki avashyakata hoti hai. bahy kalarimapak mean jal ka tap nap liya jata hai. ab plaitinam ke taroan a tatha a dvara lohe ke ek mahin tar t mean vidyuth‌ pravahit karate haian. vidyutpravah se tar t garam hokar lal ho jata hai aur pyali p mean rakha padarth aksikrit hone lagata hai. lohe ke tar ke jalane mean tatha aksikaran ki is kriya mean ushma kshepit hoti hai, jisaki matra bahy kalarimapak mean upasthit jal ke tap mean vriddhi se jnat kar li jati hai. is prayog se prapt ushma-matra mean se lohe ke jvalan mean kshepit ushma ko ghatakar padarth ke dahan dvara kshepit ushma ki matra jnat ki ja sakati hai. spasht hai ki is prayog mean mandal ka ayatan sthir rahata hai; atev is vidhi se kisi padarth ki dahan-ushma nirdharit ki ja sakati hai. 150px|left chitr 1. baratheli ka bam-kalarimapak

shithilikaran-ushma-ek gram-tuly matra kshar ko ek gram-tuly matra aml dvara shithil (nyootrailaiz) karane par ushma ki jo matra lepit hoti hai use shithilikaran-ushma kahate haian. yadi aml tatha kshar itane tanu vilayanoan mean lie jaean ki ve poornataya ayanoan mean vighatit hoan to shithilikaran ki kriya keval haidrojan tatha haidroksil ayanoan ke sanyog se avighatit anu banane ki kriya hogi. atev tanu vilayanoan mean sab prabal (str aaunh‌g) amloan dvara prabal ksharoan ke shithilikaran ki ushma saman hogi. prayog dvara is ushma ka man 13,7000 kailari ata hai. at: prabal amloan dvara prabal kshar ke shithilikaran ko nimnalikhit samikaranoan dvara vyakt kar sakate haian :

HX + MOH = MX + H2O

jahaan X ko moolak hai aur M koee dhatu hai,

arthath‌ H+ + X+ + M+ + OH- = MX + H2O

arthath‌ H+ + OH- = H2O

parantu yadi aml ya kshar durbal ho, to vah tanu vilayan mean bhi poornataya vighatit n hoga. atev aise amloan ya ksharoan ki shithilikaran ushma 13,700 kailari n aegi. udaharan ke lie amoniyam haidr aauksaid ki ayanikaran-ushma (1 gram-anu ke ayanikaran ki ushma) -1,500 kailari hai, atev amoniyam haidr aauksaid tatha kisi prabal aml (jaise haklo) ki shithilikaran ushma (13,700-1,500) =12,200 kailari hogi.

prayog dvara shithilikaran ushma ko nirdharit karane ke lie sadharanat: ek tharamas phlask mean kshar ke tanu vilayan ki ek nishchit matra lekar phlask ko sthir tapavale jal mean dubakar rakhate haian, jisase vikiran (redieshan) dvara phlask ke bhitar vilayan ke tap mean aantar n ho. ab banu vilayan mean aml ki samatuly matra lekar usaka tap kshar ke tap ke barabar sthir kar lete haian. aml ka tap sthir ho jane par use shighrata se kshar mean mila dete haian. kach ke ek vilodak (starar) dvara vilayan ko chalakar usaka uchchatam tap nap liya jata hai. ab yadi mishr vilayan ki matra, usaki vishisht-ushma (spesifik hit), tap, prayukt phlask ki ushmadharita (hit-kaipesiti) jnat ho, to shithilikaran kriya mean kshepit ushma ki matra sugamata se jnat ki ja sakati hai. isi vidhi dvara lavanoan ki vilayan-ushma bhi sugamata se nikal sakate haian.

hes ka niyam-ushma-rasayan ka sabase pramukh niyam svis vaijnanik jaramen henari hes ne sanh‌ 1840 mean pratipadit kiya tha. is niyam ke anusar kisi rasayanik kriya mean kshepit ya shoshit ushma ki matra madhyavarti kriyaoan par nirbhar nahian rahati, arthath‌ ek hi kriya ko yadi ek se adhik vidhiyoan dvara poora kiya ja sake, pratikarak tatha kriyaphal pratyek kriya mean poornataya ek hoan aur un sabaki avasthaean bhi saman hoan, to vibhinn vidhiyoan mean jo kul ushma-parivartan hoga, vah har ek vidhi ke lie saman hoga. 150px|center

is niyam ki satyata sanlagn chitr 2. se spasht hai. man lean, padarth 'a' ko a mean parivartit karane ke lie marg a k a tatha a kh a dvara jane par kramanusar k1 tatha k2 kailari ushma kshepit hoti hai. yadi k1 k man k2 se adhik hai, to marg a k a dvara a ko a mean parivartit kar aur pun: a ko a mean marg a kh a dvara badalakar (k1-k2) kailari ushma utpadit ki ja sakati hai. parantu yah oorja-avinashata niyam ke viruddh hoga, kyoanki bina kisi kary ke mandal (sistam) mean ushma utpadit karana asanbhav hai; arthath‌ (k1-k2) ka man sardav shoony hoga; at: k1 sadaiv k2 ke barabar hoga.

is niyam ki satyata dekhane ke lie nimnaankit udaharan ko le sakate haian. amoniya tatha haidrojan kloraid gaisoan ki pratikriya se amoniyam kloraid vilayan do prakar se prapt kiya ja sakata hai :

pratham vidhi

NH3 (gais) + HCl (gais) = NH4Cl (gais) + 42,100 k0

NH4Cl (gais) + jal = NH4Cl (jaliy) - 39,900 k0

NH3 (gais) + HCl (gais) + jal = NH4Cl (jaliy) + 38,200 k0

dvitiy vidhi

NH3 (gais) + jal = NH3 (jaliy) + 8,400 k0

HCl (gais) + jal = HCl (jaliy) - 17,500 k0

NH3 (jaliy) + HCl (jaliy) = NH4Cl (jaliy) + 12,300 k0

NH3 (gais) + HCl (gais) + jal = NH4Cl (jaliy) 38,200 k0

uparyukt udaharan se hes ke niyam ki satyata spasht ho jati hai.

hes ka niyam ushma-rasayan mean bahut upayogi siddh hua hai. isaki sahayata se pratyaksh roop se n ki ja sakanevali pratikriyaoan mean honevale ushma-parivartanoan ko bhi paroksh roop se nikala ja sakata hai. udaharan ke lie; sadharanat: karbanik yaugikoan ki utpadan-ushma pratyaksh kriya dvara nahian nikali ja sakati, parantu karbanik yaugik tatha isake avayav tatvoan ki dahan-ushma ko nirdharit karake yaugik ki utpadan-ushma hes ke niyam se nikal sakate haian.

udaharan ke lie methen, karban tatha haidrojan ki dahan-ushma kramanusar 2,12,800; 94,400 tatha 68,400 kailari ati hai, arthath‌

CH4 + 2O2 = C O2 + 2H2 O + 2,12,800 k0

C + O2 = C O2 + 94,300 k0

H2 + O2 = H2 O + 68,400 k0

dvitiy samikaran mean tritiy samikaran ka duguna jo dakar pratham samikaran ko ghatane par nimnalikhit samikaran prapt hoga :

C + O2 = 2H 2 + O2 -CH4 - 2O2 = C O2 + 2H2 O -C O2

- 2H2 O + (94,300 + 2 ´ 68,400 - 2,12,80000)

arthath‌ C + 2H 2 = CH4 + 18,3000 k0

uparyukt vivechan se spasht hai ki methen utpadan-ushma 18,400 kailari hai. is prakar hes ke niyam ke aanrtagat ushmarasayanik samikaranoan ko ganit ke samikaranoan ki bhaanti guna kar, vibhajit kar, jo dakar ya ghatakar abhisht pratikriya ka samikaran tatha us kriya mean honevale ushma-parivartan ke man ka pata laga lete haian.

shh

talika 1

pratyaksh sanshleshan vidhi se kuchh padarthoan ki utpadan-ushma

yaugik kilokalari/gram-anu yaugik kilokalari/gram-anu

H2o (drav) -68.317 ±0.010 HFl (gais) -64.2

CO2 (gais) -94.052 ±0.011 HCl (gais) -22.063 ± 0.012

SiO2 (kvarth‌z) -210.3 ±0.3 BCll3 (gais) -97.5 ± 0.300

Al2O3 -400.3 ±0.3 H Br (gais) -8.707 ± 0.130

SnO2 -138.8 ±0.1 Ti3Br4 (drav) -148.1 ± 0.300

ThO2 -293.2 ±0.2 AIN -57.4 ± 1.300

talika 2

paroksh vidhiyoan se prapt kuchh padarthoan ki utpadan-ushma

yogik kilokalari/gram-anu yogik kilokalari/gram-anu

EtCl (gais) -26.2 ±0.5 Si (OEt) -330.2

EtBr (ges) -15.3 ±0.5 CH3COCl -65.1

CH4 (gais) -17.889 CH2CONH2 -78.7

C2H6 (gais) -20.326 CH2COOEt -114.9

C2H6 (gais) 19.82 CdMe2 16.7 ±0.5

BCl3 (drav) -10.26 HgPh2 65.4 ±2

ushmarasayan ke audyogik upayog-rasayanik kriyaoan se prapt oorja hi hamare udyogoan ko chalane ka sadhan rahi hai. aj kritrim upagrah ke yug mean jab manav chandrama tatha any grahoan ki yatra mean prayatnashil hai to aise eedhanoan ki khoj avashyak ho gee hai jinaki sookshm se sookshm matra adhik tam oorja de sake. boran yaugik is or bahut upayogi siddh ho rahe haian, kyoanki saman matra mean karban yaugikoan se unaki dahan-ushma adhik hoti hai aur ve hamean adhik oorja dene mean saphal hote haian.

ushmarasayan ke any upayog bahut kal se hote ae haian. udaharan ke lie ;pratham talika mean ailyoominiyam auksaid ki utpadan-ushma sabase adhik dikhaee gee hai. isi gun ka upayog goldadashmit ki ushman vidhi (tharmit proses) mean kiya gaya hai. ailyoominiyam aauksaid ki utpadan-ushma itani adhik hone ke karan pratikriya,

8 Al + 3 Fe3 O4® 9 Fe + 4 Al2 O3

mean itani adhik ushma kshepit hoti hai ki mandal ka tap lagabhag 3,0000 seantigred tak pahuanch jata hai aur loha tak pighal jata hai. is prakar tooti huee rel ki patariyoan bhi bhari mashinoan ke toote hue bhagoan ko uparyukt kriya ki sahayata se pighalakar jo da ja sakata hai.

panne ki pragati avastha

adhar

prarambhik

madhyamik

poornata

shodh

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