भौतिक रसायन

bhautik rasayan (aangrezi: Physical Chemistry) rasayan vijnan ki vah shakha hai jo bhautik avadharanaoan ke adhar par rasayanik pranaliyoan mean ghatit hone vali parighatanaoan ki vyakhya karati hai. dravy ki avinashita ke niyam ke sath hi sath bhautik rasayan ki nianv p di, yadyapi 19vian shati ke aant tak bhautik rasayan ko rasayan ka prithakh‌ aang nahian mana gaya. vaant haph, vilhelm aaustavald aur ariniyas ke karyean ne bhautik rasayan ki rooparekha nirdharit ki. sthir anupat aur gunit anupat evan paraspar anupat ke niyamoan ne, aur bad ko avogadro niy, gelusaik niyam adi ne paramanu aur anu ki kalpana ko praray diya. paramanubhar aur anubhar nikalane ki vividh paddhatiyoan ka vikas kiya gaya. gais sanbandhi b aauyal aur charls ke niyamoan ne aur graham ke avisaran niyamoan ne isamean sahayata di. vilayanoan ki prakriti samajhane mean parasaran dab sanbandhi vicharoan ne ek navin yug ko janm diya. pani mean ghulakar shakkar ke anu usi prakar alag alag ho jate haian jaise shoony sthan mean gais ke anu. rault (Raoult) ka vashpadab sanbandhi samikaran vilayanoan ke sanbandh mean b de kam ka siddh hua.

b aauyal-charls samikaran

da´a=jh pa [P´V=R T]

yahaan da (P)=dab, a (V)= ayatan, pa (T)=param tap tatha jh (R) gais niyataank hai. yah samikaran 1 gram-anu gais ke lie hai. yadi gais ch (n) gram anu ho, to yah samikaran da´a=ch jh pa (P V= n R T) ho jaega.

graham ka samikaran

chitr:Chemistry-6.gif chitr:Chemistry-7.gif isamean do gaisoan ke lie kramash: visaran (diffusion) ki gatiyaan ga1 (D1) aur ga2 (D2) haian, gaisoan ke ghanatv gh1 (d1) aur gh2 (d2) hai, unake anubhar a1 (M1) aur a2 (M2) haian, evan kisi chhote se chhed mean hokar gais ke nichit ayatan ke visaran ka samay kramash: s1 (t1) aur s2 (t2) hai.

daltan ka aanshik dab ka niyam

da=d1+d2+d3+.............

[P=p1+p2+p3+..........]

yahaan kisi die hue gaisoan ke mishran mean sab gaisoan ki samavet dab da (P) hai aur un gaisoan ki prithakh‌ prithakh‌ dab d1 (p1), d2 (p2), d3 (p3)......adi. ye sab gaisean adarsh hoan, inaka param tap pa (T) ho aur sab gaisean a (v) ayatan ke patr mean hoan to-

isi prakar

chitr:Chemistry-10.gif.... ityadi

at: gais mishran mean kisi ek gais ki aanshik dab, d1 ke lie :

parasaran dab

isaka samikaran bhi gais dab ke samikaran ke saman hai. yadi kisi vilayan ki sandrata s (C) anu prati ikaee ayatan ho aur ayatan a (V) ho (a vah ayatan hai, jisamean vilayashil 1 anu ghula hai), to s (C)=1/a, (1/V). parasaran dab da ke lie samikaran yah hai :

da´a=jh ta, da=jh ta s [P´V=R T, P=R T C]

rault ka niyam

eph.em. rault ne 1887 ee. mean, lagabhag tanu vilayan mean, vashpadab ke sapeksh avanaman ke sanbandh mean yah niyam diya :

isamean vilayak ki vashpadab d (p), vilayan ki vashyadab d0 (p0), vilayak ki vashpadab mean kami D d (D p) aur chitr:Chemistry-20.gif vilayan ki dab mean sapeksh avanaman hai. vilayan mean vilayak ke anuoan ki sankhya ch2 (n2) hai, aur viley ke anuoan ki sankhya ch1 (n1) hai.

agar vilayan mean viley ka dravyaman dr (w), viley ka anubhar bh (m) shuddh vilayak ka dravyaman dra (W) aur vilayak ka anubhar bha (M) ho, to

vilayak mean viley ke ghulane par vilayak ki vashpadab mean kami a jati hai, aur isi karan shuddh vilayak ke kvathanaank se vilayan ka kvathanaank adhik, aur shuddh vilayak ke himaank se vilayan ka himaank kam, hota hai. kvathanaank ki vriddhi D pa (D T), vilayan ki saandrata aur viley ke anubhar, bh (M), aur vilayak ke niyataank (ya kvathanaank ka anavik utkarsh), kakv (Kb) par nirbhar hai. niche ke samikaran mean yah ka kakv 100 gram vilayak ki matra ke lie hai.

(k gram viley kh gram vilayak mean ghola gaya hai)

isi prakar himaank ki kami, D pa (D T) nimn samikaran dvara vyakt hoti hai niyataank, kah (Kf), himaank ka anavik avanaman kahalata hai. 100 gram vilayak ke lie yah niyataank hai.

kakv (Kb) ka sanbandh vilayak ke kvathanaank pa (T) aur usake vashpikaran gupt ooshma, gu (L), se nimnaprakar hai -

isi prakar ka samikaran himaank ke anavik avanaman niyataank kah (Kf) ke lie bhi hai.

isamean gu (L), himan ki gupt ushma aur pa (T) himaank hai.

dravyaman samanupati kriya ya dravyamatra kriya ka niyam

1894 ee. mean guldavarg (Guldberg) aur vage (Waage) ne is niyam ka pratipadan kiya. niyam yah hai : 'rasayanik abhikriya ka veg abhikriya mean bhag lenevale padarthoan ke sakriy dravyamanoan ka samanupati hota hai.' is niyam ka upayog bahudha utkramaniy (reversible) kriyaoan ke samy ke sanbandh mean bhi kiya jata hai. abhikriya vyakt karane vala sarvasamany samikaran nimnalikhit hai :

k ka+kh kha+g ga+...=k¢ ka¢+kh¢ kha¢+g¢ ga¢+...

[a A+b B+c C+. . .=a¢ A¢+b¢ B¢+c¢ C¢+. . . . ]

yahaan kriya mean bhag lene vale padarth ka, kha, ga, (A, B, C) adi haian aur kriya se utpann padarth ka¢, kha¢, ga¢.... (A¢, B¢, C¢) adi haian.

yah kriya utkramaniy hai. samy sthapit hone par yadi ka, kha, ga,.... (A, B, C....), ka¢, kha¢, ga¢..... (A¢, B¢, C¢....) adi ki saandrataean kramash: (ka), (kha), (ga),.... [(A), (B), (C),....], (ka¢), (kha¢), (ga¢),.... [(A¢), (B¢), (C¢),....] adi hoan, to samy niyataank t (K) nimnalikhit hoga :

yah niyataank t (K) tap par rnibhar hai. ooshmagatiki ke siddhaantoan ke anusar nimn samikaran dvara t par tap, pa (T), ka prabhav vyakt kiya jata hai-

is samikaran mean D oo(D u) abhikriya ki ooshma hai.

svatantr oorja, pha (F), aur samyaniyataank, t (K), mean nimn sanbandh hai, jise vaantahaph ka samapati vakr (isotherm) kahate haian :

t pha=jh pa laghu t - jh pa Su laghu s

d F=R T log K - R T Su log C

SC is abhikriya mean bhag lenevale padarthoan ki svayanmany saandrataean haian.

gibj ka kala niyam

yadi kisi nikay (system) se sanghatakoan (components) ki sankhya s (C) ho, aur kalaoan ki sankhya k (P) ho te svatantr char rashiyoan ki sankhya, ya svatantr ki matra m (F), samy sthapit hone par nimn samikaran dvara vyakt ki jati hai :

k+m=s+2, (P+F=C+2)

athava m=s-k+2, (F=C-P+2)

yah gibz ka kala niyam kahalata hai. ooshmagatiki sanbandhi lekh mean is niyam ki pratipatti di huee hai. is niyam ke adhar par anek nikayoan (jal, gandhak, miradhatu, vilayak-miran) ke vivaran rekhachitroan dvara vyakt kie jate haian.

(9) vidyudvileshan sanbandhi niyam

gaikel phairade (Faraday) ne 1883 ee. mean vidyudvileshan sanbandhi do niyam die :

(k) vidyuth‌ dhara dvara utpann rasayanik kriya vidyut dhara ki matra ki samanupati hoti hai, arthath‌ jitani dhara pravahit hogi usi ke anupat mean koee padarth nikshipt ya vilin hoga.

(kh) vidyuth‌ dhara ki ek hi matra dvara yadi kee padarth nikshipt, ya vilin ho rahe hoan, to unaki matraean usi anupat mean hogi, jisamean unake rasayanik tulyaank bhar haian.

in donoan niyamoan ko ek sammilit samikaran dvara vyakt kiya ja sakata hai. yadi kisi padarth ki nikshipat matra ya vilin matra v (w) gram, dhara ki samarthy i (I) aianpiyar ho, dhara ke pravahit hone ka samay s (t) sekand or tulyaank bhar tu (e) ho to

samean phai (F) ko phairade ikaee kahate haian. phai (phairade) vidyuth‌ ki vah matra hai, jisake pravahit hone par kisi bhi padarth ka ek gram tulyaank ya to nikshipt hota hai, ya vilin hota hai :

phe=96,500 koolanb

dhan aur rrin vidyudagroan par dhanatmak aur rrinatmak ayan ek hi tulyamatra mean visarjit hote haian, kiantu yah smaran rakhana chahie ki ye ayan ek hi gati se kaithod (cathode) ya ainod (anode) ki or agrasar nahian hote. yadi dhanayan (cation) ki gati gagh (wc) aur rrinayan (anion) ki gati ga (Ua) ho, to dhanayan ki sthanaantaran, ya parivahan (transferenc of transport) sankhya tagh (Tc) aur rrinayan ki parivahan sankhya, ta (Ta) nimnalikhit samikaranoan dvara vyakt ki jaegi-

hit aaurph (Hittorf) ne 1853 ee. mean is parivahan sankhyaoan ke nikalane ki vidhi nikali.

arreniyas ki vidyudviyojan ki kalpana

arreniyas (Arrhenius) ne 1883-87 ee. mean vidyudviyojan ki kalpana prastut ki. jal mean ghulane par vidyudvileshy, jaise namak, tootiya, aml, kshar adi, dhan aur rrin ayanoan mean viyojit ho jate haian. yah avayak nahian hai ki vidyudvileshyoan ke samast anu viyojit hote hoan. aisitik aml adi ke saman nirbal vidyudvileshy kuchh pratishat hi viyojit hote haian, kiantu sodiyam kloraid, haidroklorik aml, k aaustik soda adi ke saman sabal vidyudvileshy lagabhag shat pratishat viyojan, ya ayanan prastut karate haian. ayanan ki matra (degree of ionisation) a (ailpha) vilayan ki tanuta par nirbhar hai. arreniyas ne ayanan ki matra vilayan ki vidyuchchalakata ke adhar par nikali. yadi kisi vilayan ki vishisht chalakata (specific conductivity), arthath‌ vishisht rodhakata (resistance) ka vyutkram ch (K) ho aur vilayan ki saandrata 1 gram tuly prati ayatan a (v) ghan seanmi. ho, to usaki tuly chalakata (equivalent conductivity), t, (m), nimn samikaran dvara vyakt ki jaegi-

t=ch´a, [m=K´v]

nirbal vidyuth‌ apaghatyoan ki tuly chalakataean vilayan ki tanuta badhane par badhati jati haian, aur jab vidyuth‌ apaghatyoan shat pratishat ayanit ho jata hai to yah sthir ho jati hai. is samay ki tuly vidyuchchalakata ko anant tanuta ki vidyuchchalakata (mµ ya tµ) kahate haian. kisi tanuta, a, par vidyuchachalakata ta ho aur anant tanuta par tµ to ayanikaran ki matra, a nimn hogi :

anant tanuta par ayanik chalakataean (25° seantigred)

dhanayan	chalakata	rrinayan	chalakata
ha+ (H+)	349.82	auha- (OH-)	198.5
pa+ (K+)	73.52	bro- (Br-)	78.4
naha4+ (NH4+)	73.4	a- (I-)	76.8
so+ (Na+)	50.11	klo- (Cl-)	76.34
r+ (Ag+)	61.92	nao3- (NO3-)	71.44

nirbal amloan ke lie aaustavald (Ostwald) ne nimnalikhit tanuta niyam (dilution law) pratipadit kiya- chitr:Chemistry-37.gif isamean a (u) litar mean yah ayatan hai, jisamean vidyuth‌ apaghaty ka ek gram anu matra ghuli ho. ka (K), ko vidyuth‌ apaghaty ka viyojan niyataank (dissociation constant) kahate haian. sabal vidyuth‌ apaghaty ke lie aaustavald ke is samikaran ka upayog nahian kiya ja sakata. debaee (Debye) aur hookal (Huckel) ne 1923 ee. mean aur aaunasaigar (Onsager) ne 1926 ee. mean in sabal vidyuth‌ vighatyoan ki vidyuchchalakata ke lie doosare samikaran die. potaishiyam kloraid ke lie, jisamean do ekasanyoji ayan, haian, yah samikaran is prakar hai :

vi (D) vilayak ka paravaidyutaank (dielectric constant) hai, ta (T) param tap, y (h) yanata (viscosity) aur s (C) vilayan ki saandrata (anu prati litar, ya gram-tulyaank prati litar) hai. sankshep mean is samikaran ko is prakar likheange-

isamean ka (A) aur kha (B) die hue vilayak ke lie sthiraank haian, jo tap par hi nirbhar haian.

(12) pani nirbal vidyudvileshy hai :

ha2 au = ha+ + au ha

[H2 O = H++ O H]

pani ka ayanan niyataank kam (Kw) = (ha+) (au ha-) [H+] [OH-] = 80.·95 ´ 10-14 (25° sean. tap ke lie). pani ke is ayanan ke karan hi jal-apaghatan hota hai. jal-apaghatan ka niyataank kah (Kh) pani ke ayanan niyataank aur nirbal aml, ya nirbal kshar ke viyojan niyataank, par, kaa (Ka), aml ke lie evan kaksh (Kh) kshar ke lie, nirbhar hai.

jal-apaghatan niyataank, ka kah = chitr:Chemistry-41.gif jahaan j (h) = jal apaghatan ki matra, a (v) = litar mean vah ayatan jitane mean ek gram anu yaugik ghula ho.

kah = chitr:Chemistry-42.gif (sodiyam aisitet aise nirbal aml ke lavan ke jal-apaghatan ke lie)

kah = chitr:Chemistry-43.gif (amoniyam kloraid aise nirbal kshar ke lavan ke lie).

kah = chitr:Chemistry-44.gif (amoniyam aisitet aise nirbal kshar aur nirbal amal se bane lavan ke lie).

(13) aml aur ksharak - ayanan par jo padarth prot aaun, ya haidrojan ayan, ha+ (H+) dete haian, ve aml haian aur jo haidr aauksil ayan, auha- (OH-) dete haian, ve ksharak (base) kahalate haian :

haka = ha+ + ka-

[ HA = H+ + A- ]

aml prot aaun

kha au ha = kha+ + auha-

[ B OH = B+ + OH- ]

bransted (Bronsted) aur lauri (Lowry) ki paribhasha ke anusar us padarth ko aml kahate haian jisaki pravritti prot aaun de dene ki aur ksharak vah padarth hai jisaki pravritti prot aaun le lene ki ho

ka = ha+ + kha

[A = H+ + B]

aml protan ksharak

pani mean ghule haidroklorik aml mean nimn samy hai (pani ksharak ka kam karata hai)

haklo + ha2au = ha3au + klo

[ HCl + H2O = H3O+ + Cl ]

aml ksharak aml ksharak

(vilayak)

isi prakar pani (vilayak) mean ghule amoniya mean nimn samy hai (pani aml ka kam karata hai) :

naha3 + ha2au naha4 + auha-

[ NH3 + H2O = NH4+ + OH-

ksharak aml aml ksharak

(vilayak)

(14) haidrojan ayan saandrata evan pi-ech, (pH) ksharak - aisitik aml pani mean ghulane par shat pratishat ayanit nahian hota. isi prakar any aml bhi poorn ayanit nahian hote. vilayan ki amlata haidrojan ayan ki saandrata, saha (CH) par nirbhar hai. yah saandrata anek vidhiyoan se nikali ja sakati hai : (k) rang soochakoan ke rangoan ki tulanana karake tatha (kh) vidyudvahakabal (e. m. f.) vidhi ka prayog karake. vilayan ke haidrojan ayan ki saandrata ke anusar anek rangasoochak rangoan ka chatakilapan pradarshit karate haian.

hadadrojan ayan ki saandrata saha (CH) vyakt karane ki ek saral pranali pi-ech paddhati kahalati hai. pi-ech aur saha (CH) (si-ech) mean nimn sanbandh hai :

pi-ech = - laghu saha ya (-laghu si-ech)

[pH = -log CH,] (B) (B)

jis vilayan ka pi-ech sat se kam hota hai, vah amliy hai, sat ke nikat ke pi-ech vala vilayan shithil, ya udasin hai, aur sat se adhik pi-ech vala vilayan kshariy hai.

(15) soochak (Indicators)

bahut se karbanik rang aise haian, jo vilayan ki vishesh pi-ech ki ech sima mean rang mean parivartan pradarshit karate haian. in upayog aml ksharak anumapanoan (titration) mean hota hai. ye soochak svayan bahut nirbal aml,ya nirbal kshar, haian.

ha soo = ha+ + soo- ksharak

[ H In = H+ + In-]

is samy ke lie soochak niyataank ka

soo = chitr:Chemistry-45.gif

ilektrod vibhav

yadi ham kisi dhatu ko aise vilayan mean dubaean, jinamean usi dhatuvale ayan hoan, to parasaran dab ke karan ayanoan ki kuchh matra dhatu par jama hona chahegi aur vilayan dab ke anusar dhatu ka kuchh aansh vilayan mean ghulana chahega. in donoan prakriyaoan mean samy utpann ho jane ki cheshta rahegi. narnst (Nernst) in prakriyaoan par vichar karake ekal ilektrod vibhav (Single Electrode Potential) ki kalpana prastut ki.

soochak sarani

pi-kasoo = laghu kasoo [pKIn = logKIn]

soochak	pi-kas	pi-ech sima	rang amliy vilayan se	kshariy vilayan mean
methil vayalet	-	0.2-3.2	pila	baiangani
thayamol bloo	1.7	1.2-2.8	lal	pila
methil aaureanj	3.7	3.1-4.4	lal	pila
bromo phinol-bloo	4.0	3.0-4.6	pila	nila
methil-red	5.1	4.3-6.1	lal	pila
litamas	6.5	5.5-7.5	lal	nila
phinol-red	7.8	6.8-8.4	pila	lal
phinolfthelin	9.7	8.3-10.0	rangahin	lal

agar kisi vilayan ki saandrata, s (C) ho, athava sakriyata k (a), ho, to tap pa (T), par dhatu ilektrod vibhav, vi (E), nimn samikaran dvara vyakt kiya jaega :

vi = vi° + chitr:Chemistry-46.gif s = vi° + chitr:Chemistry-47.gif

vi° (E°) pramanik vibhav hai, jabaki s, ya k (C or a) ka man ikaee hai.

vibhavoan ke sapeksh man ke lie manak haidrojan ke ilektrod (Standard Hydrogen Electrode) ka vibhav shoony man liya gaya hai. yah pratyavarti haidrojan-ilektrod ka vibhav hai, jab 1 vayumandal dab ka haidrojan ek ikaee haidrojan ayan saandrata ke vilayan mean shanai: shanai: pravahit hota ho. is ilektrod ki apeksha se any ilektrodoan ka vibhav, [jaise dh+( M+) ayan ke vilayan ke sanpark mean dhatu dh (M) ka vibhav] pradarshit kiya jata hai.

vi (E)

is sel ka vibhav vi (E) hai.

apachayopachay (redox) tantroan ka vibhav - yadi koee abhikriya nimn ho-

apachit sthiti = upachit sthiti + ni (nE)

yahaan i (E) = ilektr aaunik avesh tatha n (n) = ilektran ki sankhya. aise tantroan ke vibhav ke lie nimn samikaran upayogi hai :

vi = vi°ile - chitr:Chemistry-50.gif

E = E°el chitr:Chemistry-51.gif

panne ki pragati avastha

adhar

prarambhik

madhyamik

poornata

shodh

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