Anorganik kimyo

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дН] = дн2 + дн3.

Tajribalar jarayonida ДН, va ДН

ju d a oson aniqlanishi m um kin.

Д Н

esa G ess q o n u n i asosida hisoblab topiladi:

ДН

= д Н | - Д Н

= -3 9 6 ,0 -(1 1 0 ,5 ) = -285,5.

R eaksiyaning issiqlik effekti sistem a ichki energiyasi va e n ta l-

piyasi o 'z g a rish i n atijasid ir. S istem an in g ichk i energiyasi un in g

b a rc h a en ergiy alari y ig 'in d isi b o 'lib , u n g a m o d d a n i tashkil etg an

a to m va m o lek u lalarn in g ilg arilan m a, ay lan m a h arak atlari h a m d a

y adro va e le k tro n la m in g enei^giyalari va h o k a z o b arc h a energiyalar

kiradi. Ich ki e n e rg iy an in g m u tla q q iy m a tin i o ‘lch a b b o 'lm a y d i,

faq a t u n in g o 'z g a rish i (Д U) ni o 'lc h a s h m u m k in .

T e rm o d in a m ik a n in g I q o n u n ig a m u v o fiq siste m a n in g ichk i

energiyasi a tro f-m u h it b ila n issiqlik alm a sh in u v i b o 'lg u n ig a q a d a r

o 'z g a rm a s b o 'lad i. A gar sistem ag a ta sh q a rid a n q o 's h im c h a issiqlik

energiyasi ( Q) berilsa, sistem a b ir h o latd a n ik k in ch i h olatga o 'ta d i.

Y utilgan issiqlik m iq d o ri sistem a ichki en erg iy asin in g o 'z g a rish ig a

va tashqi kuchlaiga qarshi bajarilgan ishning yig'indisiga teng bo'ladi:

AQ = (Q2 - Q i) = AU + A ;A U = U2 - U l

B ajarilgan ish esa, siste m a b o sim i d o im iy lig id a:

p =  const;  A  =  pA V   =  p(V2  -  Fj);

Qp  =  AU  + p(V2  -  K,) = U2  -  U,  +  p(V2  -  K,) =

= ([/2  +  pK2) - ( f / l + i pFi);

= H l -  U2 + P V2 = H 2;  Qp  =  H 2 - H ^ A H

H  = U + p V ;  A H   =  AU + p A V

A H  —   k a tta lik   e n ta lp iy a   deb  atalad i.  E n ta lp iy a n i  keng ay g an

siste m a n in g en erg iy asi d ey ish m u m k in .

O 'z g a rm a s b o s im d a b o rad ig a n kim yoviy reaksiy an in g issiqlik

effekti sistem a en ta lp iy a sin in g o 'zg arish ig a teng.

O 'z g a rm a s h a jm d a b o rad ig a n ja ra y o n la r u c h u n jism g a b e rila-

d ig an issiqlik m iq d o ri u n in g ichki en erg iy asin i o 'z g a ris h ig a (AU)

s a rf b o 'lad i:

V = const; Qv = U 2 - U X = A U \Q V = AU.

Y u q o rid a g ila r aso sid a quyidagi xu lo sag a kelish m u m k in :

Qp ~Q v = P&V

D o im iy b o sim va h a jm d a g i issiqlik effektlari ay irm asi s h u

g a z n in g k en gayish ish ig a teng. A g ar b u k a tta lik n i M en d eley ev —

K layp eron ten g lam asiga qo'yilsa:

p A V = A nR T

hosil b o 'la d i. B u n d a An — reaksiyada ish tiro k etay o tg an g a z sim o n

m o d d ala rn in g m o l m iq d o rlarin in g o 'zg arish i. A g ar sh u te n g la m a n i

iz o b a r v a iz o x o r issiqlik effektlari farqiga b o g 'la n sa :

Qp - Q y = A n R T ; A H = A U + A n R T

A g a r n = 0, b o ‘lsa A f f = U. A g a r k im y o v iy ja r a y o n d a q a ttiq va

su y u q m o d d a la r is h tiro k e ts a A n ni h is o b la s h d a u la r e ’tib o rg a

o lin m a y d i. K im y o v iy ja ra y o n J a rd a m o d d a m iq d o r in in g o 'z g a r is h

so n i (A n) s te x e o m e tr ik k o e ffits iy e n tla r o ‘z g a ris h ig a te n g lig in i h i

so b g a o lish kerak .

M a s a la n , su y u q s u v n in g h o sil b o 'lis h issiq lik e ffe k tin i h i

so b lan g .

2 9 8 К d a j a r a y o n n i n g

‘z g a r m a s h a jm d a g i is s iq lik e ffe k ti

— 2 8 4 ,2 k J / m o l g a te n g .

2H 2(g) + 0 2(g )= 2 H 20 (s)+ 5 7 1 ,6 k J

^ ~ ^ ^

m a h su lo tla r ~

^ ^

d a s tla b k i m o d d a la r

— 0 — 3 — —3.

B u q iy m a tn i q u y id a g i te n g la m a g a q o ‘y a m iz :

A H = Д U + A n R T = -2 8 4 ,2 -3 -8 ,3 1 -2 9 8 =

= - 2 8 4 , 2 - 7 , 4 = -2 91,6 — .

mol

E k z o te rm ik ja ra y o n la rd a s is te m a n in g ich k i en erg iy asi va e n ta l-

p iy a si k a m a y a d i, s h u sa b a b li: A U < 0; A H < 0.

E n d o te rm ik ja ra y o n la rd a esa siste m an in g ichki energiyasi o rta d i,

s h u sa b a b li: A U > 0; A H > 0 bo'ladi.

4 . 2 .T e n n o k i m y o v i y h i s o b l a s h l a r

T e r m o k im y o v iy h is o b la s h la rd a m o d d a la r n in g s ta n d a r t h o sil

b o 'lis h issiq lig i (e n ta lp iy a s i) tu s h u n c h a s i q o 'lla n ila d i. S ta n d a r t

s h a r o itd a

m o l m u ra k k a b m o d d a n in g o d d iy m o d d a la r d a n h o s il

b o 'lis h id a g i re a k siy a sin in g issiq lik effekti s h u m o d d a n in g s ta n d a r t

h o sil b o 'lis h issiqligi ( A № f,9g) d ey ilad i. B u y e rd a / — in gliz tilid a g i

« fo rm a tio n » — h o s il b o 'li s h ( о б р а з о в а н и е ) m a ’n o s in i b e ra d i.

B u n d a m o d d a n in g ag re g a t h o la tin i k o 'rsa tis h za ru r. O d d iy m o d d a -

la m in g s t a n d a r t h o sil b o 'lis h e n ta lp iy a la ri (g a z s im o n k is lo ro d ,

su y u q b ro m , io d k ris ta lla ri, ro m b ik o ltin g u g u rt, g ra fit b a b o s h q a

o d d iy m o d d a la r ) n o lg a te n g . B a ’zi m o d d a la r n in g h o sil b o 'lis h

issiqliklari 9 -jad v a Id a keltirilgan.

9 - ja d v a l

B a ’zi m oddalarning s ta n d a rt hosil b o ‘lish

entalpiyalari  (AH°f 2M)  qiym ati

Modda

ДН°а98  kJ/mol

Modda

ДН°Г2911  kJ/mol

Al(g)

326,3

H20 ( s )

-2 8 5 ,8

Al3+ (s)

-5 3 0 ,0

H2S 0 4(s)

-8 1 4 ,2

Al20 3(q)

-1 6 7 6 ,0

K+(s)

-2 5 1 ,2

A12(S 0 4)3

-3442,2

KCl(q)

-4 3 5 ,9

C(olmos)

1,828

KC103(q)

-3 9 1 ,2

CH4(g)

-7 4 ,8 6

K N 0 3(q)

-4 9 3 ,2

CO(g)

-1 1 0 ,5

KOH(q)

-4 2 5 ,8

co2(g)

-3 9 3 ,5

M gS 04(q)

-1 3 0 1 ,4

C aC 03(q)

-1206,9

M gS 04*7H20 (q )

-3 3 8 4

CaClj(q)

-7 9 6 ,3

N(g)

472,7

CaF 2(q)

-1220,5

NO(g)

90,25

CaO(q)

-6 3 5 ,5

N 0 2(g)

33

Ca(OH)2

-9 8 6 ,8

N O ,-(s)

-2 0 7 ,5

Cl(g)

121,3

Na (g)

108,3

ci-(g)

-2 3 3 ,6

N a+ (g)

606,1

Cl-(s)

-1 6 7 ,2

NaCl  (q)

-4 1 1 ,1

H(g)

217,98

NaOH  (q)

-4 2 5 ,6

H+(g)

1536,2

Na2S 0 4  (q)

-1 3 8 4 ,6

H*(s)

0

O(g)

246,8

HBr  (g)

-3 5 ,9 8

0 3 (g)

142,3

HCI  (g)

- 9 2 ,3

O H - ( s )

230,2

HF  (g)

-2 8 8 ,6

S  (monoklinik)

0,30

HI(g)

25,9

SO ,(g)

-2 9 6 ,9

N H ,(g)

-4 6 ,1 9

S 0 3  (g)

-3 9 6 ,1

H NO j(s)

-1 7 4 ,1

S 0 3(s)

-4 3 9 ,0

H2o (g )

-2 4 1 ,0

ZnO(q)

-3 5 0 ,8

M a s a la n : H 2( g ) + i o 2(g )= H 20 (s)+ 2 8 5 ,8 k J

H 2( g ) + ^ 0 2(g )= H 20 (g)+ 241,()kJ

Y u q o rid a t a ’rifi k eltirilg an G e ss q o n u n id a n q u y id a g i x u lo sa la r

kelib c h iq a d i:

) re a k s iy a n in g issiq lik effek ti re a k s iy a m a h s u lo tla r i h o sil

b o ‘lis h is s iq lik la ri y ig ‘in d is id a n d a s tla b k i m o d d a la r n in g h o s il

b o ‘lish issiq lik la ri y ig ‘in d is in in g a y irm a sig a ten g :

aA + bB = c C + dD

A H r e a k s iy a = X

m a h su lo tla r ~

Д Я ° / , 2 9 8 d o s t .m o d d a la r

1 А Д ° { т mahsulo„ar — s ta n d a r t s h a r o itd a m a h s u lo tla r h o s il b o '

lish issiq lik la ri y ig ‘in d isi; ХД

H ° ( m

dM moddalar - s ta n d a r t s h a r o itd a

d astlabki m o d d a la rn in g h o sil b o 'lis h issiqliklari yig‘in disi. A # ° reaksya

— s ta n d a r t s h a r o itd a k im y o v iy re a k siy a n in g issiq lik effekti.

M iso l: A l

(k) + 3 S 0

(g) = Al

( S 0

)

(k)

R e a k s iy a n in g issiq lik e ffe k tin i h iso b la n g :

ДН°Г298 Al20 3(k) = —1675,1 kJ/m ol;

ДН°Г298 S 0 3 gaz = —396,1 k J/m ol; ДН°Г298 A12( S 0 4)3 = — 3434,0

kJ/m ol

ДН°гсак5>а = ( Д Н ; 2И A12( S 0 4)3)—( д н ° Г29а

a i

3+ з д н ° г298 s o 3)=

—3434—[—1675,1 + 3(—396,1)] = - 5 7 0 ,6 kJ/m ol

2) K im y o v iy re ak siy an in g issiqlik effekti re ak siy ag a k irish u v ch i

m o d d a la r y o n is h issiq lik e ffek tlari y ig 'in d is id a n reak siy a m a h

su lo tla ri y o n is h issiqlik effektlari y ig 'in d is in in g a y irm a sig a ten g .

Y o n is h issiq lig i d e b (Д Н °с298) 1 m o l m o d d a n i m o ‘l k is lo ro d

ishtirokida o d d iy o k sid larg ach a y o n ish id a ajra lad ig an issiqlik m iq d o ri

tu s h u n ila d i.

c - h arfi c o m b itio n — in g liz tilid a g i « y o n ish » s o ‘z in in g b o s h

h arfi. Y u q o rid a g i t a ’rifga k o 'ra :

A H rea ksiy a —

^ Д

H c,2 9 % d a si.m o d d a la r

c .2 9 8 n w h su U u icr

K islo ta v a a so s re ak siy ag a k irish ib , 1 m o l su v h o sil b o 'lis h id a

ajralib c h iq q a n issiqlik m iq d o ri neytrallan ish issiqligi deyiladi. K u c h li

k islo ta v a k u c h li a s o s la rn in g s u y u ltirilg a n e r itm a la r i re a k siy a g a

k iris h g a n d a n e y tra lla n is h issiqligi s ta n d a r t s h a r o itd a o ‘z g a rm a s

q iy m atg a ega:

2 N a 0 H (s )+ H 2S 0 4(s )= N a 2S 0 4(s)+ 2 H 20 (s );

°neytrallanish

= 57,5 k J/m o l

K o ‘p d a n - k o ‘p m o d d a la r n in g s ta n d a r t s h a ro itd a g i h o sil b o 'lis h

v a y o n is h issiq lik lari ja d v a lla r d a b e r ilg a n b o 'la d i. S h u q iy m a tla r

asosida ju d a k o 'p jara y o n lam in g issiqlik effektlarini hisob lash m u m k in .

l ) e r is h ja ra y o n i:

K O H (k )+ a q = K +(a q )+ O H ' (aq);

-4 2 5 ,8 -2 5 1 ,2 -2 3 0 ,2

AH °eritm a= [(-251,2+ (—2 3 0 ,2 ) ] - ( —4 2 5 ,8 )= -5 5 ,6 k J/m o l

2

) n a triy n in g k rista ll h o l a t d a n b u g 'g a o 't i s h i u c h u n :

N a(k) -> N a ;

108,5 (g)

bugManish

= 108,3

0 = 108,

3) Ik k i a to m li m o le k u la la m in g a to m la ig a p a r c h a la n ih ja ra y o n i

u c h u n :

A H ° d i s s o t sii

= 2 1 0 5 ,3 - 0 = 210,6 kJ/m o l

4) V o d o ro d a to m in in g io n h o la tg a o 'tis h i d a io n la n ish ja ra y o n i

u c h u n :

H (g) ->

H + e -;

217,98

1356,2

AH°ioniahish = 1 3 5 6 ,2 -2 1 7 ,9 8 = 1 3 1 8 ,2 2 kJ/m ol

T e r m o k im y o v iy h is o b la r a s o s id a k im y o v iy b o g 'la r e n e rg iy a s i,

k rista ll p a n ja r a e n e rg iy a s i,s u y u q la n is h , e ris h , g id ra ta ts iy a , m o le -

k u la la r a ro t a ’s irla r, fa z a la r o 'z g a r is h id a g i v a b o s h q a h o la tla r d a g i

issiq lik e ffe k tla rin i a n iq la s h m u m k in .

E n tro p iy a . M ik x o z a rra c h a la rg a b e ta r tib h a r a k a t x o sd ir. F a ra z

q ilay lik , b irig a a z o t ik k in c h is ig a k is lo ro d t o ‘la tiIg a n ikki id is h b ir-

biri b ila n tu ta sh tirilg a n b o ‘lsin. S h u id ish la m i tu ta sh tiru v c h i jo 'm r a k

o c h ils a , g a z la r b ir-b iri b ila n a ra la s h a b o sh la y d i. A ra la sh is h a z o t va

k is lo ro d ik k a la id is h d a b ir tek is ta q s im la n g u n c h a d a v o m e ta d i. Bu

ja r a y o n h e c h q a n d a y e n e rg iy a o ‘z g a ris h is iz o 'z - o 'z i d a n s o d ir

b o ‘la d i. L e k in te sk a ri ja r a y o n , y a ’n i g a z la rn in g q a y ta td a n k is lo ro d

va a z o tg a a jra lish i o ‘z - o ‘z id a n s o d ir b o 'lm a y d i. C h u n k i g a z la r

a ra la sh ib k e tg a n d a u la rn in g b e ta rtib lig i k a tta b o ‘lad i, ajra lg an h o la t

esa ta rtib li h o la td ir.

H a r q a n d a y s is te m a o 'z in i n g b e ta rtib lig in i o s h iris h g a in tila d i.

T a rtib siz lik n in g m iq d o riy o 'lc h o v in i b e lg ila y d ig a n h o la t fu n k siy asi

e n tr o p iy a d e y ila d i v a S b ila n b e lg ila n a d i. M o d d a n in g e n tro p iy a s i

u n in g sh u h o la td a tu rish e h tim o llig in in g lo g arifm ig a to 'g 'r i p ro p o r -

sio n a ld ir:

S = k - l n W

B u te n g la m a B o lsm a n te n g la m a s i d ey ilad i. к — B o lsm a n d o i-

m iy si. W — s h u h o la tn in g e h tim o llig i.

S is te m a b ir h o la td a n ik k in c h i h o la tg a o 'tg a n d a g i e n tr o p iy a

o 'z g a rish in i o 'lc h a s h m u m k in . Iz o lirla n g an siste m a d a en tro p iy a n in g

o 'z g a r is h i S q u y id ag i fo r m u la b ila n ifo d a la n a d i:

D

2

-holatdagi tartisizlik

J — Д |^)

1

-holatdagi tartibsizlik

E n tr o p iy a n in g o 'lc h o v b irlig i — J /m o l- K .

M o d d a q a ttiq h o la td a n su y u q h o la tg a , su y u q h o la td a n g az

h o la tg a o 'tg a n d a u n in g e n tro p iy a si o rtad i.

S iste m a e n tro p iy a sin in g o 'z g a ris h i issiqlik m iq d o ri o 'z g a ris h in i

a b so lu t h a r o ra tg a n isb a tig a ten g d ir:

bunda: AQ — issiqlik miqdori o'zgarishi; T — absolut harorat, K; entropiya

birligi J/m ol-K .

M is o l. 1 m o l m u z n in g e ris h id a e n tro p iy a o 'z g a ris h in i a n iq la n g .

Q — m u z n in g e rish issiq lig i, 6 0 1 6 ,4 3 2 J / m o l; T = 2 7 3 ,1 5

A 5 = £ 0 - =

6 0 1 6 , 4 3 2

= 2 2 J / m o l K.

273,15

S is te m a h a jm i o rts a , u n in g e n tro p iy a s i o rta d i.

1) C (grafit) + C 0 2 = 2CO

2V

S[ S2; S 2 >S , AS = S 2 —

2 ) N 2 + 3 H

= 2 N H

l v

S is te m a n in g h a jm i k a m a y g a n d a , e n tro p iy a s i h a m k ic h ra y a d i:

ДS < 0.

A g a r re a k s iy a d a s is te m a n in g h a jm i o 'z g a r m a s a , u n in g

e n tro p iy a s i h a m o 'z g a r m a y d i:

H 2 + C l

= 2H C 1

l v

А 5 '= 0

K im y o v iy ja ra y o n la rn in g o ‘z - o ‘z id a n s o d ir b o ‘lish ig a ikki n arsa

ta ’sir qiladi.

B irin c h id a n siste m a o ‘z in in g en erg iy asin i k am ay tirish g a in tilad i.

Z a r r a c h a la r o ‘z a r o b irik ib y irik z a r r a c h a la r h o sil q ilis h g a in tila d i.

C h u n k i k o ‘p b irik ish re a k siy a la ri e k z o te rm ik re a k siy a la rd ir:

2 H 2 (g) + 0 2 (g) = 2 H 20 (s ) + Q;

(Д Н < 0 )

C aO (q) + H 20 (s ) = C a (O H )2 (q) + Q; (A H < 0 )

B u r e a k s iy a la r t o ‘g ‘ri y o 'n a l i s h d a b o r a d i, c h u n k i b u n d a

s is te m a n in g e n ta lp iy a s i k a m a y a d i Д Н < 0.

I k k in c h id a n y irik z a r r a c h a la r p a r c h a la n is h g a in tila d i, c h u n k i

b u n d a u la rn in g e n tro p iy a s i o rta d i:

2 N H 3(g) = N 2(g) + 3 H 2(g) + Q;

K im y o v iy ja ra y o n u c h u n e n tro p iy a n in g o 'z g a rish i (Д5) s ta n d a rt

s h a r o it d a m a h s u lo tla r a b s o lu t e n tro p iy a s i q iy m a ti y ig ‘in d is id a n

s t a n d a r t s h a r o i t d a d a s tla b k i m o d d a l a r a b s o l u t e n t r o p i y a l a r i

y ig ‘in d isin in g a y irm a sig a teng.

Д

S reaksiya —

298

dasl .moddalar

'У ', ^

298

mahsulotlar'

B a ’zi m o d d a la r n in g s t a n d a r t e n tr o p iy a la r i (S °298) q iy m a ti

1 0

-ja d v a ld a keltirilgan.

10-jadval

B a ’zi m oddalarning sta n d a rt en tro piyalari (S°298) qiymati

M odda

Co

° 298

M odda

C°

й 298

Modda

Д 298

Ag(q)

42,55

Fe(q)

60,29

NaCl(q)

72,36

AgBr(q)

107,1

FeO(q)

60,75

N a2C 0 3(q)

136,4

AgCl(q)

96,07

G e(q)

31,1

O(g)

160,95

Agl(q)

115,5

H + (s)

02(g)

205,04

Al(q)

28,35

H2(g)

130,52

0 3(g)

238,8

B a C 0 3(q)

112

H N 0 3(s)

156,6

O H -(s)

-1 0 ,8 8

BaCl2(q)

126

N H 3(g)

192,6

P(oq)

41,1

Ba(N03)2(q)

214

H20 (g )

188,72

P(qizil)

22,8

B aS 04(q)

132

H20 (s )

70,08

Pb(q)

64,81

C(olmos)

2,36

H 20 ( q )

39,33

S(g)

167,75

C(grafit)

5,74

H 2S 0 4(s)

156,9

S2(g)

228,08

CO(g)

197,54

KCl(q)

82,56

S,(g)

377

C 0 2(g)

213,68

K C103(q)

142,97

s,(g)

444,0

CH4(g)

186,19

K O H (q)

79,32

S 0 2(g)

248,1

CaCl2(q)

113,8

M gC 03(q)

65,7

S 0 3(s)

122

CaO(q)

39,7

MgO(q)

26,9

Sb(q)

45,69

C a C 0 3(q)

92,9

N 2(g)

199,9

Si(q)

18,82

Cl-(s)

56,54

N H 4N 0 3(q)

151

S i0 2(q)

42,09

Cl2(g)

222,9

N O(g)

210,6

S i0 2(shisha)

46,9

C r 0 3(q)

73,2

N 0 2(g)

140,2

Sn(q)

51,55

C r.O ^q )

27,15

N 20 5(g)

355,7

ZnO(q)

43,64

M a s a la n : N 2(g) + 3H 2(g) = 2 N H 3(g)

H a jm k a m a y g a n i u c h u n e n tr o p iy a k a m a y is h i k u z a tila d i:

A S ° r = X

S O N H

3

_ S

( S ° 2 9 S n 2

+ 3 S ° 2 9 8 H 2 ) =

= 2-(1 92,6)- [199,9+ 3(1309,52)] = - 2 0 6 ,2 6 J/g rad -m o l.

J a r a y o n d a h a jm o r t g a n i u c h u n h a n e n t r o p i y a o r tis h i y u z

b e ra d i:

AS°r= 2(197,54)—(5,74+213,68) = 175,66 J/grad-m ol

A g a r ja r a y o n d a f a q a t q a ttiq m o d d a la r is h tiro k e ts a , e n t r o

p iy a n in g o 'z g a ris h i n ih o y a td a k a m b o 'la d i.

S u y u q m o d d a n i n g b u g ‘g a o 't is h i, k ristall m o d d a n in g e r is h i,

q a ttiq m o d d a n in g s u y u q la n is h i k ab i ja ra y o n la rd a e n tro p iy a o rta d i.

B u g 'n in g k o n d e n s a ts iy a la n is h i, s u y u q lik n in g k r is ta lla n is h i, h a jm

k a m a y ish i b ila n s o d ir b o 'la d ig a n ja ra y o n la rd a e n tro p iy a k a m a y a d i.

M asalan :

H 20 (s ) = H 20 (g )

70,08 188,72

AS°r .= 1 8 8 ,7 2 -7 0 ,0 8 = 114,64J /g ra d -m o l.

Iz o b a r ik iz o te r m ik p o te n s ia l. H a r ik k a la o m iln in g re a k siy a

y o 'n a lis h ig a t a ’s irin i o 'z i d a m u ja s s a m la s h tirg a n h o la t fu n k siy a si

G ib b s energiyasi d eb a ta la d i v a G harfi b ila n belgilan adi. U en talp iy a

v a e n tro p iy a b ila n q u y id a g ic h a b o g 'la n g a n :

G = H - T S .

I z o b a r-iz o te rm ik ja r a y o n la r d a G ib b s e n e rg iy a s in in g o 'z g a ris h i

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