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811 hilu bie! vi cdu. true, niing l-u(/ng va ca cke" phdn l1ng dlli gidi cdc quy lutJ,t diin bi~n cria m9t qua trinli h6a hoc la nhiem v~ hang dtiu elia mon. hoc ROa IY. N6i each khdc, ndm ch&c cdc kitn thltc hoa Ii se giup cdc nha khoo hoc hilu stlu s&c han ban ch{{t cua qua trinh h6a h9C.

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Mu6n hiiu drtflc diiu nay khong the" kh8ng tinh thong. viqc gidi cdc -

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-biti tQ,p hoa IY. -Lam alivc nhu: v{iy khong hoan. loon dan. gidn cluu: ntlo

bdi vi til Ii thuyet d(n bai t~p lit cd m,9t ch{ing dr.titng quanh co khuc khuyu phai ton khIJng it niing 1uvng moi vu(/t qua nOi ?

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Bai tQ.p hoa Ii dl/fle xudt ban bang titng nude ngoai khcf phong ph';'

. song b&ng titng Vi~t, loai tai li~u nay l{li chua nhieu. Chink vi v~y cluing toi manh. dati suu. tdm, chon. 1{JC v~ pluin. 10".i de' kink thank CUOIt

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Biii tl}p /l.oa lj eo sd. Cuon bai tl)p nay dz/{JC chia thank 5 ph/in. gom 19

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- chuang khac nhau bao tram hdu nhtr toan. b9 cdc van dl cud chuang

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trinh. hoa lj hiqn hanh. ..

Be' ell dang cho nguiti doc trong mai chuang cluing toi lai chia lam,

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ba de muc .

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o phdn nay ohting tIJi tom tdt nhftng k_hdi niem, dinh. nghia va cdc cdng thuc quan trong de' giup d9c gid lam cac bai tij,p d hai pluin. tilp thea.

Do tinb. ch({t pluic tap clIa h6a Ii nen. cluing tdi chon

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m9t sit ~ng bai ttJ,p dr;ti d~n co liJi gidi c~ thl nhdm

phdn nao gidm bOt kh6 khan khi a9c gia gidi oic bai

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t(ip khtfc d phd..n Ill. (Di nhien. mdi dang bai t~p eo

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nhiim.nflng cao sue sang tao va vg,n dung Zf thuyet

vao bai ttJ,p.

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Trong qua trinh. bien 'soan. ·cu6"n' sach: chf:tng toi da dll{lc 8T! cd vii. va

gop yeua nhie'u dang nghiqp, song ch&c ch&n vdn con nhieu thi(u sot:

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hoa hoc 9

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Chztdng-2. Nguyen ly thii hai ella nhi~t dq:tlg 11Ic hQc'-vs. 'ca~ th'~

Chuang 3. Chuang 4 .. Chuang 5. Chuang 6.

nhi~t dQng. . , _. ; , .,3,3; ·

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C" b~ h' h "A b~ h '. 55

an ang 08 qc v~ can ang p a ~ ~ ~.~ 9 -.

Dung djch chi't khong di~n ly 93

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Dung djch chift di~Ji Iy . 117

Nhiet dong 111'c hoc th6ng ke 1·23

411 • • •

Philn B. DONG H6A HQC VA xOc lAC

Chztdng 7. D{tng hoe cua cac phin ling ddn gian va phlic t.ttp 141

•

Chztdng B. Ly thuyl!t t6c dq phan ung _· 181

ChlMng 9. . Phan Unl( Quang h6ahqc va phan -Ung day chuy«!n 197 , .

Chuaru; 10. Xue tac dang th~ va di thl· ais .

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Phin C. DIGN HOA HQC '

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-Ch~dng 14.-An moil va bao v~ kim loai ~ 275

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Chuang 16 -. H~ keo va tinh chit ~ 299

Ph~n E. H6A HOC LUQNG Til' CO so

clilirmn 17. Dai clidJIg v~ cd hoc llidng t~ ~ 'IIII.~'1111 317

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Khi mQt h~ nhiet dQllg hrc i thuc hien met ehu trinh (qua trinh

d6ng) d do n6 nhan tit moi truong ngoai lnQt'1tttJlig'ilhi~t VC) cling 11ho 5Q va sinh, ra cho ben ngoai, mot cong VQ 1 cuug ,l1hikSA. th:it ,giuarhai dai

II) ....

luong nay co mot su tuong duong duoc th.e, hien hang phll<;111g~tr~h: ;',' Jj <{~; i

" l8A= J loQ

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Dai 111<Jng J phan anh st;l ilidng duong' gina hhi~t ~ va cang va dtlQc goi 1a duong luong cd hQC cua nhi'::t'.Khi Ava:Q, ddQd'bi~'u ihrbd.ng cung

mot don vi thi

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, Trtrcng hop h~ khong thuc ,h~~n chu .trmh, ~ftG la",lt~ kho~g trd lai

trang thai xuut phat thl: "

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va do d6 oQ - SA *- O. GQi hieu (6Q - cSA),biing dl.I, ta co dol voi qua trinh

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Chuong 1. NGUYEN LY THU NHAT CUA NHlff D9NG LVC Hc;JC

dU = 8Q - oA

(1.1)

DO'i voi mQt qua trinh hiru han khi h~ chuyen tit trang thai 1 de'n - trang thai 2 thi

J

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1

D6i vdi mot chu trinh:

..

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$d U =i8Q - joA = 0 :';~\:

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, , , Phuong trinhnay cho thay dU 13. mot vi phan toan :phiin ella' met

ham trang thai nao do ella he, d61a ham nQi nang U cua h~.

~

" " ' " Ph.t!(1ng. triuh (l.i) 'bl~u tP.l..·ngi dung cila nk\ly~n:Jj; thu nhat cua

• • • • ~ • .' I .... -.t I ..... I, r.... I I •

•• .' '. . _ r.: . •. r' .. . I

nhiet dQng hjc vie't cho qua trinh vo cling nho. D81 vdi qua trinh htru han .

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, ' ,; ,',~ ,:,:' ;:,: " < '.'. ' ',. : AU'·= Q,-'A(', -: I~ r" .,,' "" •

(1.2)

Nhiet Q va cong A 13. hai dang chuyen hoa cua nang luong, do

~ .

d6 neu h~ nhan nhiet iu ben ngoai thi lucng nhiet do duoc tinh 18.

duong (Q > 0), trai lai neu h~ mat nhiet cho ben ngoai thi Q duoc tinh 13. am (Q < 0). Quy udc ve dau nay cung duoc ap dung chocong, tile 13.,,:

A < 0 khi h~ sinh cong cho ben ngoai, ,

. ~ .; '. .'. .. . . .

A > 0 khi h~' nhan cong. tit ben ngoai .

. - .

Vbi 'S~ chap nhan thong nhat v~ 'dau nay thi bi~u thitc t03.1t cua nguyen It thir nhat duoc vi€t nhu sau:'

. .

~ .

dU = oQ + oA doi voi qua trinh vo cung nho,

, ,v a ~ u ~Q -I:- A doi voi q us. trinh hiru han.

. .

Trudng hop cong A chi la~ cong g~n 1,ien vdi s~ thay dcSi th~, tich cua

"1'-.' .

h~ thi doi vdi qua trinh thuan nghich nhiet di)ng

&A ::: - PdV hoac ' J BA = - j PdV' = - P (V? - V1)

1 1

A = - p~v

~

r

~ . .

Tit bieu thuc toan cua nguyen ly thu nhat, vdi su thay SA = -PdV,

III •

ta co

.

. dU = BQ - PdV hay oQ = dU + PdV = d(U + PV)p

-

- ~:

•

....

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BAI TAP HOA lV·CO SO

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It.

Dai luong U + ,PV ::::; H, duoc goi Iil entanpi -va IA ffiQt ham trang thai cua he .

•

, . .

Ap dung nguyen ly thu nhatchoqua trinh dAng tich (V == const) ta

~

co

au oQv

dUv = oQv hay -or = dT = Cv

v

,.

Cv; la nhiet dung dang tfch.

D5i vdi qua trinh dang ap, 'mQt each tuong t\1 ta co .

(1.3)

..

. 8H dHp = SQp hay or

p

.

_ 6Qp _ C .

- - p

dT

r j ,/

Cp: 13. nhiet dung dAng a p

Thucng nhiet dung duoc quy ve 1 mol ch5t. 6 P = canst nhiet dung mol dAng ap 13. mdt dai luong phu thuec nhiet dQ va dircc cho dudi dang phuong trinh kinh nghiern:

_ Cp = a + bT + CT2 hoac Cp =a' + b'T + c' I T2

~ .

:> Ap d",ng nguyen Ij thu nhfit cho khi lj tllang

oQ =: dU + PdV RT

= CvdT + V dV

oQ = CvdT + RTdln V

, I

(1 'mol khf ly tUdng)

(1.5)

Thay Cv = Cp - R, bi~uthuc oQ ella to:

oQ = CpdT - RT ._ _ (1 mol khi ly tUdlig)

~ .. . ..

_.. ;

"? .' : .

Cac bien thuc cong va nhiet trong qua trinh thuan nghjch.

- Qua trinh d~ng tfch (dY = 0).

cSA = -PdV = 0 ~ Av =; 0

oQ = dU + PdV = dU ~ Qv = j CvdT (Lmol) ..

(1.5')

•

..

- Qua trinh dAng up (dP = 0)

.A _. ; ~, .A,A

Chuong 1. NGUYEN LY THtI NHAT eUA NHIfT.tDt)N$.!LVC'H9.C

_

;, j'8A ..... -PdV ;" Ap = - J-PdV == -P(V2 - Vl)

1

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., ~ :.;, . = -.PV2 ·+.~~Vl· = -'RT2 + RTI

, I

r .... -

Ap .- RAT· (1 mol)

(1.6)

L.

. .

oQp = dHp = CpdT

Qp = :*Hp. = j c.ar :(lm~l)

J . . _ . •.

_ T1

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- Qua trinh dAng nhiet (dT' = 0)

L

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(1 mol)

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AT = - RTln . (l·mol)!

P2

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AUT = QT +AT:= b (h.~ qua cua dinh luat Gay Lussac - Joule)

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QT = - AT = RTln (1 mol)

Vi

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- Qua trinh doan nhiet

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, _ .. .: ~ .AU. Q + A = A .

I - • • 4 • • •

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D~ sinh cong (A < 0) h~ phai lay vao nQi Dang nen nhiet d9 ha

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xuong (T2 < Tl) ,

:~' :),,'" ~ ~,:~U, .r C~dT (1 mol)

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Cong dan doan nhiet c6 th~ tfnh ttt phttcfng trinh Poisson' P.VV = canst· vdi y = Cpt Cv .

Hieu ung nhiet eua qua trinh va dinh luat Hess

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Cac he thtrc

ill

SQv = dUv hay Qv = AUy

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. r i -

'8Qp = dHp hay Qp = L1Hp "

bi~u thi thuc chat cua dinh luat Hess vg hieu ilrig -){1tl~~' dBR~r~tdti'~1 dang ap cua qua trinh. Giira ,Qp,vA,'QvcomOi ;q'UaI,.'h~~, : tc}, ~:'i :I~; :T

t

.

- 1,·

·1.

- ,

(~.9)

vdi L\n la bien thien 86 mol khf ciia qua trinh, r. '!, (','. I s]: .: •

. .,:. . ~ -. . ~ ~ - ... ' i ~ ~.. , L ~ .. " .. '1" <>: . .; ~ I .... j

. I...

Dol voi phan ung hoa hoc d T = canst, P, t::: const, hieu (1ng nhi~t

cua phan ung diroc tfnh dua vito nhiethinh tpi,nh poij.C( phi~t d6t chay:

• I. • ...

• • I I

. , ,

AHp.u = r (AHhJcuOl - ~ (AHhJd'u (1.10)

. .

l .._ • .

AHp.u = l: (AHa.c)diu '_ r (AHd.Jcui.;\~L> i(j; /),~) qAT (t11~!

. (j digu ki~n chuan P ::::,1 bar; T'= 298ita C6:'cic'gIa't~f~Ho, r.1

. - : '. . , . \ . ~ = , f ~ t.' ~ ~ . r [ ~·I f j i~'" ~ ~ r 1 ; ,.. ;. -} . ~ .'l t ... ? I i:.. ~: t· , ./ ". ' .

• I I " _ . II _ 'I • _ I ... Ir I 'I .£ Ii I ... _ .. ,._ .. I _ .,.. .. _ :Ii .. 1.

, . 0 - . 0 L ·o,·.r .. ,

AHp.d :::: I (L\Hht )cu6i - r (AHht )d4u. , '

• - .• -. j _.. - i,. . ~ .. . ! ~ ,.. "'! ~ f~' ,. r t- (r .

• -L ~ .. "III: I "I. _ I ~ . _ ... '. "I I I' .r

. . -

o _ 0 . 0 '

AHp,.u' ,'- ~ (AH,d.c)~i~,;- .. ,~:(D;¥d.~}~¥6i j '.i';~ :/.'.'!.'*':;I:. ::;

Ngoai hieu itng nhiet ella ~p,~n.,fW.g ~6~ :h9Prr~P!.~l~~l.\;fm.If~·phi~t cua die qua trinh It hoa khac nhu nhiet hoa tan, nhiet hydrat, nhi~t

. ,

trung hoa, nhiet di~n ly, v v, ..

• I; I I I.-or.

'. • _ ,- ~. ", J ( j .' - ,

= Anh hUdng cua n1ii~td9 tm.:hi¥,';': :Una nhi~t 'f, " ." .. ~ i, .:

- ...

8\1 phu thuec nhiet dQ cua hieu ung nhi~t dl1(1c th~thi~n·bAngf dinh

lui}. t Kirchhoff, theo do h~ so' nhiet ~Q ciia hieu itng nhiet bang bitn, .

thien nhiet dung: ",f'

oAU or v

= ~CV euOl .:... LCv ddu = ACv

t • • \

..

. ~

_ _. J. •. ~ J , ... { L .' .. • _. u{l 12)

. , . r I i > .,~., J t

- _. .

, J -

. .. .

BAH

! or ' = l:Cp cua'i _ LCp dairi =ACp" ;: ': ;' ',i~-.P (;" ~. (1.13)

, t .

P . ,

- -

. .

Dinh luat Kirchhoff cho phep tinh hieu ilng nin~t';IJ in~iilhi.~t, dQ .

. -

khi d"", b·"'t hie ~ hi ....... t ' ....... t nhiet A'" kh" , .~ - ( .... { t

a Ie ~u trng n ~ d mQ ~ 'uQ· ·acjI i.,. ' • .;. ; . t c.. 1 i ...

Tl1u. C va;".. y - , '. I; - I : 1· I ! , ~; .~. : ~ ~ ~ '·1 · ~i· .~; r ~ :. ~.

• . I .: 'I" ~ _ - I 1 . II .... -r _.. ~ -

,

, , - ~ I' , , ' . ; ""I· II. .: '"I •. .-

1 ' , , • - r •. -, 1; - ,

./

. (1.14) ( "l

14

. .

.A , ; ""., A..,..

Chuang 1~ NGUYEN LY THU.NHAT CUA NHIrt'D.9NG tvc HQC

....

n~u hCp Iii hang so

-

- ~ ~

trong khoang T 1 d~~ T 2.

. .. ) .

Truong hop 6Cv phu thuQc T dirdi dangphuong trinh

~Cp = 6a +'~bT + L\cT2 + .,',

th! 6HT2 = AHrl + 1 (Aa + 'dbT + L\cT2 )dT'

• . l· . Tl

• I

..

II. BAI TAP c6 LOI GIAI

lilt

(

1.1. Mgt lut1ng 0,8,50 11101 khf ly tl1dng d 300 K duqi ap "sunt 15 atm, duc;Jc din Dd dAng nhiet toi ap suat 1 atm. Tfnh cong thuc hien:

I .

a) trong chan khong:

•

b) chong ap sunt ngoai khong d6i bang 1 atrn, va '

.

"c) nlQtcach thuan nghich nhiet dQng.

• I

ou:

.

II

a) P ::: 0 ~ - Pt1 V = O~ vf}.y khong cong nao ~.tt<;lc thuc hi~n

"A = _ nRTP2 1 ~ 1

" P2 PI

1 I · (1 11

. = -(0,850 mol) (0.082 atm.ZK mol") (3001{) (1 atm) l-----·-- - _ )

. ~. . l.atm Ifiatrn

I

,. .

..

= -19,5 atm. 1

= ~19,5 x 101,34 J = -1980 J

Chu y: neu su dung h~ don vi 81 thi R= 8,314 JK-1 mort va 1 atm = 101.325 Nm-2 (101.325 Pal.

'-

c)

•

-

~ ..... 6 1# •

BAI·-TAP- H A LV CO-SOT'

.. '

-

.... l' '- . _ ' .... : • . ..

-. ~ . -' ~ . r : • '; ~ + r,

.: I. _'. .. ". I: ~:. .' '; I. I ... . I,'

• •

• . , - r I' •

• I' _ • • I

I. I. .. .

i~5

. _.. -.... ... - - - -

• r.. r - _.. .. r " .. -

- .... ' . l: . .. ,f v . ~ ·1-5

.. . ' I ' . I

. . - .

= -0,.850, x 8,314 x 30(,), x In 1 ·':1

. ... l

. ~, ,

~ 1 -:. .' ~

= -5740J '

. :

• ., ,.., 1

..

;

,. .

; ,

,

r ... ~ j: ..

I '~

I ..... tr

. ,

I .•.

1.2. Tfnh bien thien nQi nang khi lam bayhoi 109 nude d 20°C.

Chap nhan hoi nude nhu khf ly tuong va ,bo, .qua th~tich nude long. Nhi~t bay hdi cua nude d 20°C bang 2451,824 JIg.

• I' ~ I

;

,.

.. .., ,~-) ~ - . ~

, ~'l \·1

.. f 'J ''PI- . ~'"..

. ,

~

, _ J

. .

Gidi

Th~ tfch cua hoi nude a 20°C va 1 .atm: . g RT

V. ~ M· P

. --

. .

I L ~ ,

.• r

'"

I '

_ 10 0,082.293 = 13,35l

18 '... . 1 ~ f· f •

.. ~ / 'I'

. '.' ; , l' ., 1

-.. II. r" I _. _. I ..

I 1

1 - -. :

- J' •

Cong dan nb hoi JIUdc A = -PL\ V ~ -PVh r = -1 x 1·3·,35 X_1 10·'1.,34 " ~. E = -1352,889 J .

~ .

ir ..

~ _ ....

, .

Q = 2451,824 x 10 = 24518~24 PJ.

~ ~ . j 't- , ... . .. ~ ~ ~.. ; \") ... r ; .' ~ -~. _ .

. ~j;.i~ ~s~"'- ~ ~ s . r_ '. "

. , . ., . i

j + .

Bien thien nQi nang Atrkhi lambay hoi 109'1l\10C:

.,. ,

, .

. f

L1U = Q +A

. .

., ~

, - ~. .

_r

, . .,

, ,

.~ ! , i

= 24518,24 - 1352,889 = 23.165,351 J

. . .

. t .1. =

, : 1· ~ f

-, ,. .:.. 1 -

.. _. • _~ • ~ I ·',.r ..

1.3. 100g nito d oOe va 1 atm. Hay tinh Q, 6U, A.;Idri:

P. ,

- I ~., ~

.. ,- '. 1- - . ·t :1'. t .. -..,

a) dan da.ngnhi~t'dei1 th~ tich 2001; ";.; i' ,. j' :<":

b) tang ap suat toi 1,5 atrn, khi tll~ tfch khong d6i;

~ ....

.. . . .. .. =-... I .. ~ J:

\ - , I .•..

L : -...,,' .• . - .; . . (,. ~,. :" . ,-

c) dan ddng ap toi th~ tich gap doL'· ·

1 -

. .. .~

• .t ..

, ~ . ' )~ ..

Gidi

..

I • r.. - ." - . I

:' , . I· I·· . . .•. .

• '... . t... .. . . I' . I 'I •• •

.. l .

l .

J

-: .J ."-'

. I.·

;,

a) Ap dung cong thuc 6U = Q + A = 0 do ,d6. .. . ;. !

... · ." ' ' ': . , . . - { .. ' - -, '.' I, j. ~~ 1 -, f ~ I _ . .: f· ~ • :,., ~.~ 'J ~

. '.. .. I . i '. . _ • rl • • • -:. . t ~ I 'I" •• ' T .... .., •

. ,

. ., Q'.. A ,.. ., R' T- II · V 2.' ,., : · ~ .. ~; i \ . ~.I; '.:; ., ,r,: :i ., ' .'-.,

··T=-.T=n n 1_, t, .,. , •

··V ~ f' , . I ~-

~ . ~ . - L". I' ~ t •. ~

,. .. ~. . ., . 1 ' ., t ~ .,. ' .,. 1 1 . t , ' - • , .

. I _ ~ . . I : • . . ... ' .. _.. _ . . . . _ - ... . ~ . • I .... I

F ,~~. ., ' •• ~. ~

f 1··'·,· .. J r f ~; ~'. ".,: : -, 1 ~ ~~ ~ • -.

: ," ~ .' . ~ '. . j. _, ~_ ~..1 j . , ~ • • .. .. ~ • '. f 1 '. -; r , ~

' ...

'\

16

Chirong 1. NGUYEN LY THU NHAT CUA;NHltr DQNG LVC Ht;'C

-

VI = nRT = 100 x q,~~2 X _~73 :::: BOl

. PI . 2S'x 1. . ·

100 . . 200 4

·QT = 28 x 8,314 x 273 x In 80 = 7427,60 J

. ,

. . . . .

,".. ..

, , '

. AT ::: -7427,60 J

~ .

o dieu kien dang tich

= 273 1,5 = 409,,8J{

1 ':.J

, ~

100 . -

Q = x 5 x 4,18(409,8 - 273) = 10~132t32J

·28· ...

. Av= 0 ~·&U = Q +··A·:; Q. AU = 10.132,32 J

. -

c) Doi vdi qua trinh ding ap:

•

... ~.

Vi

. .

v-

T2 = Tt'" ._t = 273 x 2 = 546 V·

t

.

I .... • •

Cp = C",+ R = 5 + 2 = 7 cal. K-1.mor1

... ·'100 ......, ... ' .. ..

Qp = .28· x 7 x 4;18 (546 - 273) , 28.365~48":

. ,. ~ ~ . ~ . _. :. ~. - 1 oo ... ~ -~. - . .., .: . . i ! . .

Ap . -nR(T2- Ti) ~ . . . x 8;314(546 - 273) = ~ 8106,15 J

2 8 . I • ,I ~: - - ~ • -. '.... .. -

• __ •• L. _, •• •••• 0:... - _

. ,

.

~U = Q + A = 28.365,48 - 8.106,15 = _20.259,33 J

. - .

,.. ... - ............ -. . ...

. .

t •

1.4. Tfnh nhiet hinh thanh cua propan a 2~i8K dudi aI) suilt 1 atm

trong hai trudng hop: a) dAng ap, b). dang tich. Bi6t nhi~t dot chay ella

- . . -

propan bing ...,2220 k-I.rnol", nhiet hinh thanh cua nude bdng -286,0'

k-I.mol". va nhiet hinh thanh cua khf cacbonic bang,"7393,~ k-I.mol'".

. . - . - . .

. I' .:i. <.>, ~ ..:\. ~ \ -

.

. "

" i _

Gidi

-, ,

• t

- , .

I

~ I '. 1 .. ;,

, :, .. (~).C3H8 + 50,2 = 3C02 + 4H20 (lJ '.

- 1 ·

(2) H2 + 2"02 = H20 (l)

(3) C + O2 = CO2

., .

o . -1

LW29B ;;;=;- 2220 kJ.~ mel"

. .

. MI~'!:' ~~86:0lkJ1.motl

-

. . • I . . L

,. " . - \. 1

o· .,

~H298 = -393,5· kJ .mol"

"II

I· ~

- . I ." _ .

Vi),n dung dinh lu~t Hess bing each lay phuong trinh (2)x. 4 r6i

. .:. . • .. ' •. ,..I. "1" " I

: . '..' ,~ . ,.' j ~ I , ., ~ i . I .

cQng vdi phuong trlnh (3) x 3, ta diroc ,_.- - · - .. '

. "l

. j' ~ (4) 3e + 4H2 +502 = 3C02 + 4H20 . . L1H~98 =·:-~324,5 - .

. - . - ~. , ,

.. , . ., . ~, . ~. .

Lay phuong trinh (4) tru di phuong trinh (If'(tl1c;Jc : .... -

3C + 4H2 = C3H~ , _. ;Lili~9i', = -lQ4'i5 kJ.mor1

fiR = 6U + Pl1 V ::: aU + LlnRT ~ i\U= All _ ATiIt,,-! ; , .:; r f •• ':c.,

, -

. ". : ~ .. i

. " . r ..).~:

. , . : . 1_ _ " ." 1. ~ . . .

. \.. I , t

i !. 1 .

• L

. '. aU:;::: ~104,5 - (-3) x 8,314 x 298.10~3 =1 .. 97 kJ._mC)r1 ;'_": .. .) ir)\ I, ..

- 1

. ,

I ; "~ "

- .".. ~ ..-

1.5. Tfnh nhiet hinh thanh dung dieh nude ella hydro peroxit d~

.. :. .:

I • r • I

• f!' ..... • r". i

" " "

, .

vito cac dtl kien sau:

•

~. -~. ~ ~

1_ :.) , ~. ~:

(1) SnC12 aq. + 2HCl aq, .+ H20·2 aq. :::; SrieL. aq, T-~H2·0i . ~.- ~.

'. AH = -371,6 kJ.morl

. . -'- .

(2) SnC12 aq. + llCl aq. + HOC} ~q .. = SnCI.. aq. + H20- -

-1 . ... Mi = -3l4,O.kJ.mol

. . I .

f .

, II .

. . ~.. .

(3) 2HI aq. + HOC} aq~ = 12(r) + He} aq. + -H20.

I· ...... ..

.' 'AH-~ -215,2 kJ.mor1

T

., • , " • ..1

- .... !-A# =- -55,1 kJ.morl

Gidi

MI = -286 kJ.mol-l.

.: f

I ": •

. . '

. J ,"

r .

.. : .

. . i

• 111& iiiIIIcalili4£ .......... ~ ..... .-... .................. •

V~n dung dinh luat Hess vao phan ilng xay ra trong dung .dich,

Nhan vdi 2 cac phirong trinh phan itng (4) va (5) r6i tm «Ii nhau, ta

. ,

. .. . :

"dUde:

• •

. .l!)-O_b., ... ~ __ VJ- .. 1..{_& ~ _ ..

, , .

, : ,. :. - .... ;.: : - ' : . ~: .' ; 1

zrr ~ ~462,O kJ.mol-

, , ,

. • i· . .,.. .r ,. . rl··'-" I •

I I' I- • ..I'.:." r ", 1 :!.~ I; •

...

\

_. ,_..- . .

(6) H2 + O2 + 2HI aq.'~I2 (r) + 2H20

.... -

18

Lay phuong trinh phan ling (6) tru di phuong trinh (3): ,\l::~(.~ (7) H2 +02 + Hel aq, = HOCl aq. + H'20 :,,l, Afl='--2'46,8 kii>'morl

..

(

Lay phirong trinh (2) cqng vdi phuong trinh ,(7): .',' , ,!,~ i:"

. I -' .. . i ..... :Jo J

, . ~

~

(8) H2 + O2 + Sn'Cl, aq. + 2HCl aq. = SnC14 aq + 2It20 _ _,

j _ , . . r. ~ '. : __ . _' ~ ~ '\ :. r. ~

. . 1

~H = -560,8 kJ . mol-

. ." _ .. J.

. . . .. . .. [ .... (' ~ - ". I' .

I • r I I] . I I

Layphuong trinh (8) 'trit di phuong t~IUh (\):' :',;,:: " .'~ :. " r""

t· . : 1 • , .. .• .~. .•. . ~ ~ _ f _... I , . ..

r J -: _. .. -

· -1

H2 + O2 + _aq = H202 aq. ", , " ' •. _ !o. >~H ,= :-18~~2 ~~~mol

- ..... - ..

Day 13. dap so phai tim.,

, .

_ ~ . -,. l'

-' ~ : ~ . .. .

. .. "

_ r •• • ., _ . .. _. t

. .."" . . . . .'

T ....... ~_

1.6. So sanh su khac nhau giira AH va AU, doi vdi:sl1 b'ie'n dc5i v~t ly sau: (a) 1 molnude an -+ 1 mol mrdc tai 273,K IV~ 1 ,~tDl;:(b) 1 mol

. , . .. .. ( . ..':;.. ;.

nude ~ 1 mol hoi mrdc tai 373 K va -1 atm. Th~ ti~h mol ella .mrdc da va

..

nude d 273 K bAng 0,0196 ~a: 0,0180 1.lmorJ• Th~!tichj mol cuamrdc va

•

hoi nuoc d 373 K bang 0,0188 va 30,61l.mor1•

, ~ ~ .' _ I . .~. r

I' .' ~ _: c : I ; • 1 i

. . r . . . .! I . , . , 1· ' lo ~ • ). "f _ ., . ~_

Gidi

I I • .

. _.. -:. r l . f' . ... • ..

J ~ I' j I. I • I' i. ". . •

Ca 2 truong h<;Jp d~u xay ra d p,=. const, ,do' do.

... .

! "~' ~. : '. " j ;1 _. \ I

. ,

L\H = t1U + 6: (PV)

= L1TJ + p~V' hoiic- 'AI-I - ~U,'_·1PAV.- ','

III

. .

a) 6 V = Vel) - V (r)

,.

. , .

~ .. r, •

= 0,0180 - 0.0196 = -O.OO~6 I.morl

PL1V = (I atm) (-O,D0161.morl) ,-Oi,Og:16iat~.;~.b.IoI;~

. ~ ~ '.,. .'. _:., _ )

_. - -~ .

...

. ' .. , -I

.: ,= -0,16 J .. mol

• ~ _ " :10 I, ,

" , J~., " .: j J

b)

. . _

~V == V(h) - V (1) '~

.; '. t

. ,

, _

I

~

. ..

~: . . ':", '-

, ~ • f

, .,

, . ,

, = 30,61 _ 0,0188 = 30,59 Lmorl .

•

T

~ \\\ ~J . ;

. .

, PAY +=- (1 atm) '(30,591.mor1l =30,59atm~ l.mQF~ .. : "f

-. . ... _ .

, . ~ 3100J.mol-1" '-: ';_.';;~Jj;'/,

, .. ! ~ - .

.-.;~. ,

. Ket qua nhan dl1<;'C vg (~H - L\U) cho thay s~ khac nhau Hi ,kh6ng

. , " i

. ,. . .. , ~ .. ~

I • _. .. f .. " ,or f

dang k~ va co th~ hi) qua doi vdi nhfmg pha ngung ke-t, song PL1V Iai rat

_"

.... ...... ;, .,

BAI TAP· HOA LY·.CO~SO .. -· <.~.

. '.. --

" .

~

• p'l. ~ T ...... -. ~ ,,"

• . , ,-. I .. t":..;' ~

:. ~ "... '.. - ".. 'r.... Ij.f r.

! .. -,_

. -. ~. r" .

• _ ... 1 _ 01= I :

r - ~ _T. r

18.

. . . ..

dang k~ doi vd~ qua, trinh co.khf tham gia.; ~oi vlJi t~,uq~ h~P/(a) su > 6H vi khi da nang chay co su giam th~ tieh do do h~ nhan cang tn ben

'\,. .

ngoal ..

• .' I

- . j. ~ j--

pI: 1 -

,

\ I .

1.7. Nhiet hoa tan cua BaCb trong nude bing 8652,6 J. Nhiet hydrat' cua -BaC12 d~t~o ra BaCI2.2H20 'b~ng 29.134,~' ~f:· 'l.~ ;r" i-·-,( 1

- I .1.& .:. • ~

. - : " .. . f· - ~. . r f.· r ~ ~ ~ .. ~ ~: ; _.. I ~ , f {j ~·1 -. r: .- • i t ~.

Xac dinh nlii~t'h~~ tan ci;1~ Ba ~I~ .. ~Ii~O .. , ' , -' '. '," ,:. :", ,-'-:'. '~." f··SI

- .,. . ~. . ... .. ~. . . r . L I L. ... I 1 I .L; .. .t ~ ( • v '.) ~ · }. . .. ~ I ~ •• ... J ~. 1, 1

I • I • _. I : ~ '. J. - '. r . .. . I _..~. • ," • .i_.... .. p.. . "I • I • -. I I..... _ ...... t

.. "', .. ;a.

Giai

• ~ I ~~

- I .-. - ' , , 1 - -. t·- r ~,., r (:f r·· ., - I 1 ("\ J' J

~ .~~. !,.: , - :.. .' ..' I . \ j • ~ l , ~

I • r: ',- I • I I _ _. .' ~ -. .. I' .• ,,-_. - •

, . ..

Co th~ di~u che dungdich BaCh'J)dn~ hai p'hudngjpHap:':' !i~~>'

.. . ~-

. ~'''~'':II·,· .. :~~

1) 1 mol Bael2 hoa tan vao mdt luong mrdc rat ldn, tea ra 8652,6 's

··2) Tien hanh hydra t hoa Ba Cb theo' ph udng trhth phan itng

, .. : .. r I

Ba'Cl, + 2H20 = BaCI2. 2'H20" .

.

<, I -AH = -29~ 134,6 J

sau do lay 1 mol BaC12• 2H20 ho~ tan vao mQt'h.tC1ng nude rat ldn, hieu (tng nhiet se bang AHx• Thea djnh luQ.,t Hess, ,h~iq;ua trinh (1) va (2) co

. ... . .

. . . .

cung mot gia tri vS nhiet:

- t

.,..

v~y

-8652,6 z; -29~ 134,6 + l1Hx

. r .

~Hx = 29.134.6 - 8652,6 = 20.482 J _. '

; i

. _[

• r r : ~ I • • ~ ~

Su hoa tan Ba Cl-, 2H20 vao nude In inQt qua trinh thu nhiet,

. • 1 ..

1.8. (J digu' kien P z; i 'atm· 'va T = 298 K, phan ung

tOn ra 126t 445 J

~- : . . I. • ~- • f· r

-. ~ T- ~ ~ _; - ~. r: _..

.., j ~ : . I ~ I ' . - ,. . I .- ... :t. _;.

. . ~ . ~ - j , • .

Neu phan ltng tren x,ay ;ra l~rong ,Pjll.l d~~n,.· .thi ciing ~ ~~~q J9~,\.q~·1

cho ve ap suat va nhiet dQ~ hoa nang duoc ChUY~1l thanh di~n nang va

I , •

- .

thuc hien mot cong dien ba.ng 199.5~7~8 J. Chung~o, ~Ang trong ea hai

truong hop bien thien nQi nang In .nhu nha u, eon nhi~i thl khac nhau.· .

I

I '

.. . -

; ~ l ~

~ . ....... .. .: .

, . .

. .' .. \.

cuu

. .

~ f . .

Trong truong hop da u phan ling xay ra 18. khong thuan nghich

, : fl. ~ .

... Q '= AH· = -126~445~J I ; .~~: .. ) i ~--: ·~t .• ~ \ .. ~ - ...

. .'

"j

. ;. ~ :

, ..

.

- ~'

- -. _ .. r· ...... - _ - _ .

20

-

Chirong 1. NGUYGNLYTHiiNHAT,cliA~~irr:~~~l~;jtJ_

~ , t .

. AtT= Q' + A :::: AH - P i.\ V:::::; .dB:'~ l1nRT :~AIr+_!_RT; - .: I' ';. . '(!', L

. . ,..' ~ f t IT.

• •• ._.. • .... _ • _ , .. • • • • 01 ,. _ -! '

, I .' . - • . ,. ~ (I ~ !'.: ~ ~ . •. . _. l··. I ) I _ i· r' r: ~ , f -. t·,

. • • .. • '.. ,1 r 1 l. .. 1r "IL J _

r ,. , •• • _ _ •• ' I • ': • _ _ _ L ., _, _oI. _. • _ ..

1 . I' r: - ,., _.,

. .. ~.'r:~.J~

= -126.445 + - x 8,314 x 298 = -125,206 kJ

2

~. . ,.. .... ·r·...'

i • _. .• -, .: 1: I [ /: 1- ""

· . , • , ' • .. . IF. _ _ . . _ ~ Ii!

,

. .

. DOi vdi tntong hop .sa U, phan ~g I~~~ ra ~Qt: caqh; th.l~~ ~ ~g~;

nhiet dQng trong pin cli~n, nang l~~ng ciia phan;,~~ 1>1l~P: ~~n~huy~n thanh di~n nang vdi cong di~n -A'max = -109.557,if J, phiin -Dlio cu~ hoa

nang chuy~n thanh nhi~t nang q. ; , ).\' :'

: ....

Nguyen, Ii . thtt nhat trong ,trudng hQp cO. ~PJ jdW~, !(c9~lt;c9 Ich)

. I

. .

duoc vitt:·

. '

01 • • ..

.

. ..

- .

. . t -.... ~ -;. .

• . - - -. . I .,.- \ l I I

~. . ~ ... !., t I J

I . I I . ,.. < • i 'L _

.

. i

cSQ -; dU - f,A - cSA'D\8X .' "

. I ...,. • r ....

\ t' • ,

, (&A, ,,<0; ~,r~4!m'ax < 0).

, . ~ . . .... . .. .

. . = dU + PdV .:..: oA'max ;

· I

.' t

._ _ .

" '

I i

• I

= dH -.l>A'max ~ . ,

-

, '. ho(l~:' ", Q ~~AH -·A'm* = )q

• i

'q = -1'26.445 - (-109.5'57:8)"!

= -16~887,2 J

, .

I

I ....

. .. I· .. t I ~ - , . i

.~~ J ••••• "'~I.,

. . .... ~

.:. , . f i I . - ..

.' . .

, r

:C··1f1 (:~:·~r'·

..-

. \

,

l .

"L , '

-

4U = Q + A + A'max

. ,

. ~ 1 •.

l I f

I I I

-:: ,_

I

. .

: 10

r •.

= Q ~ PAY +,.f\'m8x =,q-J':AV ~A'ma~ ',' " '.f \

! ....11 _.. . j , - ~ I

= -16.887,2 + 1238~78() -lO~t557,8

I . .. t

• r 1 .. " .:"' , ~

. . :, ,~.."'. ...:

. = -125~206,214·J . hoac L\U = -125,20S-kJ.

1.9. Nhi~t hydro hoa buten-l d 82°C bing -126~8'25 k!1.; z!ihl~{

dung cac chi't d 298 va 400 K dtl~-cho dirdi day:'" , -"' I ;,,1, I ;--.

. - .

~ .

1 -:. •

T

}

: ~

,

.

Jo ~.

. . .. 1

CPo C"H, [J.K- ]

~ .... I

c, H2 [J.K-1] 28,808

. 1

c, C4H10 [J.K- ] 98,690 124,564

. . .

• 01 .'.... • _ • .. ,...... ,

I .. : _., . . : . ~. 1 I I .' . l ~_ I. • . ;. • i o.

Xac dinh AH29s• Chap nhan rAng (ACp)355 = 2'[(ACP)298 + i(~CP)4Oti,J . i - !

: . ; : I

89,243

I .•

. , ' ,

I • ~

: ,

I .

400 . _ ._ _ .

, 1\ •.. :. J ••. 1 . L t;.. .. v

. - I ..... . '_, • . •. ' . _: -..

11·2.,609 I . . '.- "

I :-. < i~ ~ ;,:(r, .f_·.~' .. ~.J

298

I .

29,151

, ;!o

, .

,

I

BAJTAPH6A LV COsO.". :. "., ..

• •

, ~ {,' '_ , , ~ T'

'l " , _, .", ,",

21

, ,

So sanh k~t qua tim thay vdi ke"t qua thu duqe tit su tfnh nhiet

hinh thanh ne'u: i '

I j • ' , t, r

(6HhvCfH10== ~124,614 kJ

.. . -. . .

;

..

Gidi

~ . .. ;

I • • I

DBl vdi phan tmg . I'

. (~Cp)400 =: ,124,564 .;. .112,609 -' 29,161 = -171196 JK-1 (~Cp)298 = 98,q~Q_- 89,243.- 28,808::= -~9,.361 J.K-1

(ACp)356 = ! [-17,196 - 19~361l=- ..:18l278 J.K-1 .

2 '

. .. . . '. . .

L\H29~:= AH355 + ACp[298 - - 355] .

,

, , ' 1

+

= -126;825 + 18,278.10-3.57.:.... -125,783 kJ Sv tinh ~unhi~t hinh thanh cho ke't qua:

, ,

-(1,170 + 124,614) = -125, 784 kJ

, .

, ! ,

Nhu v~y co 8\1 phu hop gifta hai phuong phap.

, '

: . ..

1.10. Doi vdi phan ung xay ra d ap suat khong d5i:

• . • I

• ~. 'I _ • ,"

: .

2H2 + co -+ CH30H (k)

I • - • I I .. •

I , ~ " I

, ,

nhiet hinh thanh chuan d 298 K cua die ch~t CO va CH30H bang

-110,5 va -201,2 kJ.mor1• Nhiet dung mol ding ap cua cac chat 13. mQt

ham cua nhiet do:

• III

, ,

,

_

, , '

, .

Cp,H2 = 27,2S + 3,26.10-3 T *.O,502.105T-2 J.K-1

Cp co = 28,41 + 4,10.10-3 T - 0,46.105T-2 J.K~l

,

C, CH OH = 15,28 + 105,2.10-3 T - 3,104.10-5T2 J.K-1

J 3 ' ,,_ '.

a) Bi~u thi AH cuaphan ung dudi dang mQ~ ham cua nhiet dO.

... . . ". . . ..

b) Tinh AH d 500 K dO'i vdi phan \:ing da cho.

o _. ....... I I, r I

~ "

..

.,

J :.

I, • _

': :' ..... \. \

( • ~ -, j .' • ' . .' i'., . .~. ~ .. ~... I }" ..

.,.j • : : , .• I. . • ; • A..; ~ .' ~. . .,. I. t

L

.a) Xac dinh ~Cp

.' · ~ i1 1 ..

• j .... 7' ". j ~ . ... r·. r ~ (1·( of' J li

.~.' , ~ ~ 7 • l~.... .. s; .iJ ' .

. ..

. .

I '. ~ - J - I . . : I ..

6a ::: 15,28 - 28,41 .; ·2.27,28 :!: -67,69

Ab = 10-3 [105,2': - '4",].0 - 2.3,e6]iJJ9~,58.10-3

+

• "I _

f',·, )

t ~ "

Ac' = 105 [0,46 - 2. O,502l'-; ~O,544.l'O~"

. . ..... . '. .. ; .. , ., ( t7

• • I • ' ••

r AH298 = -201,2,+ 110,5 ::;: -9'O;.1'kJ

j • r t

(.; ,f •.

r .' .

. ' fiHT' = JA CpdT -+: L\.Ho ..' ~ .: I .:. .. ;'. )

= f (-67,69 + 94,58.10-3T- 31'i04.10-~2

, [ . . ) ~

I: I _... _ I I -.. .

. ,

- O,544.10~.T:-~)dT + A-H'b';:' '

== -67 ,69T' +' _!'. 94~5ff 10-3rt2 ~~: If. 3't~d4~ lO~~3 ":.:;

2 3

, ...... ~... ,.~.: I I .

, Fl. I ~. :l-

I '. ~ • L .. •

r ' • . I •.. )

+ Q,544.10ST-1 + MIo , ' '..,' ,

i : : . . ~ .. .• I ~ :: ~ • . ~ i • '. -;.. "r ,\ j . ~ ....

_ • , _J . .". .. . . - .. r ..

• I I .. r

.

Xac dinh I1Ho tit gift trj AH d 298 K

~ . . ,.. . . ;'. '....:+ .. ! r ....~ t-

. ••. r· • ,. :.' .•• r J" ~. ~Ir

• I • .:. .. ~ ~ : • .! ~ ..f .:. . ~ . I, I I 1 .... -. - ~ - ~ _

AHo· = -90700 + 67,69.298 - (94,58/2).10-3.2982 •

.. . ; .', ~ . t '; ;l' il,:·

.• ,.'. ~.: 'l·

+ (31,04/3).10-s.2983 + 0,544.105/298

. ,-

~ '. • I . ...,' , L ~ ..' ,,~) ' • .;. .~\ , ......., i: ~ f r· : I" i ~ ,.~, , i ~. ~. . ~ t ; j, ~ l l r ~

• • I :" . .- .\ ..• ; ....... I l r)o~ , .. ~,.j:.l ,.fJJ,:·,

- - 74. 540 J / > . " :.' . . . " ,. ~ . . '.' I .

. ..~. .; .,' '.' . . . . t~ j' . .: • .~ . ; i ! . I. .- . ! i . r », •• • t"). v ~.' ' .. i : J

V~y ta co phuong trinh .l1H phu thuec T:

, " . ,

~ " . .~.. . r , I' .. . , .. r -4, ~

l~~: &·f,.l.: i.li ~. ''; .

. _ 1. . I .... • .. _ ft. .

+ Ot544.10~-I .. ; i. r ,

! "

.t .: " .

.. . ,

b) Xac dinh AH d 500 K· '1 ': .

4·

.. .. , . • f

L\Hsoo ~ ~74.540-" 67,t39.500·+47:29.10·a.'5002 :. ":i ;f~

~ I

.' .. • • • :- I. ... I "I 'r"'

. t '10. • •• •• ~ z • .

- lO,34.10~5.5·003 + 0,544.1'05/500 ~. -97>iSOJ

:BAITAP 'H6A L V coso ..• , ".r ; -. _.i

•

23

1.11. Nhiet hinh thanhciia axetylen va 'benzen d cac nhiet dQ khac nhau dUQc cho dudiday:

I ' -

. ' - .

T

~HC2H2 [J]

.AHcsHs [J]

1000 1100

222 810,72 ·2i22 171,18

". I "

61"-"939,24 61 i53,40

1200 1300 1400

221 552,54- "'220 917,18 220277,64

" "

• • .' I

60 693,60 "" 60 401~OO"' 60 233,80

Xac dinh nhiet dung cua hoi benzen d T = 1200' K·ne'u tai nhi~t·dQ nay C, = 69,99 J.K-I.

tC2H2

Gidi

,- -·Theo dinh Iuat -Hess, doi vdi phan ung

-

..

.

. .

" "

1 " "~

-,

. "

.. "

K6t qua,·tfnh ~H d cac nhiet dQ khac nhau:

,

T

. "

r "

" I ,

1 ~" " •

1000

, "

" ~ .

1100

1200

1300

1400

-L\H 606 492,92 605 385,22 603 964,02 "602 350,54 600 599,12

Ve d& thi AH phu thuoc T rBi ke ti€p tuyen tai T = 1200 ta duoc

f) [AHJ/dT = 15,048. - Do do

CPC C = 3~69,99 + 15,048 = 225,017.

t 6 6

: r

I" I

I I - • I I • ~

1.12. D6i vdi phan nng 2A (K) = A2 (K)

bep::: 4,18 + 8,36.10-3T J.K-1

1 "

_ .. AH~98 = -29,90 KJ.

Xac dinh nhiet dQ tai d6 dH~ = 0

. ~ .

", '

, '

G .. , II zat

" .

,... -

" 1

" ,

- "

" "' .. T '

~~2 _. fl.H~l = J ~CpdT

Tl

0-(:.20'900)= l(4,18-+8,36.10-~)dT·· --:

i "

298

" ..

..... . rIfI , ., .., ..A.A. J

24· ! Chl1dng 1~ NGUYEN LYTHUNHATCUA NHlfTDQNG-LVCHtpC

hay

= 4,18'(T - 298) + 4,18.10-3 (T2 - 2982), 20 900 = 4,18T - 1 245,64 + 4,18.10-:JT2 - 371,26 > 4-,18.10-~2 ~ 4,18T - 22 516,84 ~O _-

. .

- .

. )

- I

Giai phuong trinh theo 'I', thu.duoc T = 1880 K

. .

III. BAt T~P TV GIAr -

,.

1.13.

1

.-

O,~ mol .khf ly tUdng

• • • I •

,

co Cv = 1,50 R thuc

hien mot chu trinh

• •

nhu hinh ve.

Tfnh nhi~~ Q, cong A

. .

va bien thien nQi nang

AU cua tUng giai doan va ,ena toan b6 chu

•

p(qfm)

s

, ,

-

1

4

trtnh,

4000

2000

I

DS~· 1 ~2: Q= 304J;

.

2 ~ 3: Q == 761 J;

A = O· .6U = 304 J

, .. ~

. ~

. . - . I 1

. . ,

A = -304 J ; AU = 457 J

.. . ~ .

3 ~ 4: Q = -608,58 J; A = 0; AU = -608,58 J

4 ~ 1: Q = -253,5 J; -A":_ 101 J; AU = -152,5 J

1.14. MQt xilanh duoc dong bang rndt pittOng di dQng khong Ina

.JI

sat, chua 3 mol khf He a 1 atm va 400 K. Ap suat ducc tang thuan

nghich nhiet dQng toi 5 atm. Xac dinh As Q va AU cho qua trinh nay.

DS: 1,6.104 J; -1,6.10-4 J; O.

1.15. MQt mol khf It tUdng don nguyen tit b 300 K va 15 atm duoc dan Db tdi ap suat 1 atm. St;l dan Dd dl1<;'c thuc hien bAng con dUdng:

" ..A .; t# .,

BAI TAP HOA LV CO SO .

. , . .' -

, .

. -

. '

a) ding nhiet va thuan nghich nhi~tdQng;

. .

b) dAng nhi~t va khongthuan nghich; .. .: - . ',; 1

: ~ , - -

. . ~. . .

I

... . - ... :

- . 1.-

..

. ,

. i

. . -

. t ' : J' .. "I,

• L ~ •

. ,

c) doan nhiet va thuan nghich; d) doan nhiet va khong thuan nghich,

Trong cac qua trinh khong' thuan nghich, stl. dan Db ch6ng Iai ap

suat 1 atm. Tirih Q, A, aU va AlI· cho m8i trUdng hqp. . _ -' t- _ ;

I • • •

,

,.r • _

- .

L ,

I

~ ,

DS: a) 6,75_kJ; -6,75 kJ; 0;- 0:- -' .

. ..

. .

... • I 1 .

- I . .

b) 2,33 kJ; -2,33 kJ; 0; 0;

: I I I

. ..

~ ,i •

. . .

!

c) 0; -2,47 kJ; ':'2,47 kJ; -4,12 kJ;

I '

(I) 0; -1,4 kJ;-2,33 kJ.

I

~ ".r r . : : ~"I I . It':, . I

. I. - ..

1.18. lOOg khi CO2 (xem nhu khi Iy tl1ong) lJ Ooc va I,OI3.10?;Pa-.;

Xac dinh Q, A, ~U, L\H trong cac qua trinh sau..

a) dan "dAng nhiet tdi th@ tfch 0,2 m 3;

b) dan dAng ap tdi 0,2 rn3;

• I :. '. ~ ~ •

I. - I '1 ~_. .. I •

c) dun n6ng ding tfch tdi khi ap suat bing 2,026.106 Pa; ; ,: .";

d) nen doan nhiet Wi 2,026.105 Pa. Cho hi't CP•C02 = 87,1 J.~~morl\· i

L

• •

....,

.. _ ~ r· ~ .:

- ~

..

, . . ..

DS: a) Q = A = 707 kJ· AU='Alr=o - .. ,.-, i

, ,.

b) Q.= 67,4 kJ; A = -15 kJ; ~U = 52,4 kJ c) Q = ~U = 17,9 kJ·;.·A~.O; AH ::;·23,1 kJ

. , '

d) Q = 0; L\U = A = -2,97 kJ; MI = 3~83' kJ~'

, -

. . ,

1.1 '1. Xac dinh bien thien nQi nang khi lam bay hoi 20g etanol tdi

. ~~"j! .. ; .. ,.

nhiet dQ s&i n6u nhiet bay hoi rieng' cua etanol~tilhg'851,7 Jig; thEf tfch

hoi tai nhiet dQ soi b~ng 607 cm3/g (hi) qua th~ tich 'pha long).

-

DS: ·~,54 kJ

1.18. Tinh AU va AH cho cac qua trinh sau day:

a) MQt mol nude dong d~e 0 OoC va' 1 atm,

b) Mt?t mol nude soi d 100°C va 1 atm.

." J.. •. 1 •

" :..... :

- -

.. • r •

_ L

. ~ . ~

I •• "

~ ~ r.·

I. ...I' .

. . - .

. ',.. - . . .

,~ , .

,

26 Chuang 1. NGUYGNLYTH{JNHATC"A;NHjtt~N~w..C-Htn

bi6t rang nhiet dong d;)c va nhi~t bay hoi cuaLmol nl1& bAn.g'-6',Ol-kJ va 40,79 kJ; th~ tfch mol cuamrdc IOIlg'va nl1dcM- blng,_:O,018(ll va

0,01951. Chap nhan hoi IS. khi 1:9' tuong. . ' ! '.: , '

.... I .'

1)8: a) ~U = AlI = -6,01 kJ

• • 'I • .. • .. •

. I . ..:,.. .. ~ _

b) 37,7 kJ; 40,79 kJ. '

I : I - - ': I.' - _.. •

. ... -

-

1.19. ~ 25°C nhiet hinh thanh eua HF (aq)bAng~320 kJ moirJ-;

cua OH- (aq) bing -229,94 kJ.mor1; eua F- (aq) bAng -329,11 kJ; etia H20 (l) blng -285,84 kJ mol",

a) Tinh nhiet trung hoa ella HF (aq)

HF (aq) + OH- (aq) = H20 (l) + F- (aq)

"I 'I ."

b) Doi vdi phan itng H+ (aq) + OH- (aq) == H20 OJ, All = -55,83

..

kJ 1m O· 1-. . ., .. : .: ,r ~

r :. ~"I • I. I,

Tinh Llli dill vdi s11- phan ly HF (aq) =: H+ (aq)'+ F~ (aq) - ." - - --:' -- ' - ,j

. .

- . .

DS: a) ·-64~91·kJ; b)'~9,08 kJ.

. ,.

, .., • - . j. ,.,. .

1.20. Nhiet hinh thanh eua nuOc long va eua CO2 b~ng ~285,8 va

. -~93,5 kJ/mol d 25°C, 1 atm. Cung d di~u k1~n-nay;nbi~t dol chiy cita

. -

CH" bing -890,3 kJ/mol. Tfnh nhiet hinh thanhciia CH4'tt't cae-nguyen

· to' d digit kien ding ap va dang tich.

FJS: ~74,8 kJ/mol; 72~41 kJ/mol .

•

. -

1'.21. Tinh nhiet hinh thanh ehuiin ella CS2 long dua vao cac dtr . ' .

. kien eau:

..

l\H~98 '= -296,9 kJ .

• • ~ r • f _. _. I • ~ !

AHo' .. ~ ~lio9.kJ · .

, - ~J'. :J ..... -" •. - .,- <

• 'I' ... ). I ',' - .. _ ,.., ' __ ' . I. P ••

. ,AHo - 398 5:·kJ', {

Ll 298' .:-: ~ . ' :~ . ../:0 _ . ~ ~ .1. _

T

DS: 121,·7 kJ/niol~

S (mon) + O2 = S02

J •

eSa (l) + 302 = CO2 + 2S02

+ C (grap) + O2 = CO2

. ~ "

, .

1.22. Nhiet hmh thanh ella Fe20g (r) bing -821,S'kJ/mol; 'cua

. -

Al203 bdng -1675 kJ/mol. Tfnh hieu ilng nhi~t eua 811 Jqtu 1 mol Fe20a-'

• - I I : t

bAng nh8m kim loai. .. .., - .... .

. '

. , .... ,. . ,: .. • • . . t

. BS:'-853,7&J/moL

_.

BAI'TAP H6A LV CO sO

..

I

" .

27·

.'

-

1.23. Tren co ad cac dit kien san, hay tinh nhi~t hinh thanh eua

Al2Cla (r) khan:

.

2Al + 6HCL. aq = Al2C16 aq + 3H2

H2 + C12"= 2HCl (k)

AH~ = -1003,2 kJ " " t\Ho = -1"84 1 kJ

298 " I "

AH~ = -72,46 kJ

AH~. ~ -643,1 kJ

DB: 1347,1 kJ "

Hel (k) + aq = HC} aq Al2Cla -(r) + aq = Al2Cla- aq

1.24.Tinh hieu tmg nhiet a 25°C, 1 atm dOt vdi phan itng MgO'(r) + CO2 = MgC03 (r)

C (grap) + O2 = CO2 1

Mg (r) + 202 = MgO (r) ,

" All ="-393 5 kJ/mol

" . '"

..... "

" AlI =. ,7601: 7 J{J/mol

r I, ~ _ ~. ,I,. I' •

-

3 """ " r - : ~

• • r • I .. •

Mg (r) + C (grap) +,~ O2 = MgC03' ,MI = -1113 ~kJJmoJc' , . ,.

- 2 I '. ." - " .: ~ "

" • j ...

. ... i:' . I .. ' .

D8:·" -111,8 kJ/mol -

" •. " """ ~~ __ f"'_

• I • .J ... .

- ""

"I ..... •

• • I .-

1.25. Xae dinh nhiet hoa tan tich phan eua ~NH4Cl; n'u khr~hoa' tan 2g NH"Cl trong '100g nude, S\f ha nhiet d~ quan sat dt1~ At = O,130c. Nhi~t dung rieng cua dung dich tren bAng 4,171 kJ/dQ.kg. Nbiet

dung cua nhiet It1~lig'k13 bang 171,544 kJ/dQ.kg. ." " ".' ":, ;

• • "I. • I • .. - •

. ' <. 'nS:-15129,a kJ/lnol~

.. .

. " .

1.26. Nhi~t d6t chay chui'n ella axit fumaric va axit maleic ~ bAng .

-1336 va -1359,2 kJ/mo!. Xacdinh bi(}u WIg nhi~t ctht al/. d6ng phlii! boo:· ' ...

" .

..

I "

; 11', COO"'., ",', .

." • . . r .

\ ",/!\'. '"

c=c

I - \

Hooe" ~ !; ~".. ~H ~",."

I

HODC \. ·c=c

/ "'

H ". _H

COOH I

axit maleic

axit fumaric ~ · ~ .'

" . ~" "

BS:-23'2kJ

, ".

28

Chuong 1. NGUYEN LY THU NHAT CUANHIIT DQNG LVC Ht;JC

\.

"~

1.27. Tinh AHo ct6i vdi phan ung· .

FeD (r) + 2H+ (aq) = H20 (l) + Fe2-1- (aq)

.. -

bi6t:

-

" "

" "

3

2Fe + -02 = Fe203 2

1

2FeO + -02 + Fe20a 2

,I

H2 + -02 + H20 (l)

2 ""

1 "+

· -H2 = H (aq) 12

Fe + 2H+ (aq) = Fe2+ (aq) + H2

" "

AHo =. -822~2 kJ/mol

AHo = -284,1 kJ/mol

AHO = -286 kJ/mol

. "

AHO - -86,2 kJ/mol DS.~ -103 kJ/mol

1.28. Nhiet trung hoa axit HN03 blngxut 18. -55,9 kJ. Cfmg hi~ng dung dich xut tren ctuQc dung d~ trung hoa axit CHCl2COOH thi hi~u ling .nhiet nhan duoc blng -62,05 kJ. 'Ne'u cho 1. dUdng IUQng NaOH vao dung dich chua 1 duong IUQng HN03 va 1 duong hrong _

" "

CHCI2COOH. thi toa ra 58,41 kJ. Xac dinh sDdudng luqng gam HN03

" "

da phan tcng vdi NaOH.

os. 0,58 dlg-

" , "

1.29. Nhiet trung hoa NaOH va dung dich NHa bdng.axit Hella

. "

-55.,9 va -51,34 kJ/mol. Xac dinh nhiet di~n ly cua arnoniac.

" J

DS.~ 4,56 k-I/mol,

" .

-

1.30 •. Xac dinh nhiet chuy~n, boa hru huynhrombic sangdang don

ta neu nhiet dot chay ella Iuu huynh rombic va don ta tuong tmg bdng

r

. "

~297,5 va -300, 1 kJ/mol.

"" - DS: 2,6 kJ/mol~

1.31. Nhiet dot chayciia cacbon vo dinh hinh, cua graphit va cua kim cUdng b~ng -409~2; -394,6 va -395,3 kJ/mol. Tinh nhiet ehuy~n hoa thu hmh:

. BAI TAPH6A LV CO SO

•

29

a) cacbon vo dinh hinh sang graphit;

b) cacbon va dinh hinh sang kim ctrong; c) graphit sang kim cuong.

FJS~· -14,64; -13,9; 0, 7 kJ/mol.

1.32. Hoa tan O,632g phenol vao 135,9g clorofooc tOa ra 0,087 kJ.

Khi hoa tan 1,56g phenol vao 148,69g clorofooc thitOa ra 0,171 kJ.

Xac dinh (tinh cho Irnol phenol) nhi~t pha loang bing clorofooc d~

chuy~n dung dich thi1 hai v~ nang de} cua dung dich thu nhat, ·

FJS.~ 2,8 kJ

1.33. Phan tmg giua kern kim loai va dung dich dang sunfat xay

. - .

ra trongongnghiern thi tOa ra motnhiet 111~ng bang 230,736 kJ. Ciing

phan {tng tren cho xayra trong pin. di~n thi mQt ph§.n h6a nang chuyen

I

thanh di~n nang; cong di~n rna pin sinh ra bang 210,672 kJ. Hay chUng

to rdng trorig 2 each tie'n hanh phall (tng AU vftn giua nguyen gia tri~· nhung Iudng' nhi~,t kern thea phan ftng trong 2 trudng hop .thi khac

• .. :" • • I

[ -

1.34. MQt khf Iy tttbng co Cv = 3R khong phu thuQc T, di1~c dan no

-"'

doan nhiet trong chan khong tdi th~ tfch gi'p doL Sinh vien A 1:9' luan

r~ng dol vdi qua trinh doan nhiet thi T2trl = 01IN2)RJ3R do do T2 = T1/2113. Sinh vien B'sudung h~ thuc toan cua nguyen Iy thi1 nhat ~U =

. .

Q + A = 0 + ° = 0 va aU = CvAT = 0; Cv i= 0 nen L1T = O'vay T2 = TI. Sinh

vien nao dung ? Chi ra ehB sai cua sinh vien tra loi khong dung.

• • ) ... - I - _ •• • -

·1.35. MQt sinh vien khi lam tl1dng trinh bai thi nghiem nhiet d5t

. .

chay mQt hop ch~t hiru co dB. cho rdng ~H = AU + PA V. Su d6t chay

trong born nhiet luong ke' lam cho llV = a do ·d6AH = AU·.· Ke't Iuan Day sai d ehB nao?

1~36. (1 25°C nhiet thang hoa cua iot blng 62,3 k-I/mol; nhiet hinh thanh chuan cua HI (k) biing 24,7 kJ/mol. Xac dinh nhiet 'hinh thanh cua HI (k) tit cac nguyen to d th~ khi tai 225°C bi~t nhiet dung trung blnh trongkhoang nhiet de;> 25 - 225°C:

•

30-

Chuong 1. NGUYEN LY THU NHAT eUA NHlfT D(J~G U/e HQC

t;.

H2 Cp = 2.9,08 J.K-I mel"

12 (k) c~= 33,56 J.K-I morl·

HI (k) Cp = 29,87 J .. K-1 mol".

os. -6,74 kJ/mol.

. ... 1

1.37. Xac dinh LlH~73 dOl vdi phan Up.~ CO + 2'°2 = CO2 •. Nhif)t

hinh thanh chu~n d 298 ·K dOl vdi CO va CO2 bAng -110,5 va -393,5 kJ/mol. Nhi~t dung mol ding ap cua cac chat dUQc cho .dirdi dang ham eua nhi~t.dQ: .

Cp co = 26,53 + 7,7.10-arr - 17.10-6 T2 J.K-1

,

; I.

, -

Cp,co2: = 26, 78 + 42,26.10~arr - 14.10-6 T2. J.K-1 ..

·Cp,02 = 25,52 + 13,60.10~arr - 4,27.10-6 T2 J.K-1·

.

. OS: -283,6 kJ

'1-

, . -'I

•

1.38~ Nhiet hinh thanh khi amoniac d 298 K bing· -46,2 kJ/mol.

Nhiet dung mol cua H2, N2 va NHa trong khoang nhiet dQ 250 - 450 K dl1QC cho dudiday: .

Cp,H2 = 29,1 + 0,002 T J/mol. K

Cp,N2 = 27.1 + 0,006 T J/mol. K

Cp,NHs = 25,9 + 0,032 T J/mol. K

"I _ _. I •

Tinh AH va AU dOl vdi phan tcng tao ra amoniac d 398 K.·

BS: -48,4 va -45,1 kJ/mol.

r,' _ •

1.39. (j 900°C nhiet phan ly cua CaC03 theophan Ung .

CaCOa = CaO + CO2

bdng 178 kllmol. Nhiet dung.mol dAng ap CU~ cac chat. dllCjC cho bang

cac ham phu thuQc T nhu sa u: .'

Cp,caco3 (JIK] = 104,5 + 21,92.10-3 T - 25,94.105 T-2

Cp, CaD [JIK] = 49,63 +4,52.10-3 T - 6,95.106 T-2

BAI TAP H6A ·LV co sO .

.. .

\ .

31

Cp,C02 (JIK) = 44,14 + 9,04.10-3 T ... 8,-53.105 T-2 a) Thitt l~p-phudng trlnh t.H =. f_(T) dOl vdi phan tmg,

. .

_ b) Tfnh nhiet phan ly CaCOa dOl vdi 1 kg a 10000c

. .

. DS~· 1760 kJlkg

. 1.40. Tinh hieu ilng nhiet cua phan ung

co + 2H2 = CH30H (l)

. .

tai 500 va 1000 K n€u 0·300 K hieu tlng nhi~t cua phan ung da cho

bing 90, 72 kJ va nhiet dung cac chat du«;se cho bang phuong trinh phu .:

thuoc T:

•

I

'. .

- . -3 5· -2

epeo = 28,41 + 4,10.10 T - O,46~10 T

I '

•

J/mol~ K

Cp, H2 = 27,28 + 3,26.10-3 T + O,S02. 106 T-2 J/mol. K

Cp, CHaOH = 81,6

J/mol. K

,

DS: 89,52 kJ; 84,82 kJ

I • I •

, . 1.41. Nhiet ngung tu rieng ella benzen CJ 50°C va BOoC bAng

-414,7 va -397,1 JIg. Trong khoang nhiet dQ tren, nhiet dung rieng eua benzen long bAng 1,745 .J/g.K. Tlnh nhiet dung rieng ella .hoi benzen trong khoang nhiet dQ da cho.

DB: 1, 165 JJg~K·

-

1".42. Hieu ung nhiet cua s\l oxi h6a nhom d 25°C bang. 1669, 792 .

kJ/mol. Xac dinh nhiet hinh thanh nhom oxit tai 600 K bie't rAng: .

. -3

Cp AI = 20,66 + 12,38.10 T

f .

J/mol. K J/mol. K

. -3

CP,Oa = 31,46 + 3,389.10. T

CP.AhOa ::::: 92,38 + 37,53.10~3 T J/mol. K

DS: 1667,17 kJ/mol.

1.43. xac dinh nhiet phan tich 1 mol amoniac thanh hydro va nita. d . 1000 K bie't r~g nhiet hinh thanh chudn d 2SoC dOi. vbl amoniac bang 46,191 kJ/mol va nhi~t dung eua cac chat du(Jc cho bang cac phuong trlnh:

\ '

. .

,

32

Chuong 1. NGUYENLYTHtfNHATCUANHltrD9NGLVC·Ht;iC·

Cpo N2' = 27,865 + 4,267.10-3 T Cp, Hi = 29,078 ;.. 0,836.10-3 T

. -3

CPo NH3 =.29, 79 + 25,48.10 T

DS: -54,39 kJ/mol

1.44. Dua vao cac phuong trinh nhiet hoa hoc:

AH298 = -192,9 kJ/mol

C+02= CO2 2CO + O2 = 2C02

- - I

AH298 = -393,5 kJ/mol

. I

. . ~ I

4H298 = -5.66 kJ/mol-

va cac phuong trinh nhi~t dung phu thuQc' T trong khoang 298 d~n 423 K:

CPo N2 = 27 + 0,006 T J/mol.K'

, Cp, H2 = 25,6 + 0,014 T J/mol.K Cp,N20 = 27,2 + 0,044 T J/mol.K

Hay tfnh nhiet hinh thanh cua N20 d 423 K

~ f)_S: 82,2 kJ/mol

• ...

.1

..

-

. .

..

. .

. ~ .. I

33:·

, . -, . ~ '.'1' . , .

; ~. _. ,I: ~ . . . .

Chtidng

. • L 1

. .' I

1 -:... r .- 'j; I I

. I

, . ] ..

'. .

~ : ~ :

,

• "Ir •• ',

I I ~ 1'1 •

~

, - ~ ! .

.. ..: .

... ," , .... A

NGUYEN LY THIlHAI CUA.NHIE,J!iDONG!

! ••

LUC HOC, vA cAe, THE, NH'IEI, ·B:ONG

• • • •

,

I I .. r

. ,.. . . t·. ,~ .

;.; ~ .!" J ~.F··. - .1

Bi~u thuc dinh IUQng t6ng quatciia l1guyen.'lj,thU'haicU:a·nhi~t

.-; .

dQng luc hoc co dang . r- : •.. r : L.~ .. _~ .1. '-' .•

(2~ 1)

I • I. I

• • • I • • I I .. ~ • I •

,,' '.

dau dang thitc dl1Qc SU dung choqua trlnh thu~nng~jch::nhi~t.~<)}lg~;va,!

~ ,

dau bat diing thuc, cho qua trinh khong thuan nghich}lIV~~,~9~g,\. ";: .. ;f,"'/

:. • ," I

. ,";.

Doi vdi chu trinh thuan nghjch (2.1) trd thanh '

. . .

- -

,- .

t . '., . . , .' .... ~. . ',

~ .,' ~. 'I • I .. _ I ~ .

i oQ = 0 T

. .

_ f ! __ !'_ -'(2.2)

1 • .

. . .

dai luong 0'; 13. mdt vi phdn toan phan dung Cila~Qt ham S. do do

oQt .. -=dS

".....

• .J..

Ham S duoc goi lit entropi. · .

34

- .- ;. .,. ~.A-

Chuong 2. NGUYEN LY THY HAl CUA NHlfT D9NG LI/C Ht;>C ...

D5i vdi qua trlnh khong thuan nghich, dS > 8i. MQt each Mng ~:3~,~.d9i vdi mQt qua tr~h bat ky

dS 2: ~Q T

(2.3)

theo do

dS oQ d~"'· , '" ~ t" h thuf . hi h

= T 01 VOl qua rm u~n ng ic ,

dS > 0; doi vdi qua trinh kh9~~ thuan nghich ..

,

va

DOl vdi q~a trinh htiu han: AS = jO; , trong d6 b dieu kien dAng·

1 .'

nhiet 'th ,.,'~ h· · h· AS . Q : .

\1 ;'. u~n'~ng Ie ,il =T"' .: , . .

. .-:.

, ,

: . -

,. 1\hi qua trinh la da~g nhiet, khfmg thuan nghich thi ·

AS>Q

T

con dOl vdi qua trinh thuan nghich doan nhiet thi

l1S = 0

. Trudng hop co su trao d3i nhiet gifia h~ nhiet dQng va ngudn nhiet co nhiet dung cue Ion thi

ASh~ co l,p = (ASh(!; nhi~t dQng + ASnguiJn nhi~J ~ 0 (2.4)

N~u ASh~ cO l,p= 0 thi entropi cua h~ co li),p khong d6i d6i vdi qua

- .

trinh thuan nghjch, Ne"u AShe ~a ~p > O' thi entropi cua h~ eo l~p tang dBi :

vdi cac qua' trinh di~n ra trong d6 18. khong thuan nghich. .:

Bi6n thien entropi trongmdt so qua trinh: . ·

• dang ap (P = const) ·

•

as, = cSQp/T

• A

T

l\Sp = J CpdlnT

T1

. . '

, J

..

,,~

neu

. "

,35

• ding tich (V = const) T

~SV = J CvdlnT

TI

- '.

, ,

.. ! ' , !

T va L\8y = CvIn 2

, T1

'.

(2~6)

(Cv = canst)

., -.

" '

I

{ , t·" ,

J: . .' . ~ I

Doi vdi khf ly tlldng, bien thien .entropi diroc tfnh theo cac h~. th:qc:, ..

, " ~': , ' '.' , " ! .... ~ ., 1 '1'" '

. - '., '.' ."

dV oQ = CydT + RT - V

, .

, _ ....

1, - ,

t

•

oQ ' 'dT dV

- ~ dS = Cv -- + R -

T TL '" V

j dT V

AS.= C" T ,+ R,In V2 (Lrnol khi ly tUdng)

1rl 1 ~ (~

• I. •

I • I • 'I -_,

, '

(2.7)

1 dT P

AS = . Cy + Rin 2 (1 mol khfly tt!ong)

"'t' T, "PI '.-

,

, , ,

, -'

(2.8)

..- ,

. ' \ '

= Cae th€nhi~td9ng ,

", r .. ".

, , ' , ~" " ~ I r , Jr

S"ket hop cac bi~u thuc toan cua hai nguyen ly'd~n;td(~~c ham

~ . . I I :. ..;....; f (

nhiet dQng mdi, do 18. cac th~ nhief dQng.' Co bon' th~ nhiet dQrtg U, tr. F t'

G vdi cac c~p tham s6 tuong irng. DQ giam clla cac the' nhiet dQng trong _ cac qua trinh thuan nghich khi ceJ dinh cac c~p tham s6 se bing cong co

Ich cue dai rna he sinh ra:

~.. .

t

--

, -

(A'max)s,V = -~us,v

..

(A'max)s,~ ~ ~.AUs~p _; ~ · .:

, ,

., (A'max)T v = -AFT v (A'max)T· P ±: ~AGT p "

,:t :II • •

.

Trong b6n thEf nhiet dQng thi hai the" nhiet dQng co y nghia thirc

ti~n hon ca, d61A th6 nhiet dQng diing .nhiet ding tfch '. , 'i I. ~;,: .

,t ~

, ,

I . )1 '. . ' : ;.' ' '(2.' 9) '.

,~ ,.;,.',,",\'.' (I .... "l·~

. I . I •

. .. .

va the' nhiet dQng ddng nhiet d~ng ap (con duoc goi 18. th€ Gibbs hoac

'I I I •

nang IUQng tu do Gibbs)

! '

F = U - TS

G= H -TS

I ,

(2.10)

36

.-

..... ~, .,. ".A

Chlldng 2. - NGUYEN LY THY HAl CUA NH!P' 09f:1G WC;~.

DO'i vdiqua trinh dang nhiet

.. '. ~ , ..

. ~ ..

l1G = &H - T~S

. ~ .

I, " I

Truong hop phan trng hoa hoc tien .hanh trong pin di~n thi

LlF = ~u - Tl1S

-~GT,P = (AI max)T,P = nFE _

vdi 11- h6a tri; F - so Faraday; E- sire dien dQllg cua pin.

(2.12)

, .

A~ ~ , • •

:> n"ieu ki~n h! dien bidn va can bang cua h~

• dua van ham entropi

.. ~

" I. t

.. .. 1'1 ,

ASet> I~p > 0 ~Sco lap = 0

t\t diEhl bie'n cua qua trinh _ h~ a trang - thai can bAng

• dua vao the nhiet dQng

,

t\1 di~nbi~ll eua qua trinh d T, P ~ const hoac T, V = const

.6GT,p = 0 6.FT,v ~ 0

di~u kien can bang cua h~ d T, P hoac T. V

khong d3i ·

- .

"I~. ..

I • • 'P..... . .. .1.. :

Til bi~u thuc vi phan cua cac th6 nhiet dQug. co th~ lam x~~t hi~n

. . . . ..' .', _ ~ l,

• .. • - :' • - I. • + ~ ....

mi)t sf) thuoc tinh nhiet dQllg cua he, chang han doi vdi G, ta cO- _.-

. .. ~ t ... ~ ~ .-: I. I :

co 8P T

=-8

j.'-' ~G' I"· ~ .. - ;,.

; . 0 J • .,', • ~ I

.Gr ,"7-:'F OT2 "" '.'

p ,

r

~ :,." -_ ·.·1;· '.' "1'"

I ~ • _ :L I • L 'I'

=-V

or·

r

hoac doi vdi ham U:

~ ,

au-

-T

. -

OSv

au

=-p

BV s

l .

,

I. : ~ •. \ .

. .... .

- .

Qua day thay dtt~c sue manh cua nhiet dQllg luc hoc, <rch6ntroung : cap nhfmg h~ thuc lien h~ nhung dai Iuong khong do dUQc true ti~p vdi

... ,

nhirng dai luong co th~ do true tiep, Tit dinh nghia eu~ ham G = ,H ~ T,S. .

• . , .. . . ~ - r , ,.

" • _ '.; I • • • I r I • L ",' "

suy ra .

. :

f . • I - r .

• • I . :

J I .. I ..

H = G +TS

hay

ro

-H=G'-T ~

'or' p

-

BAI TAP H6A LV CO SO

II

37

phirong trinh nay diroc . goi la phucng trinh Gibbs Helmholtz. Dirdi dang C

MI = 6G - T or [hG]p, phuong trinh eho phep lien h~ hieu Ung nhiet CU~

qua trinh khong thuan nghich vdi cong eire dai .cua qua trinh thuan nghich.

, .-. i ~ ..,

II. BAI TAP CO LOI GIAI .

..

2.1. MQt ttl Ianh co hieu suat lam viec bang 50% hieu suat ly thuyet, co nhiet aQ ben trong Hi o'c. dl1<;1C d~t trong mdt can phong nhiet dl) 25°C. Tinh nang luong c£n cho su chuydn lkg nuoe long co nhiet de? ban ddu la OoC, thanh .nudc da. Tinh hrong nhiet rna tu lanh nhuong cho rnoi truong xung quanh trong qua trinh hoat dt)ng. Cho nhiet nong chay cua nude da bAng 334 JIg.

Gidi

GQi TI va T21a nhiet dQ cua nguon lanh va ngudn nong va Qb Q2 hI nhiet hrong rna dQng co nhiet nhuong cho nguon lanh va nhiet luong madong' co hap thu tit ngudn nong,

Hieu suat cue dai diroc xac dinh bang' h~ thuc

L llmax = --Q-- =: 2

-

Tti lanh dlt<;se xem 13. mot dQng co lam vi~c thea chieu nguoc vdi

chieu lam viec cua dQng co nhiet, do do nho nhan cong rna no lilY nhiet Q. tit ngudn lanh d nhiet dQ Tl va nhuong nhiet Q2 (Q2 = Ql +cong A) cho nguon nong d nhiet dQ T 2 cao hon,

Hieu sufit eve dai cua may lanh bang .

Vi til lanh co cong Built bang' 50% hieu suit ly thuy€t nen

. ,

Q1 O,5T1

----

-

A T2 - Tl

D~ chuyen 1 kg nude long «(j- OoC) thanh mrdc da din mQ~ nhiet

IUQng QI = 1000.334 = 334.000 J, do do '

•

38

.-. .; __ .., .......A.

Chuong 2. NGUYEN LYTHUHAI CUA NHlfTDQNG LVCHOC. ...

334000 O,5~273

A - -29-8---2-· 7-3 hay A = 61200 J; .

day lit cong' ·cftndt! chuyen nude long thanh da trong ·tit lanh. Nhiet Q2 nia tulanhtoa ra moi truong xung bang:

Q2 = Ql + A = 334.000+ 61~200 = 395~200 J

2.2. Tfnh bien thien entropi cua qua trinh trQn 109 mrdc da d OOc

. I _ ..

vdi 50g nude long d 40°C trong h~ co lap, Cho biet nhiet nong chay ella

• . . I: I

nude da bang 334,4 JIg, nhiet dung rieng cua nude long bdng 4,18 J/K.g.

" .

cu:

. .

GQi e Ia nhiet dQ can bang cua han hop nude da· va nude, ta co hie

. - .

can bang .nhiet: .

10~334,4 + 10.4,18. e = 50.4,18 (40 - 8)

suy ra Bien thien entropi ~SI dOl vdi sl/. chuyen 109 nude da tu OoC thanh

- .

nude long d 20°C.

~H 2f dT

.6.8 = n.c + Cp -

1 Tn.c 273 T

~ 33~~~~:lq+ 10.418 .2 3031g 293= 15 21 J / K

273 " 273 '

..

Bien thien entropi 1\S2 cua SlJ chuyen SOg nude til 40~. xuong 20°C:

_ 2T dT / _. . 293 _

AS2 - C, 7T - 4,18.50 . 2,3031g - 13,77 J/K

. 313 T 313·

AS = .6.S1 + hS2 = 15,21 - 13,77 = 1,44 J/K

2.3. 'fiuh L\~ trong qua trinh nen diing nhiet thuan nghich

a) 1 mol oxi tit PI = 0,001 de"n P2 = 0,01 atm.

b) i mol metan tit PI = 0,1 de'n P2 . 1 atm.

-

Trong ea hai truong hop, khf duoc xem Ia ly tuong.

lilt. ,A, # ~ ..,.

BAI TAP HOA L(Y CO SO

•

39

Gidi

a)

P . 0·'001 ~ .

L1S == Rln 1 = Bt314In t ;::: -19,143 J/K

P2 0,01

- - .

AS = RIn' PI ;::: 8,3141n 0,1 ::: -1'9,143 J/K

P2 1

K6t qua tinh ilS trong hai truong hQP eho thB:'y bien thien entropi cua khf If tl1dng khong phu thuoc ban chat hoa hoc ciia chung rna chi

dl1(1C xac dinh bang ty so' ap suat, '

, r ,

1

b)

,.

2.4. Xac dinh biin thien 'entropi trong sv chuy~n 2g nude thanh

." : .

hoi tai ap sufft 1,013.105 N/m2 va nhiet dQ bie'n thien ttl oOe de'n 150°C,

bie't nhiet bay hoi cua nude ~H = 2,255 kJ/g va nhiet dung mol cua hoi nl1dc··Cp,h == 30,13 + 11,3.10-3 T J/mol.K, nhiet dung cua nude long bang 75,30 J/molaK.

.-

Gidi

-

Qua trinh gam ba giai doan:

a) chuyen nude long tit o'c den ioo'c (~Sl);' ' .

b) chuyen nude long thanh hoi lJ IOOoe (~S2); . c) dun d~ dua hoi nude ti11000C len 150°C (~S3)

2 373

giai doan (a): AS} = · 75,30.ln = 2,61 J I K

18 273

~

-II .

giai doan (b):

AS2 ::: 2. 2,255.103/373 = 12,09 J/K

. 2 423 2

AS3= .30J3.ln +'.11,3.10-3(423-373)

18.:.·· 373· .18

= 049 J/K

,

giai dean (c):

= 2,61 + 12,09 + 0,49 = 15,19 J/K

,

2.~. MQt blnh kin 2 ngan, ngantlnr nhat co th~ tfch 0,1 rn3 chua

oxi; nganthu hai co th~ tfch 0,4 rn3 chua nito. Hai ngan d~u d cung mot

,.

40

.AI ,.; ,......A p , • _-

Ch uong 2. NGUYEN LY THU HAl CUA NHlfT D9NG'II/C .HtpClo~~

I

diE!u kien vg nhiet d(> 17°C va ap suat 1,013.105 N/m2• Tfnhbien thien

entropi khi 2 khf khuech bin vao nhau,

Gidi

Tfnh so mol cua lnoi khi

1,013.105 .0,1

n02 = 8,314."290 =. 4,2

_ 1,013.106• 0,4 = 16,8 8,314~290

T

• I'· ~ ,

. ..

Bien thien entropiqiia s11 khuech tan khi d P, T~ const du~ tinh

. .

theo tong thuc ..._ . , .!'

..

- .' ... • . ~ • r r I .. .

/ . . _:.. - ..

,V Vl. ,

6.8 = R n.Jn + 112111 . j , '." '-',""

V1 V2 " ,: ' ,

0,5 0,5

::: 8,314 4,21n + 16,8111 = 91,46 J/K

0,1 0,4

I, : .". •

.

. ..

Su khuech tan khi 13. lTIQt qua trinh t\1 di~n bien do do 48> O.

. . . - . "I"

2.6. Tfnh bien thien entropi cua qua trinh dang ds)c benzen cham dong d -5°C neu tai ~oC, (~Hn,c )C614 = 9906,6 c:J,

CP•t (C6H6) = 126,65 J/K

t .

~ .

• . r

, ;

I '

..

cui

8\1 dong d~c cua benzend -SoC La qua trinh kh8ng thuan nghich.

D~ tfnh ~S cho qua trinh Hay hay tl1dng .ttrong qua trtnh dong d~c g6m 3 giai doan thuan nghich sau:

..

.&83

• CeH6 (r, SOC)

~ .

. I "1 i 1:. • t . 1

" 11. _ .' .. '

•

BAI TAP H6A LV CO SO·.

. ,

'41

L\S = AS} + AS2 + AS3

2T . -9906 6 2T

= 126,65 dInT + . , + 122;47dlnT

268 278 278 .

= -35,44 J/K

r •

D~ xet digu kien tlj di8n bien cua qua trinh h6a ~iin benzend _5°C!

phai baa gam h~ khao sat (d day 18. benzen) vdi moi truong thanh h~ co l~p ..

. . .

- . 0

. _ 85 L\Hnc (-5 C)

- . - - 44 + -

. ' , 268

-

AH;~ = AH278 + 2f[Cp,r - Cp•l] dT

278

= -9906,6 + (122 - 126,65) (268 - 278) = -9864,8 J . .

ASmoi trllong = 9864,81 ~68 = 36,8 J/K

. ,

.

L\SCQ l~p = -35,44 + 36,8 = 1,36 J/K > 0

2.7. Tfnh AS cua phan (tng Cd + -2AgCl = CdCl2 + 2Ag di~n ra trong pin dien co sue di~n dQng E = 0,6753 V. Cho nhiet hinh thanh

,

chuan cua CdC12 va AgCI b~ng -389158 J; -126654 J; P = 1; T·= 298 .

. '

Giai

..

Phan (tng dB. cho di~n ra a di~u kien thu~n nghich dAng· nhiet

trong pin di~n nen

L\H = AG + TAS = -A'max + q

do do q = AH + At max

I .

= [AHht (CdCI2) - 2AHht (Agel)] + 2~ F. E

• I .. I

= .~,389158 + 2~ 126654 + 2. 96500. 0,6753 = -135. 850 + 130332,9 = -5517,1 J

AS == qlT = -5517,1/298 = -18t51 JIK -

42

Chuang 2. NGUYEN LY THU HAl CUA NHlfT D9NG LI/e H('JC.l.

-

2.8. Cho bie't dau cua ~G dO'i voi cac qua trinh:

a)

CsHs· (l, OoC) ---+' e6H6 (r, OoC) CaH6 (l, 5,50C) -4 CsHs (r, 5,50C)

- .

o ~ 0 .

C6R6 (l, 10 C) ~ CsHa (r, 10 C) ~ -

b)

c)

. ,

, :

, , I

Gidi

)

Tai o'c va looe, benzen long va benzen r!n khong nam can bdng

vdi rihau nen ~G cua cac qua .trtnh (a) va (c) khong bdng khong, con d6i vdi qua trinh (b) 811 chuy~n trang thai cua benzen xay ra tai 5,50C nen c6 can bdng l zq'" r do do AGb = O. Dei vdi qua trinh (a) 13. diing nhiet

.nen dGT = -SdT. Qua trinh (a) duoc tl1dng tuong chia lam 3 qua trinh ·nhc,:

. 0" - 0'·

CsHa (l, 0 C) -4 CsHs (I, 5,5 C)

27j5

:~GI = -8 (l)dT

273

- I . • . .

·0· 0

CeH6 -(l, 5,5 C) ~ CaRs (r, 5,5 C)

, r

6.02 = 0 .

: :.. J .....

~G3·::: 2f -S (r)dT

. ; ,278t5

·0 0

CaH6 (r, 5,5 C) -4 C6Ha (r, 0 C)

- .

to

AGa = AGI + AG2 + 603 = AGI + AGa

. ~ .

Vi S (1) :> S (r) nen AG1 + A03 ~ AGa < O. (j digu kien dd cho ~g

, .

nhiet dQ va ap suilt, benzen riin bE!n hen benzen long.

, Doi vdi qua trinh (c) cting tfnh ~Ge tirong tl1 qua trinh (a).

I .... •

215 2'F

AGe = -S(l)dT + 0 + J -S(r)dT> 0

273

. 278.6

V~y d io'c benzen long 1a pha ben,

r

2.9. Tinh bien thien th~ ddng ap khi nen dA.ng nhiet 10 rna oxi tit

1,013.105 d~n 10,13.105 Pa tai is'c Chap nhan-oxi lA khi 19 tl1dng.

G· ? .. tat

86 mol oxi bi nen bang

,._, "Ar,. ;..,. ,.,

BAI TAP HOA LV CO SO

•

• I' ~ .. _.. • =- I I

. -, . .. ~: ~ -

43

. . ... - - .... .... - .--

PV 1,013.105.10

n = - = 41'8,7 L .: }

RT 8,314.291

-. .... \.. » ~ I

] - :t" ~ '.

. . .:......- tr., • I' ',-.-

l "

" J < , • t,

"_. .. . -

, , P

dGT = VdP = RTdPlP ~ aGT = RTln 2 (Lmolj.

, " '. ~ ,"p ~ ;,

" "1" : ~ ', '

, • r :, • t ..- l

" J 0' a :105 r' - 1" ,

'..,' , : ' ", . : :, ~ 1 : ,1 ' .. I' 1,,',' ,5 ~', ,~ -',"! :,

dOl vdi 418,7 mol, AGT = 418,7. 8,314. 291 In 5

L013~10

I . '.

~ , :

• I': _.

, AGT = 2332,5 kJ

, , .

-~, -_.!'.!' ,I",'r .:

• " r • ..' _

,...._, , - r-

" . " . I" I

, ' -;, " ~ -, - t

2.10. Bien thien the'dAng ap chuan ciia phan tlng d 250Ci! •• .'.: :!':~'I

H2 + CI2 = 2HCI (k)

- - L

, L

-

.. ' ...!

b~ng -190348,84 J.

, ~ !

Xac dinh bien thien the' dAng ap tai 25°C dOi vdi phan ling

I\" .... -.. , . p

. !t '1 • t-· ... I r'

, .; , r-

T '

, I

, ,

H2 (2 atm) + Cl2 (1 atm) = ~HCI (0,1, atrn). . .

Giai

•• '!"

" S'

. . "

: I r I =i - •• 'I :.' _ .. , I • .,-', .. I" ~

, ~,',' " ,J ~ ~ ,

:,

,

Xufft phat tit bi~u thtrc vi phan cua t~6 dang ap .

. . .. .' .

I~ ~ i j

dO = VdP ~'SdT

•

J

- - ..I

" , ~ . ;

- - - , , ,

!

ta c6 doi vdi qua trinh ding nhiet

. I I • •

,

, ,-

dGT =VdP

I ,

dol vdi 1 mol khf ly tl1dng: V = RT/P do d6 r I ., ·:·,.'r , '. ? I ' I . f ,; i.

, L I

, - ' i

dG RTdl' p' ; '.. Ii'

T ,= n' . : .: " ~; _\ "~ '~ '- ,:' ~ .i ~ 'z ; i ~ I' t; ~ ~

I

I I

1

1 ,-

, , ,

, '

, . -

" ~ : " ,

f '. ' ,~ ,I ," _ ~. :

P.. • I' •

r '~ c-. ~ .' ~

• "" I J. i '-

• • ~ II I r. ~ .:.

Neu trang thai (1) 1.3. t~~u,.g thai c~~~n. thl tq p~1l1dng;. \~~ tren, ta co

• r • - I' _. ~. I • I • ,''I

, "

•

AGT = AG~ + RT [(Ih P) - (In P)O]

•

, ,

Thay so, ta duoc

• • III .! ., ',1' ~.

'.. "\. •• ~ :: I· _ _ ." _ \' "

• I. I' f ,.. r I -. '. '. ... , •• ": • - (....-:... .... ~ PI I ~

AGT = -190348,84 + 8,314.298 [21n Ot1 -:.,lnl, -102]

Ii,'

•

, ,

, .-

= -200040, 737 J -

. , L

-

r-: - ..

-', ~

Chuong 2. NGUYEN LYTHtiHAI CUA NHltr~N~'J.(1cH~~~

, ,

2 .. 11.DOi vdi phan itng -

: ~ I ~

, '

.. .. ..

. , ~ ~ -:~.. .

l1H~98 ::;: 19~376,4 J; L1G~98 = 139862,8 J. '

Tinh AG~, chap nhan Llli~98 khong phu th~Qc T.

. - . .

. . , '

, ~ J ' , - ..

I, " • ..'I ,

, L : ~~~'~'I

• ", 'j,' ': I;, ,:, '

Giai

-' ..

, '

Trude h6t hay tim bi~u thtrc AG~- phu' thllQ'c T. Xuat phat tit djnh

nghla ham G:

.I'

I J" ~ r'" ~ - •

; r I.... .

G = H - TS

..

OG =H+TGrp

, ,

.

I' . .

~ ,

, , ' I

.. .I I _, ~ t ..... 'I _ .-.:

I I" .; • • • '.... ... ', ..

: .:

,

: I

G H OG aG G-H

----- ~ ---

T - 'T - or or - T ",' i

; • G - 1 00:' G

Lay dao ham eua - thea T, ta dude -- , '_ -

~ T · Tor, T2

- ',~ ~

"I 1 I • ••

~ ! I
•
1 G-H G 0 G
........ hay ........... -- - -
~T2 -, T ~
T T err , ...

- ,

H ~ AG' ~- ',',~,', 'JAH' ;'-'", :~';'~ ~'·i"::

U Ll .... Ll . - I I I".. . .

~ = ~ AG: = - T dT + IT

T2 or, T ,I ' : - T2

i '

~,-

-~ ,

I 13. hang so tich phan... _ r . ;' A !, -, )'i ::;,

I _ _ _

, -

, I ,

Trudng hop ella bai toan AH ~ canst do: d6 ~TI ~ dT:::MJ va

l. J ,- T

~' .' -

AG ::;: AH + L T._ D~ tinh I, sit dung dil ki~nda cho d 2,98K, ta duC'jC:

, ' _, ~" , ' ,i .

-, , I· , .....

- .' .. . . . . : . l ,I· 1 I. • I r ~ J I

, -

139862,8 ::;: 196376,4 + 298 I, suy ra I = -189,.64

, ,

.. _. .

.. -. . .

, ~G~ ::;: l1~ - 189,64.600" 196376,4 '~·JI89~64. 60'0

, .

VOl

: ,

, -

AG~ = 82. 592,4 J

i I ;

2.12 .. Chung minh ra.ng dOt v8i khi ly tuang.

, "

, ,:..

o~ :,

a) = -8 - R

Ofp

, .

" ,

sAl T~P H6A LV CO SO

. .' .. , I

45~

. .

- .. .. . --._ ....

-

: .

1

b)

· ,.

.. '

.aF

=--v BP T

• ·

. . .

Gidi

a)

. .

.

G = H - TS =:U + PV - TS = F + PV -+ F =IG-~ PV

of OG av

,

I • • •

.. .

. ~ .. :

-

-

-

Grp

. . ..

r I ... •• r ~ - I

. .a. ..•• I _~ " .. n'

Ofp

or

p

; i

• - 'I ~ l . . J ~

;. .,

. , .

..

aF . R

=-S~P-=-S-R

or p , p' .

b) -

...

av

. _ -.V

ap T ..

of

....... • ,T

- .

oP T

. -

.

! '. Ir• , • .; -.

( ', .. • I' ••

. .

oP

T

, -

- .

t I" .. ., I: - .. ,

. . _.. p: iii-

• I

. .

.. I ~~-

~.

. -

J •

· .

·

.. '

=V - V - V=-V

;; t ... t ' • ";,.

• . . J L ~

. .

2.13. Tinh Q, A, AU, L.\S, l1H, L\F va AG trong qua trinh bay hdi 1

. .

mol nude tai P = 0,15 atm, t = 53,6°C hitt r~ng th~ tfchpha hoi va pha

. .

long bdng 10,21 m3/kg va 0,0010137 m3/kg;, ~~t hca P~i.. ll~qg 2370 .

,.: .. - • ~ . ~,;.1 .•

Jig. f

•

...

. I

. . ~ : ."" . ~ ... - .

~ I ~ • j.:

Gidi

.

. • f i . ~ .',

- . ~

Q = 2370 X· 18 = 42660 J/~ol.

-

. ..

I .. • • ~ _

A = -P(VH - ViJ == 0,15 (10,21 - 0,0010137). 18. 101,156

.'. = ~2788,29! .J ..

.~ • ~ r· : j,

~. . .... ' ~ . J . . ~.f

. . ....

AU = Q + A = 42660 - 2788,29 -r- 39871,_71 J

..

. • I

LlH = Q = 42660 J.

t

.,

..

.,

I . •

. .

Q 42660 , " ,:'.'

AS = - = .: = 130,61 JIK mol.·

. T 326,6

.. .! _. . ! • ,

• • :. • . .' • _ ; • t •• r-. ~ .: ... r . ~ 'j .

'~F = l\U -:TA.S ='Q + A - Q ='A - -278'8,29 J" ". :' .,,'

~ ... -, ~ .

.. l .» .} i: .•

. . . ,

. .

, . . . AG = 0, vi qua trinh bay hoi 13. thuan nghieh 'ding' nhi~~ dA.ng ap,

, . .

. 2.14. Dua vao ca~ nguyen ly'thtl nhat va thit hai cli~ nhi~t dQng

· .

l\ic hoc cung nhfmg h~ thtrc nhiet dQng khat suy ra t~, hai nguyen It,

.. -.

hay chung minh rang dOi vdi mQt chfit bat ky:;'

/

. .

~ ~

.. 1 r

. '

J

.....

46

Chuang 2. NGUYEN LV THU HAl CUA NHltr D9NG we H()C~.:

. -

au op

EN =Tor ~P

T v

all 8'1

=V-T -

. op· T or P

Gidi '

Til bi~u thuc thong nhat hai nguyen If ta co

...

au os·

dU = TdS - PdV ~ = T - P

aVT aVT

(1)

M~t khac d6i vdi the" nhiet dQ,ng dAng tfch F, ta c6 bi~u thtrc vi phan: dF = -PdV - SdT. Vi dF la vi phan toan phan nen h~ thuc Euler . cho ta:

_.

av T ,or v .

. . . au -·ap

Thay vao (1), ta diroc fN . == T ·ar - P

T V

Til bi~u thitc vi phan dol vdi the- nhiet dQng dAng entropi dAng ap

es oP

'r .

ta co:

oR OS

dH=TdS+VdP~ =T +'1

I . oP T.. oP T

M~t khac dO = VdP - SdT, v«)n dung h~ thirc Euler ta co

oS oV

(2)

oP T err p

8H av

Thay vao (2) ta dtt<;fC = --- T + V

j oPT or p

4·

-

-- -

-

Chu y: t~ cac h~ tlnrc phai clnmg minh, thiiy r~ng d6i vdi chat la

khi ly tliong

.<. ~ au

~ T·!' oP RT · 1 NQt nang 'va entanpi

~ - p = -- P ::: o. ,

BV T or v . V cua khi - If tuong

. I khong ·phv· thuoc V

, fJV·. RT' - .. va P .

~. ~ T + V = -- -- + V· ::-:- OJ

err p' .

.P ..

aH

: ,oP T

.... ""'" ~.,. .,

BAI TAP, HOA LV CO SO

•

,.

• ~. . '! .'!I I· =

III. BAI T~PTV GIAI

. .

-

r - . r '1_

' ..

< I I , . r

• I I r

,

r _.. "I •

. . . !I. ,I It":..

. .. 'r. - . . _ • -I ...

• ~ • I I ( ..

' .•. ~ o-t ~,~i I.:·

2.15. Tfnh bien thien entropi cua qua trinh dun n6ng 2 mol nito (duec xem IiI khf Iy tl1dng) tii 300 K d6n' 600 K dudi ap suat khi quyEin trong 2 truong hop: a) ding ap; b) da.ng tfch, bie't rlng,~nhi~t dung Cp . cua nito trong khoang nhiet dQ 300 - 600 K du<,~ cho -bl'J1.g phuong.trinh

. '.. . ; :' . . . . - . : .. it..

...

Cp = 27 + e.io=r J/moLK.

, ·1 .

. .... ,

. i 1 .. " . ).,,

.

DS: 41; 29,5 JIK

2.16. Tinh bie'n thien entropi trong qua trinhkh.~6ch tt~ V8.0 nhau ciia 28g nito va 32goxi; khi hi) vach .ngan ngan each 2 bu6ng chiJa khf co th~ tfch nhu nhau blng 30 l va cO cung mQt di~u ki~n v~ nhi~t de}

va ap sua't

• '1 •

- I·· : . . ,~, ~ . ~ -,

'" • • ~. • ~I " .~. ~ :

:. . .

D8: 11,51 JIK.

,2.17. Tinh bien thien entropi kbi chuy~n lOQg nud<f ~ O~C(thAnh'

• . . i. I I' • • L 11 - .'

hoi d 120°C, cho bie't:< , ' _ _ , ,;,,;,:;!:/,': u' ;_

- nhiet bay hoi cua nude" 100°C bAng 2253 JIg;: _'

~.. •• ~ "I

.- ~ I ··0 I • ~ : to

• . . _. I.· "

...

, - nhiet dung rieng cua nude long bAng. 4, 18:JlK.g;

- nhi~t dung riengcua hoi nUde bdng 1,91 JIK.g.

of

- DB: 744 J/K.

- .. , .--: $. .")

. -.. .

'- 1. k-- • ;

•

2.18. Xac dinh bien thien entropi khi chuy~n 19 ntrdc cham :d6ng

thanh nude da (s .io'c bie't rdng: , " ,', '::i, I' :<' I -' _ ~,

_.

- nhiet dung rieng ciia nude b4ng4,18 J/K.,g; ,-:-

- nhietdung rieng cua nude dB. bAng 1,_86 ~lKg;

r .

.. • • 1

-

, ... ··.1

,

.

- nhiet nong chiiy ella Dl.tOC da bdng 334,4 J IKg ... ,'t, _ ,

.. .

. .

• - 1 •

, :,lJ8.~ 1,147 JlK:g.-

. . - ..

- ,

- \

~' . '- . : . !. .

_ 2.19. Me dinh nhiet dQ Inc din bAng nhiet va-bi6n,thiell entropikhi .

. . .

. trQD 19 ~uOcda b OoC viii 109 nude {j 100°C. Cho ~~t n6~gchay C1ianUdc

da bang 3~4~4 JIg vanhiet dung rieng eua nude bAng 4,I~JlK.g. '~" _. _: _',

• • • •• "I.. ..-

,f)S:',83~64oC; O~;465 JIK

·48

Chuang 2. NGUYEN LY THU HAl CUA NHltr: D9N9-I.I/OHtJ)Q.~

2.20.' Xac dinh bi6n thien entropi khi dun nong lOOg hruhujnh t~

. .

300 K de'n 400 K dua vao cac du kien sau:

• •

• I I J

: . _. . . 3·-

Cp (Srombic) = 14,964 + 26,O~.10- ,.T

. . .

- - .

. . -3

Cp (Sddn ta) = 14t88 + 29,09.-10 T.

,

. -

Nhi~t dQchuy~n Sl'ombic ~ Sddn tala -36:8,6 K vanhi~t chuyifn,'h6a'

nay bang 296,78 J/mol.

I .

: ,

. .

. . .

J •

. .

. ,

. . .. i

+

~ t t-·,·t :

. 'I" •

DS: 24,33 JIK .

2.21. Nhiet dung cua 1 mol CO co phuong trinh phu thuQc T:,

",:' "

Cp(CO) = 26,51 + 7,6,7.10~3T s: , .r ; - ; ~,,' • '

'. . -

8H ~ ~ .j' ";.',

UO :_ ."-".

Tim gia tri cac dai hrong or p va -or p t~.i_T = 500 K CU~ PC?, ;f, .

DS: 30,34 JIK; 0,06 JIK.2

2.22. AR cua qua trinh nong chay 'nude da d ooC bAng :6002,48 J/mol. Nhiet dung mol cua nude da va nUde long bing 37,:202 va! r5~24 JIK. Xac dinh AR, &8 tai P = 1 atm dOl vCsi qua.trinh " .'

H21 (r, - 10°C) --+ H20 (1,~10oc) :. I :.

BS: 5622; 1 J/mol; 20,52 JIK.,

2.23. Tfnh bien thien entropi trong qua trinh dun nong 1 mol nude

til .. 50°C tdi 500°0 dirdi ap'suat khf ql,ly~n, cho bilt: ; ;

- nhiet nong chay cua nude da a OOC;bAng 6004 J/nloi;' _.

. ... 1;-

.' ,! . ~

-

- nhiet bay hoi cua nude eioo'c bdng40660 j/mdl;-

~ - .

- nhiet dung trungbinh cua nude da bing 35',5,6J/rnol.K;

- .

- nhiet dungtrung bmh ciia nude-long b4ng75,31 J/tnol.K;

- nhiet dung cua hoi nude d P. ~ canst bAng (30,20 + 0,00992 T).

J/mol~K~ +

~ .~:- I

. I ~ ~

;' DB: '187,7 JIK

.j. ., . . 1

I ... •• •

. . ." • ! •. -

- .

2.24. 0,35 mol khf ly tltdng d 15,6oC duc;sc dan nCs ttl 1,2 dg-il7~4' t.

TfnhQ~ At ~U, AH, L\S va dG doi vdi qua trinh tren thuc hi~n:

• • I •

J;:-~j6L-~~ ......... ~""'-, ...•. - .- ~-. -- .,-

BA-I TAP H6A LV CO sO

•

49 .

.... '. - - - •• I

a) ding nhiet thuan nghich; ,

- .

. _, r ! . l' .j.~ •.• ~.~-:. q

.. . • ,. II~}

b) dAng nhiet khong thuarrnghich chong :apsuat ngoai b&hg~ [Ii

atm.

DS: a) 1530 J; -1530 J; 0;,0; 5,3 JJ~;-~~30 J

, ~ L • ., • • • ;'., - •

I I - I ... ..

.. . .' -'.

b) ,628 J; -628 J; 0; 0;. Pt:3 J~-1~~9 ~i ,';t

. ~ . .

2.25. Nhiet dung cua hydro Hi mQt ham cuaT:

- ~

. I '~ r

I ~ I·.

. -

.

Tfnh bien thien entropi d6i vdi h~, doi vdi mdi truCJng xung quanh

va dOl vdi h~ co li).p trong hai trudng' h(jp san: " ' " " .. '; ; ,',.. ' '. : ,.J

. . ..... . ..... i '. . .. ~ . . . I .. : -.

'a) dUD n6ng thuan nghich 1 mol hydro tit 300 K den 600 K ya " '

... I '.. : • •• .. .. -' .' •• ' ~ r' • J. _.

I r •• .' I • .

• • of. ••

b) dun n6ng khfmg thuan nghich.

Chu y: d Call (b) gia thi~t moi trtldng xung quanh d 600 K DS: a) 1,74'J/l{; -i,74'JJK; o .: ,::,

..

-

b) 1,74 J/K; ·.;.1,27-rJlK; 0,47 JIK

2.28. Tinh bien thien entropi ciia neon lJ 25°C va i atm cO th~ tich 0,78 I dl1(J~ dan Db tdi 1,25 I va d6ng thoi dtlc;le dun n6ng'tdi 86°C;., (CAll

, y: Vi S la met ham trang thai nen trudc tien co th& tfnh ~s cho qua trlnh dan Db rc3i tinh t1S cho qua trinh dun nong dth~ tech cum khong

d~~) ,

01 .

... . FJS~~ 0,198 JIK

..

-

2.27. (j 25°C entropi cua luu huynh rombic va hru huynh don ta,

bdng 31,88 va 32,55 J/mol.K. Nhiet hinh thanh ella 2 dang tttdng ilng ,

. . '

b~ng o~oo va 0,30 kJ/mol.' Tfnh AG va AF dal vdisr/. chuy~ri. S~~bie --+

. Sddn ta d 2:S°C. EO qua ty trong cua 2 dang S d 25°C, dang thu hinh nao

...

cua S bgn hon ? Xac dinh nhiet deS tai d6 co can bing gifta 2 dang '.

chlly~n hoa, Chap nhan AS va L1H kheng phu thuQc nhiet dQ.

, DS: lOO,34J! 448 K ~

2.28. 0 25°C entropi cua graphit va 'ct1a kim cuong bAng 5,74 va 2,38 J'IK.mol. Nhiet d6t chay cua kim cuong ,ldn hon nhi~t 'dol thay'cu{l

50

~ ;; , ~ ~

Chuong 2. NGUYEN LY THY HAl CUA NHlfJ D9NG LVC H()C.';J

graphit 752 J. Tfnh l1G ung vdi 811 chuyen graphit thanh kim .ctrong.

Cho k6t luan rut ra ttl k6t qua tfnh toan. . ' ,

•

2.29. Xac dinh bien thien th€ dang tfch va bien thien nQi nang khi

lam bay hoi _thu~n nghich '1 mol brom (j ap suat khf quy~n bang 1,013.105 Pa va tai nhi~t dQ s8i cua brom la -7,30C. Nhiet bay .hoi cua .

• • - - • - 'I

brom b&ng 31 k-I/mol. '

~

DS.~ -2,21· kJ/mol; 28, 79 k.I/mol.

. I I

2.30. Nhiet nang chay cua mrdc da 0 o~c bang 335 JIg.' Nhiet dung

.. +. I

rieng cua mrdc bdng 4,18 J/K.g, cua nude -da bAng 2,01 J/K.g. Xac dinh

AG, .&H, AS trong su chuyen 1 mol n,1dc cham dongthanh aa d -5°C.

£)S~· -70 J/mol; -5,83 kJ/mol; -21,5 J/K .

. ,

2.31. Tinh L\H~9S va L\G~98 doi vdi phan ung

2C"+ 2H2· = C2H4 (a)

2C + 3H2 = C2H& (b)

dna vao cac dtt kien sau:

• •

Chat

. () .

S29s[J/Kl

.

AHo da't cbay [kJ Imol]

c

.

5,9

130,5 218,8 230,1

.

-394

-286

-1393

·-1560

.. .

Lieu co khli nang tang hop etylen va etan t~ ,di~~ kien da cho ?

. .

D.S: a) 33 kJ; 49,1 kJ

.' ~

-,' "

~ .

.. b) "-86 kJ; -34,4 kJ.

+

I· •

2 .32~ Dol vdi phan trng

2H2 +.82 .(k) .~ .. 2.H28 (k)

• • I I •

. . . .

bie'n thHln.thedAng apchuan.phu thuQc:nhi~t dQ theophuong trinh

. _. . . .

BAI TAp H6A LV CO S'O "

..

..

... , .

~ r. . I

.'

~GO = (-162400 + 64,48 TIgT -,8,642~10-~T2 - 104,6 T) J

Tinh l\H~ooo va ~s ~ooo

+

. DS: -18~; kJ; -99,5 J/K.

,

2.33. Cho phan ung 2H2S (k) + 302 = 2802 + 2H20 (1) vdi cac du

~H~98 = -1130,5 kJ; ~S~98 = -388,3 J/K; AC~ = 74' JIK ,

Hay bi~u thi ~Ho, ~lf, AGO va ASo dudi dang mQt ham cua T.

2.34. Phan irng

1

Ag + 2 Cl2 = Agel

xay ra trong pin dien vdi sue di~n d{)ng b5.ng 1,132 V d 17°C. Xac dinh AG va AF eua phan tmg. :so qua th~ tfch cua Ag va Agel. Xem C12 13. khi ly tl1dng .

•

DS: ~109139.,8 J; -107927,6 J

-

,2.35. Tinh A, Q, ~H, AU, AS, AF va i1G trong qua trinh nen ddng

nhiet 1 mol khi 1:9' tuong tit 0,05 atm tdi 0,1 atm b soo'c.

DS.~ 2880· J; Q = -2880;

• f

, r

-

AU . 0; ~H = 0; AS =. -5, 76;

AF = -2880; AG = 2880.

2..,38. MQt s6 vi khuan trong dilt c'n'DlQt nang hrong: xae dinh cho

sl/. sinh trudng hang each oxi hoa nitritthanh nitrat: ",

,

. .

I : I '1

, 2NO 2 (aq) + O2 = 2.NOg (aq) .

Cho bi~t nang luong t~ do chuan cua.su hinh thanhNO, va NOg

. : .. I . r. •

b~ng -34,6 kJ/mol va -110,5 kJ/mol. Tinh hrong nang IU<1ng t\i do thoat ·

ra khi 1 mol NO;.bj oxi hoa thanh 1 mol NO.3: .. . ., .

..

FJS.~ -75,9 kJ .. ~

_ L

·2.37.; Dua vao dinh nghia 'va' cac thuQc ' tfnhciia . ham d~~c. 'trtlng

I •• •

- .

hay chirng rninh:

..A. _.till ., .A. ....

52 Chudng 2. NGUYEN LY THU HAl CUA NHIfJ;:fJQ~',W~:~f_;

.... ..... ... :z . "r ... • V? "... _" .. _ _ , 1 __ .. r ,

eo' '00

U=G-T -p ..

or p oP T

. ,

, .

~ ~ .

•

. ": , • l "':

r I" • : '

.. .". ~ "

dG = V oP dV + V oP - S dT

fJV T or. V

. ,

..

. . I i ~. i i " l

, ' 'I _ ,

I .; j ~ ~

~"" .i'.I· ,

, "J ~ "I_ , • • __

••

,

, .: L

"!:

. 1 r

, (fJ2F I errav)2 ,

Cp - CV =-0- T (ifF I aV2)T '

dG

C, = -T 2 orp

I ' , ' , I

:.. .'.:

r "

,

, ,

,

.. ~ "- .. .,;..1 _

.

.. '

au oV .

s.

-

-

of ... ev );

, .

r . .

. ..' I .. ~,j. •

, _'" " : ... "

,. !: ~. .1·

'I - _r I ..

I ;. ,

" .

.. ,," p - ,

: ~ _ ~ i

j ).,.,,. ~

oR .

..

. ... ~ . . ..

·t":· P .. ;' ~: " . .j,

, .~ __ r , "I !

-

-

oP s·' 'oP T '

Ofv

iJrp

i

: .. ~:

'r :."" ~" "",,..- "'~L

of

. OG

-

-

I •

I I" • ~ I ,il''' P

, .. ~,," ., I~ , .: - ... " .. - ~

, - ,I '. ;. "" I " ... " - I p ,,", ' I" ~ ~ : ".

,

2.38~ Tinh bi~n thien nang 111cjng tt1·do 60 khi ~en 7 g nito iJ' 270C

tit PI = 0,5 atm de'n P2 = 3 atm.

DS: 1114,80 J. · ; ·2.39. D'Oi voi phan itng FeeDs: ::::FeD + C02bi6n :thien',nal1e~1tlcptg Gibbs phu thudc nhi~t'dQ dU<jc biEiu thi blng·phtiangtrlnh:,!.t .. ~ f;'!l~ ~; .

.t1G~ =. 73555~46 +, 125,90 T _:48,23'·TmT,+ 48,38.10-3 T2

. . ~. _ l • '.

. . I '. • _ r • I . . ~ . t"')

- .... ~ I ... '. . ~ • ! \ I ~ I . r· _.

,

. ,

Xac dinh L\H~ va AS~ ..

. ~ . ~. .

: .

l ~ • '

" '.. : t z : - : j : ~ "!,... • i"· .

.. ~ ... { ~. .' ::I:... I r

, L

, .,

.

~ -Ii ...' ". ; 1·· "r ,;) "

. i." : .. ~ 1 ~. I

. DS: 87917~94 J; 175,7.7 JIK

"

2.40.Tlm phuong trinh bigl,l di&~ ~G~ phu thuQC; ~tt d9 ~ vdi

. : . I , ., ,. ' ~. '~~

phan Ung '. -: ! 'If-; '.

,

BAI TAP H6A LV CO sO

..

53

1 1

-:- H2 + ~C12 = Hel

2. 2

cho biet:

~H~98 = -92223,34 J ~G~98 = -95174,42 J

Cp'H2 = 29,05 - 0,836.10-3 T + 2.10-6 T2 J/Kmol

Cp,CI2 = 36,65 + 1,045.10-3 T - 25,20.105 T-2 JIK.mol

..

J/KAffiol -

DS: -89732,06 + 6,35 TInT - 2,246.10-3 T2 + 16,72.10-6-T3 -:-1,173.105T-1 - 52,41 T.

2.41. Tfnh AG~98 dO'i vdi cac phan ung:

. N204 (1 atm) = 2N02 (1 atm) ·N204 (10 atm) = 2N02 (1 atm) N20, (1 atm) = 2N02 (10 atm)·

n~u AG~98 cua phan l1ng N204::: 2N02 bang 5392,2 J

FJS~~ 5392,2; -296, 78; 16770,16 J.

2.42. D6i vdi 8\1 hinh thanh 1 mol nude long a trang thai chuan

- .

. AG~98 = -236964,2 J/mol. Tinh i\G~98 dOl vdi 8V hinh thanh mroc long

....

.. neu hydro dUQc lay d ap suat 0,01 atm con oxi a 0,25 atm. .

BS: -223868,26 J

2.43. Hieu l1ng nhiet ding ap chuan va nang 111(Jng Gibbs chuan cua su thang hoa yang b~ng .6H~9S = 378290 J, .1G~98 = 338580 J. Tim

phirong trinh L\G~. phu thuQc T va tinh .6Giooo dOl vdi 8\1 thang hoa eua

•

, I"!!

yang neu

Cp (Au (k» = 20,9 J/Kmol

Cp (Au (r) = 23,65 + 5,18.10-3 T J/K.mol

D8: AG~ = 379343,36 + 6,34 T IgT + 2,59.10-3 T2 - 153,28 T

r ,

.. - r "

,

..

_I '

: j i ;

J

J.. r::l I

. .. .d J -!L

I· f

i ' ~

~ 1 ' .1.. ,

. ( ~

I. _

r·

...

... - - .. .. ...

I I" \ "

j (;.,:

F l.

..... -

I ':.

- ~.

~ -; j

;:

. .-

t

I

,'1

, .

~.

~ f

! l

-i - \_

... , ...

.~ ~ {.1.1

" .J - ~

.... ...

\

L ..

J. ....

. ~.

p

...;. . !

r •

i, f

. i ' J

.' L

_.

.. ~ ';

. ,_ .... ~

.r j.

, , .

.Po

t '.

.:..

........

~.: - j

..

. . .

r

....

: , ~

-, ..

. - -::

! oi.

4

• "L ,

..: : ~ ~

•

t » l .

, .

/.

i··

) ,-

o t .., I .

~ . _

} ..

... ,

l'

-

t '.

1

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. .... .~ .J I. -' , ~

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• •

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,

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j • f

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,

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f

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) '. r

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....

L • ,

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j

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..... '. ]

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r I·

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.,. ..

I .... I

{_ , 1.

.. .,

\. .:

•. +

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:' •

r

~

t i i

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':'.: I , .'

~. (.~ '.. >] .,

[ . r

~ 1

t -.

1 '

-

j

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t

,

.J t i

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.. -

t

.~ .

-

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I ......

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.

. .-

•

t

t .

, -

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)

., (

r t f . 1

. .. ~

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f

)

- L

..

.• :t

.. r

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.,

-.....

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L

r r

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,,(

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,

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'. - •. ·1 '.

.~ .

:·, .. t·~ll

\... p. I .'

, ,

C f 1 j

. ,. ...11.

..

L & ~ ..

\ . .-.

, +

..

,

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t F

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L." J

(

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r-. ~

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lj .f j

J- ~ ~ ,:.-

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·.-111

.~ ~.\

.. t

• ~

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j.

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1

.

! I

j . , ~_ l . rll; ~

.-

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,

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; . ~

Chudng

, ,

CAN BANG HOA H·OC vA· CAN BANG PHA

I j.

, 4 ;. J

I. TOM TAT LV THUVET

1.1. Can bang h6a h9C

•

-(j T, P = const, doivdi phan ung di~n ra theo phuong trinh:

. . .

vIAl + V2A2 + .. ~ = v'lB1 + V'2B2 + ....

digu kien din b~ng 18.:

i

. .

Trong truong hop cac chat phan tmg Ai va cac SaD phcim phan tmg

• r

~dgu 13. chat khf If tudng thi -- ,

r

. [ -

..

i i

i

i

.

Vi J.l~ (T) 13. nang hrong Gibbs doi vdi 1 mol khf ly -tudng nguyen

• I • •

chflt d di~u kien chud~ (T va P = 1 bar) nen _

L Vi J.1~ (T) = ~G~= - RT L Vi In ~

i

i

...... ~, ....... ~ .

56 Chudng 3. CAN BANG HOA HQC VA CAN BANG PI:IA

hoac dG~ = - RTLln~Yi

•

1

~ .

o day nPiYi la tfch cua ap suat can bang cua chat i voi luy thira

~

thfch nghi vi,·D61 vdi phan ung trong pha khf da cho d tren ta co:

t

Vi nFri ladai IUQng kh6ng d5i (j·nhi~t d{> xac dinh nen d~t no bang

Kp do do

.. .

...

'.. o·

- AGT = - RTlnKp

I

Kp 13. h~ng so CaD b~ng hoa hoc, Kp chi phu thudc nhiet uQ, khong phu thuQc ap suat, th~ tich va hrong cac chat co m~t trong h~ phan tmg.

Phuong trinh Day bi~u thi dinh luat tac dung kh81 luong,

DOl voi khi Ij tl1dng gifia ap suat Pi va nang dQ C: co mal quan h~ Pi = CiRT~ Thay Pi tIt phuong trinh nay vao phuong trinh Kp ta dU<;1C

vdi 6.n. = (v' 1 + V'2 +. ~~) - (VI + V2 + ... )

• I • •

Vi Kp chi phu thuQc T nen ve phai cua phuong trinh Kp cting mang

. .

tfnh chat nay. D~t

..

Kc 13. h~ng s6 can bAng b6a .hoc ung vdi n~ng di? C va cling chi phu

thuQc T, khong phu thuQc n6ng dQ. Phuong trinh Kc d trenla mQt dang cua dinh luat tac dung khdi Iudng Guldberg - Waage. Tir phuong trinh

I· .

.

_ Kp suy ra moi lien h~ giua Kp va Kc:

... #'ft.. ;-.,. .,

BAI TAp· HOA LV co SO

•

57

N€u Pi tfnh bA~g atm va th~ tfch tfnh bang' lit thi

. . I

R = 0,082 t. atm/mol.K

Gina Pi va phan mol Xi cua khf trong h6n hop khi Iy ttlang co h~ thuc Pi = P. Xi, P 18. ap suat chung ciia h6nhQp khf. Dua Pi- tit h~ thiic

. _ I )

I .: L

• I " • I'" •

tren vao phuong trinh Kp se duoc

Kp = Kx_. pAD

_ _ I

.. . ...

.. '

, I .

_

' __

1 . _. i

. ,

: I

... .

: \:

. _ t

. ' .

Xi III phan mol cua chat khf Inc can bang.

.. 1

l ,i

, Kx phu thuQc T va P. .: .

r

II) ....

Su lien h~ gitia ba dai hrong Kp, Kc, Kx dl1Qc thehien. banght:

thirc:

Kp = Re. '(RTr~n = x, pAD

DO'i vdi phan (trig hoa hoc trang- h~ di th~ vdi su tham gia eua chat

khi:

. .

aA (r) + bB (k) = gG(k)

~.

. . _

hang so can bang Kp duoc bi~u thj qua ap .suat rieng hie can 'b~ng:

K -.P~

- P- pb

B

..

'I'ruong hop din bang h6a hoc xay ra trong dung dich loang ta co

hang s6 din b~ng · - .

,

_ . , -, ~: I~: :

• ~.r I I ...

_

[] bi~u thi nang dQ molll hie can bilng eua chat,

..

Neu dung dich khong dli loang, thay n6ng ~Q dung dich bAng hoat d{), khi d6 ta co hang so can b~ng ung vdi hoat di} Ka:

, ~

~ '. r ~: ... ~ .. .

I •• P .. I ~ I

Ka=

r.... _

58

.-,a, til "'.A. ~

Chuong 3. CAN BANG HOA H9C VA CAN BANG PHA .

D§ danh gia chieu di~n I bien cua phan ling hoa hoc, Iigudi ta sit dung phuong trinh dang nhiet Van't Hoff co dang

!

zo = RT [lnII(p;ri -.lnKp]

P\ Ii ap snal rieng cua chat khf .i d thdi di~m bat kyo Dua vao dau cua AG co th~ tien doan chieu phan ung. aG < 0, phan ling t\1 di~n ra theo chieu thuan, ~G > 0, phan ung xay ra theo chien nguoc lai, Co th~ dung AGo d~ danh gia kha nang thuc hien phan ung, nha't la khi ~Go« 0, phu hop hop vdi h~ thtrc AGo = -RTlnKp; h~ng so can bang' Kp se rat ldn, do do phan tmg v~ nguyen t&c co kha nang di@:n ra khong nhung d di~u kien chuan rna con d dit1u kien bat ky; Con ~Go » 0 phan irng se khong di~n ra.

D~ xet ap suat c6 anh huang the: nao tdi can-bAng h6a hoc phai sil

dung oong thtrc i

8lnKx dP

An P

!J.V

- - ._..

~ RT I

Cong thuc Day bi~u thi ffiQt each dinh hrong nguyen 1:9' chuy~n dich can b~ng Le Chatelier.

Hang so can bang se thay d5i khi nhiet de} thay d6i. M6i quan h~ ham s6 nay dl1~C bi~u di~n bAng phuong trinh ding ap Van't Hoff:.

8lnKp

---

-

dT ·RT2

AH

811 tich phan gftn dung phuong trinh tren cho ta

AHfdT AH

1nKp = R T2 + I ~ - RT + I

trong do: I 13. hang so tfch phan,

Khi tich phan giin dung phuong trinh Van't Hoff d gidi han hai nhiet dQ Tl va T2, ta c6

~ .

I '

Truong hop .1H la mQt ham cua nhiet, dQ, su tich phan chfnh xac

•

hen phuong trinh Van't Hoff cho ta

'" #fit. ,. '" •

BAI TAP HOA LV CO SO

III

AHo l1a l1b Ac 2 ~Cf 2· .

InKp = - +. In T + . T·+ T + ., T-·:+ I~·~·.·' .

RT R 2R \ 6R ~ 2R _

AHo 13. hdng 96 tfch phan khi lay tfch asn

phuong trinh Kirchhoff dT = l1Cp .

phan 'kh8ng dinh h~n

,

J

~ I _ . .

~ . '_ r

!. ..":

I 1ft hang' ;so tfch phan,

D~ tinh Kp d T bat ky b~ng phuong trmh tren c~n phai bitt hang so I; th l1dng I duoc xac dinh khi bie't Kp d mf}.t nhiet dQ nao do.

r .-:

. _~ ...

.. ~

1.2. Can bang pha

I •

.. '

• • - ... L

:> He mot cdu tit

.. ..

. "Doi vdi chat nguyen chat vi~c chuy8n tit tr~ng'thar't~p h~p iJ.a~

sang trang thai t~p hop khac, ty nhu s~ nong .chay, s~ 'bay 'hdi ·d8i. v~ chat long; sQ thang hoa doi vdi chat riln, sf/. bien hoa tft dang thu 'liini} Day sang dang thu hlnh khac eua mQt chat r1ri, 'duC1c 'nlO" ' ta.' bAng

, _ .

. .

- ~ ', ..

• l . . :. ~

phuong trinh Clapeyron - Clausius, dang chinh xac

dP AH

--_ .........

dT TAV

. - .. ~ ..

d day AH 13. nhiet chuyen pha; A V la bien thien th~ tfch trong sT/. chuy~n

pha, T la nhiet de? tuyet dOl cua su chuyen pha, dP/dT bi~tiL~ th] s~ phu

thuoc cua ap suat chuyen pha vao Iihi~tdQ. - ... - ., '~.;

Phuong trinh Clapeyron - Clausius c6 y nghia 1a' bi~u ihitc dinh luong cua nguyen ly chuy~n·dich tan 'bang ap 'dvng cho ·sf!.·chuy'~h pha

loai 1~

•

, .

, Ap dung cho qua trinh bay hoi va thang hoa cq.~_ch~t l).guy~~ cll~~;

phuong trinh Clapeyron - Clausius co dang

I _ ...

i ~. I':

. ~

L I I P

I. t

: I .: ,.~,. t '

:. I .;. ~.:.. _.. •

. ; I ~ ~

L .. _ I _, .,'

- • p • • ...

•

t

I I I .

... .' ..: , ~ -:

_ . . f. : .' . I _;

Neu hoi duoc coi la khf If tUdng thi dol ivdi 1 mol Vb ,=. RTIP;' thay

vao phirong trtnh 6Hh , se dtroc .... . . L' - r. .

dlnP. AHh - dT ~ RT2

•

. I': .. ,

. ~ .

- :.- I • • • .:

~ . I I I ~ _. - .', I I .

. • r : J, '.

• • : ~-4 .~ 1 •. _ !

- .~ .

, : )

. , , i

.: I

. .. _..

60

.. .

Chuang 3. CAN sANG HOA H"C VA CAN BANt;-PH14.

. .

Su tfch phan khong xac dinh phuong trinh Day cho ta ",

. ,

, ~H 1

InP = - h. - + const . (AHh ;= const) .

R T

Khi tich phan xac dinh, ta duoc

P2 AHh ( 1 1 1

In - l - J

PI R T} T2

.. ,

j ...

. I

'(l1Hh = const trong khoang

•

• •

, ~ Quy tde pha

~ I

Nguoi ta goi pha, mQt h~ dang th~ co thuoc tinh -h'6a' hoc .'va nhi~t

dQng hoc nhu nhau d khap moi phan cua h~ va phan cachvdi cac 'p'MIi khac bang' bg mat phan chiao Quy tilc pha la mdt quy , tAc, cho phep xac

• • ." I

dinh cac di~u kien thea do co 8\1 bao toan so pha trong Jl)Qt he .can bA:Q.g

di th~. - ." , , '

II .• •..

Quy t~c pha diroc bi~u thi bang phuong trinh

., I; .

I. • ~ ~ :. •

.: .: '. i

f= K -, + 2~ f la so bac tu do cua he;

K la so cau ttl;

q, 18. so pha.

r t'.. p:

~ • I ..

I ' , .

. I

(

" ._ ;. I

" ,

MQt h~ nhiet dQng eo th~ dl1~C phan loai.

a) thea so pha: h~ 1 pha, 2 pha, 3 pha, r>, .

i

, .'

-. • I

.

, . . ..

~ "

. ~ . ,

b) theo so eft u ttl: h~ .lea u tit (h~ ba.c .nhat), h~ 2· ca u. tit, (h~ ~b4e:

hai), h~ 3 c~u tu (h~ bac ba)... _ ,

e Phiin tich lj h6a

, '

_ • I I I T I .

.: .' • I 'I J ~.' -

Phan tfch 1:9' hoa la mot phuong phap nghien ctru nhtmg thudc tinh

vat ly cua h~ theo thanh phan eua he, rna dang ph5 bie'n lit phan tich nhiet dua tren sl1 quan sat tOe dQ nguoi lanh cua cac chat nguyen chat

nong chay va cac hop kim nong chay. ' ;,

'I'ren Cd Sd gian d~ nong chay (tren d6 eo nhftng dl1dhg': nguQi lanh) nguoi ta xdy dung gian db pha cua h~. D6 Iii nhfmg gian dt1 ding ap (nhiet dQ - thanh phan) hoac gian dQ dAng nhiet (ap suat - thanh phan), Hmh ve dudi day bi~u thi gian d~ nguoi lanh va gian d& pha (dAng ap)

"" - ", ~ 'II

BAI TAP HOA LV CO SO

- .... ,.

-.

cua h~ 2 cau ttl hoa tan hoan toan vao nhau a trang thai 19n9 va kh9qg: tan VaG nhau d trang thai.ran (h~ Bi - Cd)., " ". j j • ;' • ;.; l

I

-j, '.

.-"

- l

.

... I ~. ~

r •

1

.. -

r "I ~ • ~ ...

. r.l .• :' ' _. r . .

r -

t' 8 321

2 J 4 5 6

I

.............................. - _ ....... ,._. ....

, I '

_ • r

_I: ..

- ..

I

1lI

f

. ,

I'

- ~ -·1 ,--

. ,j. , .

• . I ,

,} ....

J I
1l t J
I I I t
t I J . I
, I
H Cel I J ,

J

Thi; 9ian Bi

Doi vdi h~ b~c 2 nay f = K - ~ + 1 vi P = canst'. S6b~c t\1 do cue dai bang f= 2 - 1 + 1 ::: 2. ,

Gian dB pha chia lam 4 khu vue. Khu V\1c I (trig·' vdi h~ dang th~ cua pha long Bi - Cd. Khu vue III . ding nhu IV ung vdi h~ dj th~ 2 pha:

Bi (r) + han hop long Bi - Cd va Cd (r) + han hop long Cd - Bi. Duong

, cong A E B la duong long tren do lA h~ 1 phatso btc t\1 do f = 2 - 1 + 1 = 2. DQc thea duong long xiiy ra su k€t tinh Bi va Cd, h~ 13. 2 pha va f::: 2 _ 2 + 1 = 1. Tai di~m otecti E, h~ g6m 3 pha dang thai Wn tai, do la 1 pha long va 2 pha riin cua tinh th~ Cd va Bi.,

I •• • _

.. .

- T~i di~m E, f = 2 - 3 + 1 -:-. O~ , '., " ~' .: !L'

Duong th~Dg CD di qua E .la duong,riin, dudi do (khu \,'\fell) chi

I • .,

. tan tai 2 pha tinh th~ Bi * Cd. _ ....'. >; ,;(,,:

D~ xac dinh thanh phan % cua pha long n~m canibAtig 'vlir pli~'; tinh th~ Cd tai nhiet dQ T nao ·do thi ke 1 dUdlig .thing di qua di~m' -F!: chAng han (irng voi T). Duong thing di qua F· se cdt·'ltl.1dnit' cong' BE t~it M. Ttl' di~m M ha dtldng th£ng goc voi true thanh ph!n,gia 'su c't t~i'H.!·:

• r:,' ~ ~ .:. •

I • .. _.

62

Chuong 3. CAN BANG HOA Ht;>C'VA CAN BANG·PHA

Di~m H se itng vdi thanh phan % ciia 2 cau tit Cd va Bi trorig pha long. Tj du T = 210°C thl H se ung vdi 65% Cd va 35% Bi trong pha long. Con ' muO"n xac dinh luong tuong dol cua 2 pha tai 1 di~ln Khat ky tren gian d6 thi sa dung quy t~e don bffy theo do tai K

. ~

Iuong cau tit fall Cd

htQng pha long (Cd + Bi) eo thanh phtin H

MK

- -==-

FK

Ne'u h6n hop 2 cau tit khi n6ng chay tao ra rndt hop chat h6a hQC b~n vftng, khong hj phan huy, co thanh phan cua han hop ri1n va cua pha long trung nhau thi tren gian dB pha co cue dai, ung vdi hop chat nong chay hoan nguyen co cong thtrc AxBy. Thi du h~ Mg - Zn.

tc

411 400 i;

t

- --,

. E ~-- -----

JOO 1 J Ez

. ,

I

0; •

600

500

-..----- .......................... -. ...........

J •

: 0 In.

411 61) 80

% .

, 0 MS - ""

~ i

: • I

Gian do pha cua h~ co hQp chat nong chay hoan nguyen dU<Jc coi I:}

s11 ke't hop 2 gian dB n6i tie'p nhau co chung mQt tung dQ.

__ " 'So vdi h~ bac 2, h~ 3 cau tit co them mQt bien so nfia, d ap suat kh8ng d6i, gian dQ pha cua h~ 3 cau tit phai bi~u thi su phu thuoc gina 2 n~ng dQ bien thien va nhiet dQ. D~ xay dung gian d6 nay, nguoi ta sU dung phuong phap Gibbs - Rozeboom theo ,d6 gian d6la mQt tam giac d~u_ma moi dinh bi~u thj 100% cau t..:1. M6i canh (tng vdi mQt h~ 2 cau

~tit.)dai di~m trong tam giac itng vdi mQt thanh phan xac dinh cua h~ 3 c[u~ t~1i.·

BA. TAP' H6A LV CO SO

..

63~

c

T~i 1 di~m P batky trong tam giac ke 3 dlldng thAng song song vdi canh dO'i dien vdi dinh,

'T6ng cac doan

-

. Pa + Ph + Pc = AB ;:: 100.

A

c . 8

Nhu vay theo tfnh ch§.'t nay cua tam giac d~u Rozeboom,

. ,

tai P, thanh phan c·ua chd't A

· IS. 20%, chat B IS. 50%, chat C la 30%~

...

".,A. ~" .,

II. BAI TAP CO LOt GIAI

0IIII

}C 3.1. Dun nong tdi 4450CmQt binh kin ~hita 8 mol r, va 5,3 mol H2

I • • I

J

thi tao ra 9,5 mol HI hie can b~ng. Xac dinh 111Qng HI thu dl1qc khi xuai

phat tir B mol 12 va 3 mol H2-

Gitii ...

I I

Hclng so can bang ciia phan ung

.

H2 + 12 _ .... 2HI

co dang:

.

Vi phan ung dii cho di~n ra kh6ng co su bien thien th~ tich nen Kc vAn giu nguyen tri sokhi thay n&ng dQ biing s6 mol .

Kc = . (9,5)e = 50,9

. 95 95

8- ' 53- ' 2 ' 2

[HI]2

50,9 = ._.,.....---~.--....,.....---"""T""'"

8 - [HI] 3 ~ [HI]

2 2

[HI] = 5, 75 mol.

64

A ~ til "".... ~

Chuong 3. 'CAN BANG HOA HC;>C VA CAN BANG PHA;

/'l3.2. 0 200°C hdng s6 din bang Kp cua phan tmg de hydro h6a ruou isopropylic .trong pha khf

CH3CHOHCH3 (k)

HaC CaCH3 (k) + H2 (Ie)

b~ng 6,92.104 Pa. Tfnh de? phan ly cua ruou Day d 200°C va dudi ap suat

~ -

9,7.104Pa. Khi tfnh chap nhan han hop khi tUo.11 thea dinh luat khf ly

,

tuong,

•

. Gidi ~

Goi n la so mol ruou isapropylic va a 13. dQ phan ly, sO' mol ruou con lai tai hie CaD biing 19.

n - na = n(l - a)

so mol axeton duoc tao ra cling bang so mol hydro va bclng no; T6ng sO' mol chat trong han hop khf hIC can b~ng la

~ni = n(l - a) + no; + no. = n(l + a)

,; - - .....

Ap dung dinh Iuat Dalton doi vdi hon hop khf hie can bang ta co

• dO'i voi ruou isopropylic, ap suat rieng phan bang

1- a

p = P

R 1 + a

..

• doi voi axeton cling nhu doi voi hydro ta co

suy ra

a·

PA= PH= P

1+ a

Dinh Iuat tac dung khO'i luong cho ta:

PA • PH ,[ex. 1(1 +a)r . p2 a2p

K p = ....... _.:::: = ------

PH [(I-a) 1(1 +a)]P 1- a2

211

a - ---- - ---- = 0,415

1 + (P 1 Kp) 9,7.104

1-+~-~

6,92.104

...

a = 0,645

hoac

•

64,5%

- ,

65·

..

3.3. T~i 500e va dudiap.sudt 0,344 atm de? phan ly cua N204 .

.....

thanh N02 bang 63%. Xac dinh Kp va Kc.

Gidi

..

Doi .. vdi phan irng

h~ng s6 can bang Kp co dang:

..

Ne'u a Iii de} phan ly thi t5ng so mol hie can bAng se 13.(1 _·ct) + 20. = 1 + o; neu xuat phat tit 1 mol N204

2a

PNO = .. P

2 1 + ex

I-a

- p

- ....

,

1+0,

, . j

- I • • _

. Khi thay cac h~ thtrc nay vao phuong trinh Kp, ta duqc ·

.. -._

•

4a2 4.(0,63)2

Kp ~ 2 • P := ? • 0,344 = 0,867

1 - a 1. - (0.63) r •

Kc = Kp (RT)-lHl. Vi ill1 = 1

r..

nen

Kc = KplRT = 0,86·7/0,082.323 Re'::: O,034~

~ I •

3.4. Tai 1080 K h~llg se; carl bang cua ph~l1 trng

, .

;

I

CO + H20 (k) ~-- CO2 + Hi

bang 1. Ttrn thanh phan cua hBn hop khf hie can bang neu xuat phat ttl 2 th~ tich co va 3 th~ tich H20.

. +

Gidi

. Vi th~tich ty Ie vci s6 mol nen co th~ xem han hop dau g5Jn 21nol

, .

co va 3 mol H20. GQi x 13 s~ mol CO2 tao ra va cung I1h1.1 v~y doi voi

hydro, do d6

... .

I

X - .,

K = 1 = ---- ~ suy ra x = 1,2

(2 - x) (3 -~ x) -

66

..-..&. ~ .....A . ~

Chuang 3. CAN BANG HOA, Ht;>C VA CA_N BANG PHA

., Han hop khf can bang co: Mng se) mol bArig 5, .nen thanh phan

phan tram cac chat nhu sau: _ _': /

co. 1,2 x 100· 2 0

2 : = 4%

5

1,2 x 100 .

H2 : ' = 24%

5 .

CO : 0,8 x 100 = 16% 5

.. ~ .

.' . .

. 18 100 .

H O· t x-36o

2 • - %

: 5 .

-

3.5. MQt h8n hop khf g6m 1 mol nito va 3 mol hydroduecgia nhiet

•

. tdi 387°C. 'I'ai ap suat 10 atm, han hop can bltng chua 3,85% (mol)

amoniac. Xac dinh Kp va Kc.

. .. I 1 I

., I ... •

Guii

-

. .

Vi nita va hydro dUQc lay viii 111Qng phu hop vdi h~s6 ty 111<;Jng ella

. . . - -

, . ,

phan tmg nen hBn hop can bang cung co quan h~ ty luong d6. Do d6 til

thanh phan amoniac 3',85%. c6 th~ d'~ dang tinh ra thanh phan 'ella cac chat con lai; C\1 th~ d6i vdi nito taoo

va doi vdi hydro:

100 - 3,85 ~ ------ = 24 04%

4 '

(100 - 3,85)

--------- X 3 =.72,1-1% 4 .

Tinh ap suat rieng phan d6i v{ji tUng chat:

PNH = 0,0385 x 10 = 0,385 atm

3 .

. - .' . I . .

PN2 = 0,2404 ~' 10 = 2,404 atm PH2 = 0, 7211 x 10 ;::: 7,211 atm.

n

p£ - . 2

. K~ = - NHa 3:: (0,385) 3 = 1,644.10-4

PN2 • PH2 2,404. (7,211)

. . .

_ Kc= 'Kp. '(R'i'rAD = 1(1,644.10-4) (0,082.660)2 :::: 0,4825

, ;

3.6. d 63°C hang so can bang Kp ciia phan ung

. b~ng 1,27.

'r

BAI TAp H6ALV co SO

I .," "

67

Xac dinh thanh ph'n hBn hc;1P din bang khi: a) ap s:uat chung bang 1 atm;

- " I

,

. b) ap sus:t chung bAng 10 atm.

ous

I .... • •

. " '.' .

, -

Ap dung dinh lu~t tacdung kh6i hlc)ng vao phan itng di. cho ta 00:

.

a) PN02 + + PN204 = L suy ra PN20 .. = 1- PN02

P~o

-

b) Tnidng hop ap suat chung bang 10 atm.

10- PN02 Giai ra ta dtC<]c; PN02 = 2,98 va P~204 = 7,02 ung vdi thanh phan %

la. 29,8% N02 va 70,2% N204• , l- "_

" .

" ,

.

3.7. (j ooc va dl10i ap suat P 7 1 atrn, hang sc5 can bang Kp cua

phanung -

• "" t

bdng 0,049, itng vdi de- phan ly IS. 11%.

,

,

" "

a) Cung a nhiet dQ da cho, khi giam ap 8U(t ttl 1 atm xu6ng 0,8

atm, dl) phan ly thay d8i th6 nao? . -' . ,: ~ i·

.

b)i)~ d{j phan ly dat 8% thi phai Den han hop khftdi ap suat bao·

.nhieu ?

-'

." ·68

~ ,

Chuong 3. CAN sANG HOA H"C·VA cAN MNS·PHA·

Gidi

: . ~ .)

i •

I

.. I :" r .' :.

N204 - - 2N02

a)

Phan (tng

Han hop ddu (mol)

Han hop can bIing (mol)

1

. 0 2a

1- ex

,.

~.

. . -

1+a,

... :

a la de) phan ly

(2a)2 1 4a2

Kp == . · - p =.. ·2 P

I-a l+a I-a

40.2 0,049

2 = = 0,0612

1- a 0,8

, .-

Giai ra a ~ 0, 123 tu~ 13. 12,3%, so vdi 11 % d P ~1 atrn thi tang

11,8%~ ~.. . . . .

. .

• ',I

b)

· .. '4. (0,08)2

0,049 = 2 • P

1 - (0,08)

. ,

,

suy ra P = 1,9· atm.

..

/!3.8~ Chung to rang' doi vdi phan ung 1

802 + -02.= 803 (k)

2·

,

, ~

mite dQ oxi hoa cua 802 thanh S03 dllQC bi~u thj -biing phuong trinh

..

- K. pl/2,.

p. 0

_ 2

Y - 1 + K, .P~2

C6 th~ rut ra nhirng k~t luan gl titphlldng trinh duoc thi6t lap ?

. -

. ..

.. ':' .. .

... : .

, .

.

. ..

_.

Gidi

.... .

_. ,

. ,

Hang s6 can bang' Kp dO'i vdi phan (tng dAcha ducc vie't

. .

p..

K,SOa

P = P pl/2

. S02 01 02

•• I l-

I : ~

.BAI T~P. t16A LV co.so

• • • .. • r • I

: .,

69

I • I _ l ' .. ", I

suyra

Ps~

----

P K Pt12

80a p' O2

~

1

,-. v . PS02 1 .

hoac P .... _ + 1 = K . 'p' 1/2 "+ 1 .. .i.' . -

SOa 'P a 02

,

• I' ..

4- r

. .. ~.,

J • •

l+,Kp .p1_l2 .1 .. , .

, °2 ' ...

--

-

y

•• L

~ . -

. .

JX73.9. Tfnh hang sCf can bAng Kp d250C dOl vdi phan ung

- .... --

bi6t rang nang hrong t\l do chu&n aGo dal vdi phan ftng

co + 2H2 = CH30H (l) !

. . ~ '.

bAng -29,1 kJ/mol va ap suat hoi cua rnetanol d 25°C bang 1620 Pa.

I' '. • '. I' . , -. • ..' ..

• r I I '. .. .

Gidi

.. - .' . .. . • I - . .

- Dei voi phan ung-chuy~nh6a'CH30H (l) = CH'30H-(k),

- .

-. -

.' . .. .. . ' .. 16200

AGo = -RTlnP = -8,314. 298 In = 4540 J/mol

101325· , ..

: '

Ma t khac ta lai co:

• •

. ,

~

. t\GO = -29100 J/mol + .,

- AGo = 4540 J/mol .

+

, CH30H (l) = CH30H (k)

-

______ ~-J.

,.

~GO = -24560 J/mol

I

co + 2H2 = ~H30H_,(k) .' '. _, ,

I. •• •

Hang 96 can blng Kp dUQc tinh:

•

. j

Kp = exp (-AGo I RT)

Kp = exp [24560 I (8,314. 298)] = 2,02.10" atm-2

.. ,-

~ . .

• I _. • • .'

/~ 3.10. HAng so can blllg cuaphan WIg ... -

.. .. I • • • • ... •

.... -

r

•

70- Chl.1dng 3. CAN sANG H6A HQC'vA cAN BANG PHA -

,

- bA.ng' 1,4 t(l,i 1000.~ , -,

Hoi phan tcng se di@n ra theo chieu nao khi hAn hop phan i1ng g6m 5.0% (mol) CO; 5% (mol) ,H20; 20% (mol) CO2 va 25% (mol) H2 ?

Gidi

I· . . .

Phuong trinh dAng nhiet Van't Hoff cho ta

, I'

L\G = - RT {lnKp -lnD(P\)}

,

- ,

, 0,20. '0,25

= -8,314. 1000 In L4 ..... In 0

' 0,50. 0, 6

&G = + 2965,40 J > 0

•

Vf1.y pha~ ung aii cho diAn ra theo chisu tit phai sang trai,

,// 3.11. Tinh -hAng se> can ,bing l{p d 600 K dO'i vdi phan llng

, , ,

2R2 + CO ~rt CH30H (k)

· bi~t rang tai nhiet de;> nay phan trng

, .

"

,

co

CH30R (k) + CO • CH3COOH (k)

Kp,l = 2,78.10-9 Pa-I- " • -

(1)

.

va phin flng .: "

, ,

• ' j

2H2 + CH3COOH (k)

, , I

-' n' 2CH30H (k)

(2)

,

co

. ,

Kp,2 = 6,5.10-6 Pa-i. ,

t

Plian ang co h~ng' s6 can bing. phai tmh 19. ktt qua eua' su cQng 'hai phan WIg (1) va (2), do do bi~n thien nang ht~ng Gibbs'cu~ phan

, .

mig phiii tim ~G~ se bang t\G~ + -&G~.

",,,,,. ill' ~. •

BAI TAP HOA'·LY CO'SO·" .. ,';

•

..

"'t .. • . ~

, . ,

... 71

11 G ~ = - RTlnKp,r _,\: _ RT ., {}{p, ~ . Kp, ~ l ~ .; R~r fu ~pi

i\G~ = -RTlnKp, 2' . ;. .':; =:.,

K - K K --... 2 78 10-9 6 5 10-6 - 1 8 10-L-4~p" -1 ~ " I: i . (_.. L' •. 1 .~_t J

suy ra p - P,l II P,2 - ,.. ~,... -,.. .-:~ a- .. , ·-";.·f: .·.l~J;.'~

- . .... _." I,

: ..' -:... ; • I .:. ~ ~ ~ II • ~ • • • - J :;: I I -. I ... •

;0 3.i2. d 813 K ap suatphan ly cua,:M~CQ~·bfing:q-t·~96.~10~,~~~.?

843 K, ap suat Day bang' 1, 786.105 Pat Tfnh hieu trng nhi~t cfia s~ phan

tfch MgC03 thea phan ung ._ .... v

M·gCOa· = == MgO·+ C02~ , 'r~ ..

- 1

. . 1 - t I I'

• . II I

'I'ai nhiet di} nao thi ap suat phan ly b~ng 1,013.105 Pa'1'-' __ ; i. ~ " . ;

•

. ~

.. .: r· I· : .

Gidi

. ,

- .

Chap nhan hieu tmg nhi~t khong phu thuQc T, do d6 .

I • 1 '.' I .' • I, I • •••• .;

RTt • m2' ·In KK,-Pl'r, ~ 1· < 1,786.10~ ·l

11 ~ 1 ;~. 83i4~·8· .a:S43'Iii . .. ..- .J

.P~Tl -~ ~ . 0,996.105

AH = ----____...- =,L_......----~----

T2 - T, 843 - 813

=C·'111.'30t(J) .:_: .,: '! .• \ '.J

'-

Xac dinh nhiet dQ' T d~ ap suat phan .ly b~ng 1,013.105~Pa _ ..

T - Tl RTI IIi (Kp.T'l i/ K~'~l) :

-~-

-

T AH :

." • PJ •

f '

., . . "!.. .

~ I ~; - i-.

,

. , .

. '

• L

• r 1'1 I

i

. ,

, '

suy ra T = 814 K~ -

f. -

. t _

I .

. ,

. ,

" ,'~_ . _l ~ , , ..

: ~ J :

~ . • I i I

~ .:... -..~.

t ~ .

;',- _l~ 'Y

. , . 1 J 1· -

· . .. . . . egl' + CO2 -: 2CO _ .,; -': . . _;.~ . f· 1(1) .

trang thai din bang'dtlQc xacdinh bAng c~cdu ki~n:·: ,:' '. :,'! t ; •. r

II

., . :- .

,

.. ~. ..

1

% CO trong h3n hop

.. .

'. _ ." . 74;5.5

. .... : - 93·,08; ... ··r ~.:.: •. -.

-

nhiet d6 fe

.. ...

ap sual toan ph§.n /atrn

····:'800 900

·2,57 2,30 ..

. .

..' . '.

t

72

, .A"" ~ " "'...&-

Chuong 3~ CAN BANG HOA HOC-~VA CAN4BANG PHA

H!ng so can blng d soo'c dCii vdi phan ung· " 2Q02 « "2CO + O2

(2)

...

bdng 1,25.10-16 atm. , '.

, Bi6t rlng nhiet hinh thanh d soo'c dO'i vdi CO2'bdng ~390, 7

kJ/m~l, ha,y'tiiih dR, L\S a soo'c doi vdi phan tmg (2). . -, .

. ~ .

r "

" " "

" _ ~

Giai

1

I • i

- ,I" ~ .

" .

i :

Chap nhan khf 13. khi}Iy tl1dng, ap'sua't can bdng dol vdi phan tlng

.. _... ....

(1) nhu sau:, _ "

1073 1173

.

1(co2) .'

2;57 t 0,2545 atm ""2,30. 0,0692 atm

;

1(co)

2,57. 0,7455 atm 2,30. 0,930"8 atm "

nhiet do / K

... .

HAng 'so CaD b~ng ~p 1 ciia phanung (1):

I " " ,. •

.

Kp,l = P~o 1PC02 .

d 1073 K . Kp,l = (2,57. 0,7455)2/ (2,57, 0.2545) - 5,612atm

" "

~ . " 2

o 1173 K Kp, 1 = (2,30. 0,9308) I (2,3.0. 0.0692) = 28,Sp atm

6H diroc tfnh tit phuong trinh dang ap

KPT MI ( 1 1 ')

1 ~ 2 l )

n Kp,T1 :::: R Tl ' _ T2

",

In 28,80 '_ L\_~-!_. 1 _ 1 5,612 8,314 107"3 1173

{

suy ra flH ~ 171,2 kJ/lnol.

Vi AH = const trong khoang 1073 - 1173 K nen ~6 th~ xem gia tri IlH tinh dl1<}c In ling vdi nhiet deS 11 73 K dOl vdi phan ung (1).

. '.. .

D~ tfnh 6Hl173 d6i vdi phan itq.g (2). .hay v~n dung dinh luatHess:

. . I I -' • , • t ..

.. • • • _ I r .. _. • •

" ~

.. C~r + CO2 . sc - 2CO _ l1H1173 = 171,~ kJhnol '

• •• I

•

" ' .

~Hl173 = -390, 7 kJ/inol

Lay 2 ph irong trinh tru di nha u, ta dU(Jc ~

...

BAI TAP H6A LV CO sO

•

73

2C02 = 2CO + O2 Mil173 = 561,9 kJ/mol

..

DOl vdi phan ling (2), ~Go = -RTlnKp

-:--

,

~G~173 = -8,314. 11731n(1,25.10-H)

• • • I •

"

::= 357200 J'/mol ..

'. - .

l1H - L\G 561~900 - 357200 J K

LlS1173 =. = . =.174,4 /

T 1173'

/ 3.14. Xac dinh hi~u ling nhiet cua phail ttng

(1)

Khi bi~t s11 phu thuoc nhiet de? cua hang so can b~ng doi vdi cac phan ung sa u:

• j

2H2 + CHaCOOH (k) - - 2CH30H (k)

(2)

I • 3149 '

19Kp, 2 = - T + 5,43

, .

CH30H (k) + CO c-_ CH3COOH (k)

1835 .

IgKp,3 = - T + 6,61

(3)

Gidi

Doi voi phan -(tng (2)

r

o .

dG 2 = -2,303 RTIgKp,2

,.6G~ = -2,303 RTIgKp•3 AG~ =: ~2,30B RTIgKp,l ,

Dol vdi phan ung (3) DO'i vdi phan ung (1)

-RT. 2,3031g Kp,l = -2,303 RTIgKp,2 - 2,303 RTIgKp,3

.. ~

/

4984

19Kp•1 = IgKp•2 + 19Kp,3 = - T + 12,04' .

, d In Kp,l d r 4984 ' 1 2,'303. 4984 .,

= l2,303 - + 12,04 J = T2

dT dT T

VfJ.y flH = 2,303. 8,314. 4984 = 95.400 J/mol

.. ,.

. ,.

, .

74

Chuong 3. CAN BANG HOA H()C' VA CAN sANS PHA

)1 3.15. Tinh hang se; can b~ng Kp d 1100 Kd81 vdi 'phiin ilng

.

..

., .

. I ,

• , L

C+C02 24 2CO

bie't Mi298 = 171.923,4 J; Kp 1000 ::;; 1,793 atm.

, . , -

,

t

va nhiet dung mol dAng ap cua cac chat co dang

Cp,co2 [J/mol.K] 43,221 + II,453.10-3T - 9,614.105 T-2

CP•co [J/mol.K] CP.c [J/mol.K]

27,588 + 5,016.10-3 T

, I .

,

Gidi

,

., .

Phuong trlnh diing ap Van't Hoff dUQc vie't

I •

- - K If

. 2 P 1100 . AH

, .", .. ' dlnKp/dT = AHIRT hay In K ' = .: ' 2 dT

, , . P,lOiX) , 1000 RT

Tit phuong trinh Kirchhoff AHT = ,~Ho + J Ll CpdT ,

= 0,794 - 12,373.10-3 T + 14,50.105 T-2

L\HT = AHo + 0,794 T - 6,186.10-3 T2 - 14,50.105.T-1

• I

Thay ~HT = 171.923,4 J va T = 298 vao phuong trinh AHT, suy ra

AHo:= 177106,6 J, dodo phuong trinh AHT co dang: '

ART = 177106,6 + 0,794 T - 6, 186. 10-3;T2 - 14,50~105 T~l

In Kp,l100 1 If 177106,6 + 0,794 T - 6,186.10-3 T2 - 14,50.105 T-1 T

:- 2 d

1, 793 R 1000 T ",' .

= 2,0799

..

suy ra Kp,llOO = 14,35 atm.

3.16. Tinh nhiet nong chay cua 1 mol diphenylarnin n611 lk~ diphenylamin nang chay lam tang th~ tfch len 9,58,.10-5 m3 cho bie't

. ,

BAI TAP H6A LV CO SO

•

75

dT/dP :::: 2,67.10-7 K.m2/N; nhiet d(> n6ng chay cua diphenylamin la 54°C, kh6i luong mol cua chat nay bang 169.:

.1

Gidi

,

Ap dung phuong trinh Clapeyron - Clausius, ta co

T~V dT/dP = T.~V/L\H hay ~H = ----......-(dT I dP)'

!J. V = 9,58.10-5 X 169.10-3 = 1,619.10-5 m3/mol 327 x 1,619.10-5

!J.H = - 7 = 19,84.103 J/mol

2,67~10~

':_., I

3.1 '1. Xac dinh nhiet dQ bay hoi cua nude d 2 atm neu d 100°C nhiet bay hoi cua nude b~ng 2254, 757 JIg.

_ Gidi

Nhiet bay hoi eua 1 mol nude bang

2254, 757 x 18 = 40584,8 J/mol Phuong trinh Clapeyron - Clausius cho ta:

AH dP/dT=---T(Vh - Vt)

Vdi bien thien hfru han nho eua T va P thi phuong trinh tren trd .thanh

AP dP AH

- ~ =-------

AT dT T(Vh - Vi)

v. = 0,018Z

V - 22,4 x 373 - 6 1

h- - 30

273 '

+

_ .

L1T = AP x T(Vh - V,) = 1 x 373(30,6 - 0,018) = 28,5.: _

L\H 0,00987 x 40584,8. _....

\ _

.' _ 0

T2 - Tl = AH ~ T2 = 373 + 28,5 = 401,5 Khay .1·28,5 C

76

... '" """"...a.

Chuong 3. CAN BAft:JG HOA Ht;JC VA CAN BANS PHA~

3.18. Xac dinh nhiet dQ soi cua benzoatetyl C9HlO02 d P = 200 mmHg biet rlng nhiet d{) soi chuan cuabenzoatetyl Ia 213 va nhiet bay hoi b~l1g 44157,52 J.

Guii

" P2 fiR ( 1 1 ')

Ap dung cong thuc In -- l -.. ) ta co

Pi - R r; T2

760 8,314 486 T2

T2 ::;; 433,1 hay 160,1 °c

3.19. Xae dinh luong CS2 dl1<;1C lay ra khi thc3iO,005 m'' khong khi vao CS2 d ap suat 720 mmHg va 40°C. cho bl€t' nhiet h6a hoi cua CS2 d . nhiet de? soi chuan 46,50C 18. 355,8 JIg.

Gidi

,;

Ap dung phuong trinh Clapeyron - Clausius d dang

ta co

P2 355,8.76

In -

760 8,314

1 319,5

1 313

SUY ra P2 = 615,18 mmHg

Tai ap suat toan phtin 720 mmHg thi ap suat rieng phjin cua

,

khong khi bang 720 - 615,18 = 104,82 mmHg. Dinh luat Boyle -

Mariette cho ta

PlV] = P2V2 ~ 720 x 0,005 = 104,82 x V

BUY ra V 13. th~ tfch han hop khi lei 0,0343 m'', S6 mol CS2 hoi se bang PV 615,15 x 0,0343 x 1;013.105

n ::= = = 1,16

RT 760 x 8,314 x 313

do d6 khO'i hrong CS2 thu dl1~C 18.: 1,16 x 76 = 88,5 g .

•

"'-' - ,,~ ..

BAI TAP HOA LV CO SO .

. .

77

3.20. Ap suat hoi cua niken cacbonyl d Ooc va l30e 13. 129 va 224 InmHg.

TIm nhiet dQ soi chuan cua niken cacbonyl.

...

Gidi

,

Ap dung phuong trinh Clapeyron - Clausius dang

A

19P = _- + B

T

ta co

A . 1

19129 = - 273 + B

A

. Ig224 == - + B

I 286

1442

V$y 19 760 =. - T + 7,3888, suy ra T:::: 319,9 K (46, 7°C)

suy ra A = 1442 B = 7,3888

3.21. V~n dung quy t~e Gibbs, xac dinh sO' b~c tl1 do cua h~ g6m

h6n hop NH4CI, NH3 va HCl khi:

a) nhiet dQ rat thap;

b) nhiet de. kha cao; c) dun nong,

Gidi

a) Khi nhiet d9 rat thap, h~ co 3 cau ttl, 3 pha tinh th~ f=3-3+2=2

b) Khi nhiet dQ kha eao thi co phan ung . .~

NH4CI = NH3 + Hel (k)

. I •

...

S5 cau tit bang 2; co th~ chon 2 trong 3 chat hopphan tren lam sO'

",' ~

cau ttl.

,

f = 2 - 2 + 2 = 2. H~ la nhi bien vi d~ xac dinh up suat. cua h~ c€ln

chi ra nhiet di) va ndng dQ cua pha hoi.

c) Khi dun nong h~ se eo su phdn tfch NH4CI d~ taora pha hoi ggm . NH3 va Hfll hoac co s11 tuong tile giua NH3 va H'Cl, H~ 18. 1 cau tit tr~g

, y

2 pha ran va hoi, f = 1 - 2 + 2 = 1, h~ 1a nhat bien.·

I

..

78

.A...a. , . ".A. ~

Chuong 3~ CAN BANG HOA H"C VA CAN BANG PHA

3.22. Giai thfch vi sao h~ KCl - NaCl - H20.la- h~ 3 cau tit trong khi do h~ KCl- NaBr - H20 lai 13. h~ 4 cau til.

Gidi

.

D6i vdi h~ KCl - NaCl - H20, sf) chat hop phan b~ng 3, sf) cau ti1 (hoac chat hop phdn dQC lap) cfing bang 3 vi khong co phan tmghoa hoc nao xay ra giua chiing.

DO'i vdi h~ KCl- NaBr - H20, s6 chat hop phan Ia 5 (KCl - NaBr - H20 - NaCl- KBr) 86 cau til (chat hop phan dQC l~p) bAng 4 vi co 1 phan

.. trng giira cluing KCI + NaBr =m KBr + Na'Cl.

3.23. Chi:> bi~t s6 cau tit trong cac 'h~ sau:

a) NH4CI (r), NH+4 aq, cr aq, H20 (l), H20 (l), H30+ aq H20 (k), NH3, OH- aq, dung dich NH3

. .

b) NH4CI (r), NH3, nc: (k); PNHa = PHC1 (k)

Gidi

a) SO' chat hop phan: NH4Cl, H20 tu. H2Q (k), NH3 (4)

r. ..

• ...

SO' phan tmg: NH4CI NH+4 + cr

NH3 + H20 ;.. NH+4 + OR-

so ca u til: 4 - 2 = 2.

b) 3 chat hop phan: NH4Cl, NH3, HCI

Co 1 phan ung NH4CI sc·' NH3 + HCl (k)

C6 1 phuong trinh lienhe .. ap suat rieng PNHa = PHC1

.A'

Vf!.y so cau tit: 3 - 2 = 1.

3.24. Ve gian de; pha cua h~ Sb - Ph dua vao cac du kien cho d bangsau .

t

Thanh phan hon hop long, % kh6i ludng Nhiet de. bAt dan
Sb Ph thoat tinh th~, °c
100 0 632
80 20 580
60 . 40 520 •

, ..01IIII.. .; ~ •

BAI TAP HOA LV CO SO

•

79 -

40 60 433
-
80 300 -
20 .
-
" "
10 90 273
0 100 326 .
I f

, I

a) Xac dinh thanh phan otecti.

b) Co bao nhieu Sb tach ra neu lOkg han hop long chtra 409G-iPb, , duoc HIm nguQi tdi 433°C?

Gidi

c

,
J
I
I
I
t I
] f
I t
I
I
20 " 40 J J

8 326

A

600

I K

520 - - - - - 1- - - - - -

Fl' I N

433 - -- -.. - -4 - - - - -I - :_ "_ -

400 M"I

I
J
I
I
60
% n: .. IE 0

t )

J J

r I , I

I I

zoo

o 5b

80 87 100

a) Hai duong long AE va BE cAt nhau tai E ilng vdi thanh ph~n .: otecti 87% Ph va 13% Sh." "

" -

b) Neu hBn hop long chua 40% Pb duqc lam nguQi .tdi 43SoC thi

i1ng vdi di~m M tren gian d6. 'I'ai thanh ph~n 40% Pb, tinh th~ d&u tien. tach khoi h8n hop long la Sb tai 520°C (di~m K tren giaD d6). D4n theo slJ, tach. Sb J han hop long cang gi~ u Ph hon do do di~ni K chuy~n dich ten N chang han (60% Pb). GQi L la hrong pha long tai di@m K" Ria h.tcjng

, .

• .. '!I -" -

..

80

"'" ~ ; ,. "" .A ~

Chuong 3~ CAN BANG HOA Ht;JC VA CAN BANG PHA

Sb tinh th~ tach khoi han hop long tai K. Theo quy tiic don b~y R~FM = LMN hay

MN 20

R = L. = 10~ - ... = 5 kg

FM 40

,~ ..,

III. BAI T~P TV GIAI

? '

3.25. 0 900 K hang sO' can bAng Kp cua phan (lng

co + 3H2 _?- CH4 + H20 (k)

bang' 1,25.10-10• So mol hie din bang cua CO, H2• H20 (k) bang' nhau va bang 1. Xac dinh hang sO' can bang Kc, va K, d6i vdi h~ eo th~ tfch 0.1 3

dm .

3.26. 1 mol hoi nude bi phan tfch thanh hydro va oxy. V lit th~ tfch cua han hop can bc1ng va ex 13. dQ phan tfch cua hoi nude. Xac dinh hang so can bang Kc dO'i vdi phan ling phan tfch h :i nude theo phuong trinh phan ling.

3 -, a

DS.~ K = __ ___.....__

c 2V(I-a)2

3.27. D(> phan tfch N204 (k) thanh N02 d 25°C b&ng 16, 7%, dudi ap suat 1 atm.

Tfnh hang so can bang Kp va nang luong Gibbs chuan cua phan

~ .

-'

(tng

thz

3.28. Nang hrong Gibbs chuan cua su hlnh thanh 2 dang phan cis va trans - 2 - buten la 67,15 kJ/mol va 64,10 kJ/mol. Tinh ty s6 ap suat can bang cua 2 khi d~ng phan d 25°C.

DS:· Ptrabs / r., ::= 3,43

•

" "". ;.". .

BAI TAP HOA LV CO SO

•

81

?

3.29. o 457 Kva dudiap Built chung 1 atm, 5% N02 bi phan tich

thea phan ling

Tinh hang sCi can bang Kp va Kc cua phan ung

;, -5· -6

DS.~ 6,76.10 ; 1,80.10

3.30. Trcn axit axetic vdi 0,18 mol ruou etylic d 282 K tao ra 0,171 mol este hie can bang. M~t khac cling tai nhiet df} trent h6n hop gdm 1

...

mol axit axetic va 1 mol ruou tao ra 0,667 mol este Inc can bang, Trang

2 truong hop, tinh hang so can bang Kc va ki~m tra xem dinh luat tac dung kh6i hrong co diroc nghiern dung? Tinh ~Go cua phan ling .

.

DS: 3,92; 4; 8G~82 = -3;23 kJ

3.31. CJ 510 K hang s6 can bang Kp ciia phan {tng

bang 1. Xac dinh:

a) Dc? phdn tfch PCl5 d ap suat 5 atm:

b) Tfnh ap suat tai do 20% PC15 bi phan tich;

c) Phai them baa nhieu mol clo vao.d mol pel5 d~ dQ phan tich giarn di_ con 20% d 5 atm.

DS: 0,41; 24 atrn; 3,8 mol

3.32. 0 445°C hang sf) din bang cua phan ung trong pha khi

H2 + 12 (k) c 2HI (k)

bang 50. Hoi co baa nhieu mol HI duoc tao ra neu dun tdi nhiet de? tren, 1,27g 12 va O,02g H2 ? Tinh ap suat rieng cua tUng khi trong han hop can bang eo th@ tich II.

. -3 .

DS: 9,348610 ; 418, 7; 238,5; 14,6 mmHg~

3.33. D~t mdt ang thuy tinh diroc hall kin, chua 4,6g N204 long vao mdt binh dung tich 5, 71 dii loai bo khong khf. Dap vd ang thuy tinh

.

r5i nang nhiet dQ'cu.a binh len so'c. N204 long bay hoi va bi phan tich, .

tip suat do duoc trong binh 13. 0,4586 atrn ..

82

.-.a.;I- ""'.A ~

Chirong 3. CAN BANG HOA Ht;>C VA CAN BANG PH~

,

Tfnh dQ phan tich a va hang so can bang Kc va Kp cua phan ung:

DB: 97,4%; 0,324; 8,5836

3.34. Dun n6ng tOi 1000 K dudi ap suat 1 atm vdi su co mat cua mQt xuc tac, mQt hAn hop 7% 802, 11 % O2 va 82% N 2. Sa u khi can bang duoc thie't l~p, 802 co thanh phan 4, 7%.

Tim de? oxi hoa cua 902, hAng so can bang Kp va Kc ella phan ung

DS.A 32,9%; 2,44; 200

3.35. d 230°C hAng 86 din bang' Kp cua phan ung

C2H4 + Hel (k) _tr C2H5Cl (k) b~ng 0,128.10-5 Pa-1

Xac djnh thanh phan (% th~ tich) han hop CaD b~ng d ap suat 10,13.105 Pa neu xuat phattu 2 mol C2H4 va 1 mol HeI. .

DS: 60,94% ,C2H4; 21,88% HeI; 17,18% C2HsCI

3.36. D~ nghien CUll phan uug

H2+ 12 c .... 2HI

d 440°C nguoi ta Stl nhirng Iuong khac nhau cua H2 va 12 rc5i xac dinh lueng san pham din bang, Ket qua dUQC ghi Iai d bang sau:

H2t mol I2, mol HI, mol
2,94 8,10 5,64
5,20 7,94 9,40
14,44 8,12 14,93 Tinh cac hang so Call b~ng rai tit tri so trung binh cua hang so can

.....

bang, xac dinh so mol HI duoc tao ra khi dun nong tdi nhiet de? tren

27,58 mol H2 va 8,02 mol 12•

DS: 50; 15,58 mol.

" .. .; _". "t

BAI TAP HOA LV CO SO

..

83

3.37. MQt binh phan ung chua 15 mmol cha:t A va 18 mmol chat B, dUQc dun nong tdi 600 K thl can b&ng duoc thie't l~p theo phan tmg

A+B ... 2C+3D

Han hop din bang co ap suat 108.5 torr va chtra 10 mmol chat C.

Xac dinh Kp va L\Go tai 600 K. Chap nhan cac chat lit khi ly tl1dng.

DS: 0,0709; 13,2 kJ/mol~

3.38. 0 1000 K hAng 86 CaD b~ng cua phan ung

CO2 ac> C + O2 Kp = 1, 778.10-21 DQ phan tfch CO2 theo phan {tng

2C02 cung d nhiet dQ tren b&ng 2.10-5 Xac dinh Kp cua phan (tng

..

2CO 2C+02

d 1000 K

DS: 7,907.10-28

3.39. DQ phan tfch cua phosgen d 600°C va 1,38.105 Pa theo phan

img COCl2 CO + Cl2 b~ng 0,90. Xac dinh chieu eua phan ung tren

co Sd cac dft kien sau:

•

STT PCOC12' Pa Pea, Pa PC12' Pa
1 5 5 5
1,013~ 10 1,013.10 1,013~ 10
2 5 5 3,039.105
1,048~ 10~ 2,026.10
3 5 5 5
1,048~ 10 3,039.10 3,039~ 10 ..

DS: hGl = -12,76 kJ~ hG2 = 0; AG3 = 2,93 kJ.

3.40. 0 500 K hang' sO' can bAng Kp cua phan (tng

PC13 + ·C12 -= PCl5

84

- A ~.; '" _ ~

Chucng 3. CAN BANG HOA H"C VA CAN BANG PHA

bang 2,962.10-5 Pa-1

- ,

Lieu PCl5 co duoc tao ra trong hon hop can bang vdi pels va

C12, ne'u ap suat rieng phari cua cac chat trong ph an (tng bang:

PPCla::: 1,013.104 Pa, PPCl5 :..... 5,07.104 Pa va PCI2• = 2,026.105 Pa ?

•

DS: ~G = -0,76 kJ

3.41. (j 450°C ap suat phan ly cua NiO theo phan ung

2NiO (r) ~~ 2Ni + O2

bang' 5,181.10-26 mmHg. 811 phan ly NiD co xay ra dUQc khong trong khong khf neu ap suat rieng phan cua oxi bang 0,203.105 Pa ?

L\G phai bang baa nhieu d~ dao nguoc qua trinh

. .

- .

DS: -399,6 kJ

3.42. 0 25°C doi vdi phan ung'

•

~GO ~ 5395 J .

Xac dinh de} phan tich a cua N204 trong cac dieu kien sau:

,

a) 25°C va 1,013.105 Pa

b) 25°C va 10,13.10.5 Pa

o«. 0,165%; 0,0529%

.3.43. Cho cac dfl kien sau:

~

CD

Pb o

o 26,50

PbD -219,03

-189,14

46,27

~H°ht 298 [kJhnol] '-110,43 -393,13

,

L\GOht 298 [kJ/mol] -137,14 -394,00

,

Cp [J IK.lnol]

29,05

36,61

.

Chap nhan nhiet dung khong d6i trong khoang 25 - 127°C

a) Tim AHo, taGo, Kp d 25°C dOl vdi phan ung

-

PbD (r) + CO 24== Pb·+ CO2

b) Bi~u thi L\H~ dudi dang m(>t ham cua T.

c) Tfnh Kp d 127°C.

... ~ , ~ ,.

BAI TAP HOA LV CO SO .

..

85

DS: ~Ho = - 63,66 kJ; l1Go = - 67,71 kJ;

6 All 2 7

- 7, ~1 ; ~1.10.

3.44. Doi vdi phan trng

2C02 - > 2CO + O2

hang so din bang Kp d 1000 K bang 4,033.10-16 Pa. Tfnh hang so Call bang cua phan irng' da cho d 2000 K neu hieu (lng nhiet trung binh b~ng 561,3 kJ.

DS: 1,91.10-1 Pa.

3.45. Tinh hang so' Call bang d 298 K doi vdi phan img

2ND + O2 ~az 2N02

dua VaG cac du kien Salt:

• •

S ~98 [J IK. mol]

l1H~t.298 [kJ/mol]

NO

210,6 205,0 240.5

90,37 o 33~85

Xac dinh hang so can bang d 373 K

lJS: 1,66.1012 atrn': 1,73.108 atm-1

3.46. 17,8% hoi HI hi phan tich d 280°C COIl d 520°C de? phan tfch

In 24,48%. Xac dinh dQ phan tfch d 300°C. .

os. 18,35%.

3.47. Khi N204 bi nhiet phan, co can bang'

N204 - 2N02

Khi dun nong 9,2g N204 tdi 27°C, dudi ap suat 1,013.105 Pa, th~ tich cua khi do duoc 13. 0,00295 m'', dun tie"p tdi 110°C thi co su dan lld th~ tich tdi 0,00607 In3. Tfnh de? nhiet phan d 27°C va 110°C, hang so can bang Kc d 2 nhiet dQ tren va hieu ung nhiet cua phan itng trong khoang nhiet dQ da cho.

us. 20%; 93%; 147,1; 1,226; -54,48 kJ

86

.A ~,; ott-.A '"

Chuang 3. CAN BANG HOA HQC VA CAN BANG PHA

3.48. Xac dinh h~ng so can bang Kp d 800 K dOl vdi phan tmg

co + 2H2 - CHaOR

~

bi6t r~ng d 2SOC, ~Ho = -90,64 kJ/mol va Kp = 4,23

Cp co = 27,61 + 5,02.10-3 T

,

Cp,H2 = 29,07 - 0,84.10-3 T + 2.10-6 T2 Cp,CHaOH = 20,4 + 100.10-3 T - 24,6.10-6 T2

DS: 5,22.10-6

3.49. Doi vdi phan ung C + CO2 ,- = 2CO h~ng so din bang Kp d 1000 K bang 1,862. Xac dinh thanh phan han hqp kill d 1200 K dirdi ap Bunt 1· atm n~u hieu ung nhiet trung binh cua phan tmg b~ng 169419,58 J

DS: 98,28% co va 1,72% CO2

.,

3.50. o 676 K hang sa can b~ng cua phan tmg

MgC03 ==== MgO + CO2

bang 1 atm. L\R~98 = 117491,44 J

va .1Cp = 8,82 - 41,38.10-3 T + 2,67.105 T-2

,

Thie't li}.p phuong trinh 19 Pco2 phu thuoc T.

3.51. Doi vdi phan (tng

ta co

3378

IgKp = - - + 3,648

T

. do'i vdi phan ung

-.

1 K - 748

g p - - + 0,573

T

.

BAI TAP H6A LV CO SO

•

87

Xac dinh thanh phan han hop khf can bang (% mol) d aoo'c dOl voi phan ttng

-

Fe304 + 4H2 • 3Fe + 4H20

DS.~ 51,8% va 48,2%

3.52. Xac dinh hang' sO' can bang Kp d 400 K d6i vdi phan ung

~. PhD + 803 (k)

PbS04 PhO 803

-

L1HOht, 298 [kJ/mol] -917510 -2-17652,6 -394801

SO 29B [J/niol] 147,136 69,338 25.5,983

Cp,PbSO" = 45,81 + 129,58.10-3 T + 17,55.105 T-2

Cp, PhO = 44,30 + 16, 72.10-3 T

Cp,soa = 57,26 + 26,83.10-3 T + 13,04.105 T-2

DS: 4,074.10-31

3.53. Doi vdi s~ tao ra chi clorua tit chi r~n, ta co

~Go = 356152,72 - 34,62 TInT + 15,1.10-3 T2 - . - 12,45.10-6 T3 + 100,36 T;

tit chi long:

.c1Go = 347240,96 - 39,1 TinT + 5,90.10-3 T2 + 24,45.10-6 T3 + + 214,01 T

Tim phuong trinh IgK = f(T) dO'i vdi qua trinh

, ,

Ph (l) ~ Ph (r)

3.54. Nhiet dQ nong chay chuan cua Bi 13. 271°C. d nhfrng di~u kien d6 ty trong cua Bi r&n va Bi long 13. 9,673 va 10gicm3. M~t khac khi ap suat tang len 1 .atm thi nhiet dQ nong chay giam di 0,00354 K Tinh nhiet nong chay cua Bi.

£)S~~ 11 kJ/mol

88

......_a., iIIII..-,.).

Chuong 3. CAN BANG HOA H(?C VA CAN BANG PHA

3.55. Tai 127°C HgI2 bi chuyen hoa da hinh tii dang do sang dang vang, Nhiet chuyen hoa la 1250 J/mol; AV = 5,4 cm3/mol dang do co ty. trong nho hon dang yang. Xac dinh dT/dP. tai 127°C.

DS: -1, 7~.10-6 KlPa

3.56. Xac djnh nhiet d9 nong chay cua Bi dudi ap suat 10 atm biet r~ng ty trong cua Bi long va Bi riin Ifrn luot bang 10 va 9,673 g/em3 va nhiet nong chay cua Bi 1a 54,392 kJlkg.

3.57. Khi dun nong hru huynh rombic chuyen thanh hru huynh don ta kern theo bien thien th~ tfch IlV = 0,0000138 m3/kg. Nhiet de?

chuyen hoa chuan bang 96,7°C va dT/dP = 3,25.10~7 :a. Xac dinh nhiet

chuyen pha nay.

DB: 501,24 kJlkg - nguyen ta.

3.58. Xac dinh th~ tfch rieng ella thi6c long tai nhiet dQ nong chay chuan 232°C neu nhiet nong chay rieng 1a 59,413 JIg; ty trong cua thiec rfin 13. 7,18 g/cm3 va dT/dP = 3,2567.10-8 KlPa.

3.59. Nhiet dQ soi chuan ciia iot ·lll. IS50C. Nhiet bay hoi la 164~013 JIg. Muon chung i6t d ap suat thap 100 mmHg thi c&n phai dun nong iot tdi nhiet dQ nao ?

3.60. d 200 mmHg metanol soi a 34,7°C con khi tang ap suit len gap doi thl nhiet dQ soi la 49~90C. Tfnh nhi~taQ soi chuan cua metanol,

DS: 65,4°C

3.61. 0 70°C ap suat hoi cua CC14 bang 621,15 mmHg, nhiet bay hoi bang 30781,688 J/mol. Tinh nhiet dQ soi chuan cua CC14•

£)8: 76,50C

.... A. *' #- •

8AI, TI.tP HOA LV C9 $0

,

.. .

89

, '

r

3.6~.',Xac dinh s6b~c t\1 do cue dai trong cac h~ 1 ~au tit~-'2·cau til

va 3 cau tit.

. .

DS: 2; 3; 4

... :

. ..

3.63. X~c dinh 96 pha c1;1C dai trong cac h~ 1 cau tit, 2 cau tit.

, ;

. .

.

. .

, . -

DS: 3; 4

-'3;.64. Xac dinh so pha cue 'd~i trong h~ CaD bAng 'g6m nude va du~ng.

• I

FJS: 4

, 3.65. Dung dichnudc co chua cac ion Na+, K+,' Crt NO-3. Xac dinh so that hop phanva so.cau tit. '

..

os. 5; 4

3.66. Khi hoa tan NaCl va CaCl2 V8.0 n1.tOc thi khong,xay ra phan

, -

ung nao, song khi tan Na2S04 va CaC12 vao mrdc thi co phan nng

, .'

. ,

.

. .

3,,67. Tren gian ct6,trlilngt,hai cua nude hay xac dinh: '

, ( ,

, p 'a) trang thai cua h~ tai rung I,

·11, III

: I· .

- • I ..

8

b) trang thai eua h~ tai di~m b, c,va ·A.

I ~

•

e) mrdc long eo Wn tai (j vung I ? d) 96 bac tv do cua h~' tai ,vilng , '

I •

. I, II.,· III; tai cac dUdng cong

. AB, AC, AD; tai A~

. . D

•

90

.. 3.68. Hinh ben lai ghlD d6 trang thai cua h~KCl' - uci. Hay xac

dinh: i ~ .. ~ ,_ "

a •

c

a) so pha, thanh phan pha va nhiet eta tai cac di~m

.. . .. : .

a, b, c; 'el, eva n .

b) thanh phan ciia h~ du<1c bi~u . di~n , bAng., ·,di~m M

.. . . , t

tren giaD dB bang. quy

t~c don b§:y

c) khoi hrong KCI c~n them vao 1,5 kg LiOl ··d~ ha nhi~t dQ' nong .chay' eua Li'Cl xuong tdi 500oe.

800

700

6JO

d .. 6DO

_ .

. .

J6f ........... --+---____._--~

I . t

•

• I

- .. -

"-I • r

. .

I LO 40 460 86 100

_. ~ %rLiCl.

HI J(Cl .. uct

•

..

.

-

DS: a) . di~m a: "Lphalong chua 40% LiCI, 700°C. di~m b: 2 pha chua 80% LiCIlJ 510°C ndm CaD b~ng vdi tinh th~ Lie}.

di~m c: 1 pha nong chay cua LiCl d 650°C.

• - p ...

1~ • ~ . _ • ~ .... 0'·.

diem d: .lpba tinhthe·KCI a 625 C.

; di~m e: 2 pha r~n g6m tinh th~ Lifll 80% va KC120%a

di~m E: otecti, h~ 3'pha (2 pha tinh th~ + 1

..

pha long) pha clang chua 58,5%

LiCI. Nhiet do otecti a6IoC.

.. • j

. .

. _

" , b) di~m Mung viii h~ 2 pha d 450°C; pha long

,chiia 20% LrCl va 80~ Kel. Luong pha rAn

_. . ,. MN 30

KClIll1dng pha long = = ..

· MP 20

. c) 0,6595 g ..

.

BAI TAPH6A LV CO sO

"

91

3.89. Hinh ben IS. gian d6 nong chay cua h~ b~c 2.

Xac dinh khOi luong cau tit . A can phai them vao 200g han hop n6ng chay chua 30% A ·d~ lam tang nhiet dQ bA.t d~u ket tinh tdi 360°C.

tt

400

JOO I
r DS: 266,66 g
I f
tM
I
200

8" 507- A •

3.70.

Axeton

Hinh ben la gian d& pha cua h~ bac 3 g6m axeton - ete - nude a 30°C va' 1 atm. DOi vdi h~ nay, nude va axeton boa tan khdng han che vao nha u. Axeton va ete

~

;

NtMc . C

.

cting vi).y. Nude va ete hoa tan

han che'vao nha u. Hayxac dinh.

a) so pha tai 1 di~m nAm ken va dudi duang CFKHD.

b) s6 pha va thanh ph~n pha tai di.$m F va H~

•

f)S: a) 1 pha;"2 pha.

b) 1 pha mrdc va ete (giau nude, ngheo ete); 1 pha ete va nude (gia u ete va ngheo nude). 2 pha Day nAm can bang vdi nhau .

•

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DUNG DleH'CHAT HONG BI~N LY

• • • •

'.

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rl : ~ \. ~ 'I

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I. 16M TAT LYTHUVET .

..

Dung dich 180 mQt h~ d~ng th~ chiti tit 2 c~u til t~a:'teh~IVii~]ii~ a~ cau tii nen d~c trung ra't quan trong cira. dungdich ;la thanh phan, CO nhieu each bi~u th] thanh phan dung dich,

~- .

;i

~

. -

. ..

n, la so mol chat i

. . . .. . .:

• . .. t· t J • i -'

.1''' :. ~ } .. J. I • I •

b) N6ng dQ mol th~tfch c,

. ,

.I

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,:' . I , ". ' , ,'. r "ila'1h@"tfch,(lllrig djch

; • • •• ~ • .,: .. :.... :..;' ." ~ :. '. -, ~ <; '. ~ .:~.... .:. _ r J "II. :-1: (t.

• • •• • - • .' • L • ,. J .• -...- .. J • -, ~ _I f' -_ . :. " -. _ -.' ~ •

c) Molal m.; s6 mol chat tan i quy v~ mQt kh81111<;Jng dung moi xac

dinh (thuong lit 1 kg). .(

. . ~

d) Phiin tram v~ kho"i I uqftg

.. ~ .." ',....., i. . .J- r .

. .. r I .. • I

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. - .,

goi gj va g la kh6i 111~ng chat i va khoi hrong dung dich tIiin8n~:d~

% nude bi~u thinhu sau: ; ;' "'.' i,'-; '-, t .: -i,':' .

~ ~

" .

, 'gj' "_'

-.100%

-

._ .: i .

- .

~ ....

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. '. . ~ " . II., _ I

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g

94

-

Chuang 4. DUNG DlcH CHAT KHONG DIIN LY

Vi th@ tfch dung dich thay d6i theo T va P nen Ci ciing thay d6i

+

theo T va P nhung Xi va IDi khong phu thuoc T va P.

MQt trong nhfing thuec tinh nhi~t dQng luc eua dung dich la dai htQng mol rieng phan, dUQ.c dinh nghia nhu sau:

(ax 1

x. = l )

1 lnl. ~

1 T .P.nj~",·~~e

. ~.. . _.,

x 13 thuQc tfnh khuech dQ ba't ky cua:'~~"~l1 th~ tfch v. .entrepi s,

•• -"T,. ._. _.' • r .•

..; .: ., , :

ham Gibbs 0, ham nQi nang U...···~·~·;:,;') .. ' .; " '. '. " .'~'

. - . .

• r- " _ I •

.. · . (j'T, P = const, X'~a'Xi .quanhe ~di nhau bd~g h~ thirc:

\ ' ~

: .

....... ~ ....!.~ ~.L _....' •• _. X:I'"" ., , - .

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-I .. ." II; - o'I!. • -, • -.- ." l .~ .... ~ .. ,j., .. ,:.., l:r i·· ;-:\,.. ~ "'·.1 ~. •. ..:

,. •• ." I, • ..r'· i .. r _...... : _ • - • P":..I r.. . '. ~. .. •• '.~ .- ~ ~ . r •

. . ~ . . . . . • . . , ... . .' • :_.. 011,( , . t' • ~,~ - l' • '

•

X = nLxiXi n = Lni;

. .

GQi XO 19. thuQc tinh khuech dQ cua h~ a d6 cac chat i nguyen chat

chua tham gia vao dung dich, thi

x<> = DIiX~ ella chat i nguyen chat, .

hoac

•

'. • r

.

, . X - x" ~ AXm = Lni (Xi. - X~) .

L ' • .~.,

~m=Lni~mi

,

: .

- .

6.Xm 18. dai hrong trQD ella h~

, , ,

.

r

. ~

.

:> Nhi2ng djnh luv,t vi dung djc!J va cung lodng

,

•

Dung dich vo eung loang la· mQt dung dich trong db phan mol cua

dung moi (A) diin tdi 1; phan mol ciia chat tan (B) d~n tdi khong:

, .

I : I

I ~ I • • ~

XB~O

1 ' ,

.

DQi vdi dung dich vB cung loang,'nhi~t dQng IllP hoc d~· thi6t l~p

~u~c ri~g.: . . . . .

" .. I r' I I

,

- Ap suat hoi bao hoa eua dung moi tren dung dich vo cung loing

ty l~ vdi phan mol cua dung rnoi (dinh lu~t Raoult dOl vdi dung moi)

..

r· _

BAI"T~P H6A LV CO SO--,' ','

~,

• • •• _.I '. ,' ..

P~ Ia ap suitt hoibao hoa cua dung m,8i p.gu~~n, cP.~t_}9 ~;Wtg T, P

vdi dung dich loang. .

-

Tit phuong trinh tren BUY ra

, ,

:' • r ...

. . .. .. ~ . , .

(P1 - p ~ I P~ = XB

, , r , , , ' " ' t ,{;

• •• r I .' I '.' '. .....;; I I .. ... .. , ..

. .' ,-, ," .... -, .,~ ! .. ',;,,~ , ..

Dai 11.1~ng (P1 - P.J I P~ 19.- d9 giarn tuong dai ,ap ,9uat_ hoi b~o hoa. L

, f ,I.. t I ~ ,I .. i t ,- • (! _ .: [~ l ; ;}

.' N~l,l gci gA' -~l! ~a ~hoi ~¥<jng;dung~oi ~a ch~t tan v~,;Mt'\J~ khOi

- I '. r _ •

luong mol chat dung moithi titdinh luat Raoult ta co, dOi.vdi chat tan: t

, •• , ' " ., II ~,- , ,,~ ~ t J' . r ( . 1") • ~ • • f·

• • I ... ~. ." f ,I I • : 1.·oJ. !, .:. ~ •.

,

- pO

gsMA "

M8 = ·

gA >: L1P -

MB.l~ ~6i luong mol ehal tan; *p =_ p~_ ~ P A .~ dq h~. *P. s~t hoi

r,_ • , , , ,T, • ", r _ ; .' ~ ~, , ,.' ;'" t ~ ,- : J .' •

bao hoa cua dung moi. ': :" ,. :_~-I,q':, _ -t j-',

- Ne'u chat tan trong dung dich vo cling loang cung bay hoi thi ap suat hoi ciia chat tan ty 1~ vdi ph~:o. mol eha't tan (dinh lu,t Henry)

, ,

. . ..

, , '

.. - r" .

........... '

: : ' -', i i

... ...

r

i - - ' , fB ~ ~B ~ _f-B,: " '_ , ,!;' ;',! .. j t » .» , ".; " ~:, \

trong do: kB 13. h~ so Henry, khong eo y nghia 13. P~.

, '

- Di~m soi va di~m dong d~e cua dung djch vo cung' loang,

I' • .. I ~ _ : I I • ., _. I . I .'

',' ~ ~ ',... ' • ,~ : ,,' .' ' ' "J:,: ~, ",' ;' ; ': - , ,- '7 :": ~ ~ ~ ~ ~ :' ~ : ~ ,

, , ,D81 ,~oi dung dich va c~g:, loang. ch¥~. : cl1~t_ .tan. I,Iqt~p.g,· ,t;tt~y :,d~i

trang thai khi boa _ tan (khong phan ly, kh6ng, lien, -D;(jp)~ _ ~Q' ~n~, d?-~~

soi, de> ha di~m dong d(ic ty l~ voi dQ molal ciia chat tan. . - __ I _,

I I I I

• .-.. r. t..· ,J • .J

, ., ' 1

I. ~ 1 I.' r • I !

- _. I' ",

, ' . ~ , I ......

". t" ( ~

, ' ,

L\Ts: dQ tang di~m soi, m la de;» molal ch~t tan;

. )' I I '. • I .'

t

.

Ks 13. h~ng s6 nghiern soi

R(To')2 M'

K' - b A ..

S -. ,

- 1000 ~Hb.h.A

, ~

"

~ "

. " ,

,

~ " '

r _.. i. I ';

, , ..

, r ,- -" ".' ;", L

,

• I Ii

, ,

• ( , , 'i. ;

.

.

ATb ladQ ha di~m dong d(lc; Kb Itt hing so nghiem lanh c6 gi4 tri

o 2 r

~. R(Ts) MA

bang K = .

b ,1000 ~H

nctA

, ,

1 ,

I

.. ~ .,

, "

,

~ .

- ~ 'I •

_- " J

- .

. "."

Clnrong 4. DUNGD/CHCHATKH6NG f)IINLY

'96

--Ap suat thim thau dttQc tfnh thee; phuong trinh

. . .

I •

+

7t = CRT

.: \

C 18. n6ng de) malll

. .

_ Dinh luat phan bo Nernst v~ 811 phan b6 cua mQt cau tl1 trong 2

dung moi it tan vao nhau. -

, ; N€u 'C1' v~ C2 13. 'n6ng dQl ella cau tit tan trong 2 dung .mei i va 2

.. ' .

khi din b~ng a T = canst, thi ty so C1 I C2 la mQt hdng s6 va duqc goi 13.

h~ so phan bo K

. . ".

Trudng hop chat tan hi phan Iy hay hi lien hop - trong - mi)t dung

moi, dung moi 2 chang han, thi - - -

·c K = c~-

2

-

. ,~

-

vdi n 13. ty so khdi IUQng mol trung binh cua chat tan trong 2 dung moi,

i

" '

~ '.. . .

Dinh luat phan b6 duoc ung dung trong chie't tach. G9i go va gl 18.

. .

kh6i luong (g) ban d~u cua chat 'c~n'chi6t ra va -khO'i lti~ng cha:'t con lai

sau l~n chiet thu nhal.voi th~ tfch V (ml); v; lit th~ tfch ban d'Au chua g~

- chat can tach, -

Dinh luat phan bo cho ta;

, gt/VO - -, -" KVo

K = ., suyra gl'-- go ----

(go _-_gl)/V _ - KVo + V

~ .

Sau l~n chiet thtr 2 vdi cung th~ tfch V ta co

~

..

SU\· ra

....

KYo I ,g2 ·=·go

KVo+V

Sau IAn chiet thu D, Iucng chat con IQ,i trong Vo 'se bling

• L

..

BAITAP H6A LV CO sO

•

9.7

n

* .

:> Can #Jdng lflng hai d6i viii dung:"djch-lj tudng. S" clit -h~'t h9P: '

hoi chtit long di bay hai. _ _ _' .

. I . • I',

, J: \ ..:,: .: 1

: ;. I

NE!'u cac cau tit ciia dung, dich long ly t\1dng d~u ~,bay hoi thl khi W,

-:- • .' I • I

can bAng long - hoi, pha hoi nlm can bAng vdi dung dicb Jo~ MlJ ~~ IllQi

. I· .

, cau tu. DOl vdi h~ b~c hai, ap suat hoi -toan phin bing P ~ P A + P~Vi dw;w:

dich 13. IY tuong nen moi cau tu phai tudn theo djnh I~~t RaouJt:-., ',:! •

• 1 •

P A = P~ XA PB = P: XB, ,. ,_ - ~.

p = P A + PB = P~ XA + P: XB = p! XA + P: (1 - x~ - _ - -~ -

= (P~ - ~) XA + ~: ; :',' -

Gia thi6t hoi nam can bang vdi dung dich laJehllYtltdng d~ c6,th~:

. . I. I.:

ap dung dinh luat Dalton, ta co PA = Px~; PB = Px~ vdi x~ va x~ 13

thanh ph~n trong pha hoi cua A va B. ,,' _ , _

Tt'.t cac phuong trinh tren, sau mQt soldn bie'n d8i toan tadl1(fc , , "

•• 0

xA IXB PA

-

- 0

xA IXB PB

N€u p1 > P~ (cau tti A nguyen chat d~ bay hoi cB:'u til B nguyen

x' x '. , "-

chat) thi A > A: pha hoi se tuong doi giau cau til 4~-bay hoi so vdi

x'B XB

dung dich (x~ > XA va xk < XB). Do thanh ph~n hoi va thanh ph~n long khac nhau nen co th~ dung phuong phap cal,- nhat la cat phin doan d~ tach mQt cau t11 khoi dung djch,

Dung dich Ij tl.1dng duoc hinh thanh til cac chat nguyen chat khong kern thea bie'n thien th~ tfch (A V m = 0)· va hi~u' ung nhi~t (AHm = 0) song ~Sm *- O,

. .

zs, = R L n, lnx, hay zs, = nR Dei lnx, vdi n = L n, ;

i i

:> Dung dich. kh6ng Ij tuling. 8'1 sai l;ch so Wi trqng thai Ij tllang

. . ....

, ~ol vdi dung dich khong It tUdng, A V m ¢ 0, 'M1m ¢- O~ Pi I ~o ¢ 'Xi

song Pi I Pia = a, . a, Iii. hoat de? cua eha't i. Giita ai'vA' Xi c6 lien h~'bliig

. .

he thuc ' .

..

98

Chuong 4. DUNG otc« CHAT KH6NG DIIN LV

Dai hrong 'Yi = a, I Xi 13. h~ s(Jho~t dQ, bi~u thi muc dQ sai lech v~

"'.

tnuQc tfnh nhiet di}ng Iuc cua dung dich khong Iy tl1dng so vdi trang thai

ly tUdrtg d cung digu ki~n v~ T va P. ":

D6i vdi dung dich khong ly tUdng, ap suilt hoirieng. ph'n cua cau tit i laP, khong con phu thuoc tuye'n .tfnh vao Xi. Tren 'gian 'd6 ding'

., .

nhiet.: S\t phu thuoc Pi vao Xi 18. duang cong.vdo d6" dudng·ap' su~t hoi

toan phan phu thudc Xi cting 13. nhtrng 'dttdng .cong. Trudng', hop xuatl

, . -

, . . - ..,

hien nhung cue tri (eire dai hoac cl1cti@u) tren d~~ng cong ap suat hoi>

. ..

· thanh phdn (hay nhiet d? soi\ - thanh philn)' tht t~i nhirng eire tri nay

'. -

thanh phan cua h~ 13. co djnh; do do thanh ph'n long' va' thanh -ph~n hoi

. ,.

13. nhu nhau. Han hop ung vdithanh ph§.n nay 13. han hop dAng phi.

:

II.: BAI TAP c6 LOI GIAI

•

4.1. d 15°C, dung dich H2S04 20% co ty, trong bang 1,145g/cm3• , Tinh nang dQ mol1th~ -tich, nang dQ nguyen chuan, nang dQmolal va 115ng de? phan mol cua dung dich.

. .

Gidi

,

, .

C ~ lOOOpg ~ 1000. 1,145.20 =2 31mol/.f.

M.I00 98.100 J

. 1000~ 1,14·5.20 .

N = 2 x C ~ 98 ' = 4,31 d 19l f

-·.100

2

. lOOOg 1000.20

m = =.. = 2,55 mol/lOOOg

" M2 (100 - g)" 98(100 ~ 20)

g/M2 20/98

x =' '100 =, 100 20 =·0,044 ..

g/M2 + -M- g (20/98) + - ,

1 18

. .

4.2. Dungdich ruou etylie 20% va 80% c6 ty trQng tuong fLng la . 0,9708 va 0,8478 g/cm3• Xac dinhkhoi hrong 1 mol dung dich va th~ tich

- ~ .

cua 1 mol trong 2 truong hQP. '

BA-I TAp H6A LV CO SO

•

·99

~

• • t

a .. ,,., . zaz

~ . .

DOl vdi dung dich 20%, n~ng dQ ph~n mol cQ.:;t nude x~ eua ruqu 11

,

X' 2

· 80/18 .. · ~ . ·

x~ = 80 20. = 0,911 va x; = 1 - O,~11 ::: O,08~ .

-+ ~

18 46

D3i vdi dung dich 80%, n6ng dQ ph~n mol ciia nude 18. .x~, CU~ I11Cju

, .

• I' I I ~

. 20/18.· ....

x~= 20 80 = 0,39 va x; :::: 1 - 0,39 = 0,61

_......_....... .. + -

18 46

..

.

Kh6i h1Qng 1 mol dung dich 20% rucu:

\ M' = 0,911 x 18 + 0,089 x 46 = 20,50 g

KhOi hrong 1 mol dung. dich 80% rirou:

Mil = 0,39 x 18 + 0,61 x 46 ~ 35,08 g . D6i vdi dung dich 20% ruou, th@ tfch rieng 18.:

11 0,9708 = 1,030 cm3/g

•

. I

.

.

va dol vdi dung dich 80% ruou:

I

11 0,8478 = 1,180 cm3/g

....

, I

V~y th~ tfch mol dung dich 20% ruou la

1,030 x 20,50 = 21,12 cm3/mol va dOl vdi dung dich 80% ruou:

. ~

._ ..... '.

t

, .

..

• •

" p ....

l I ," ... . ..,.;.. .. ..

'L" ..... '"Ii ~ -e ,

~. \ I •

4.3. Xac dinh ty trong cua dung dich 40% nt"u 'irletylic bje'i ih4

. '

tfch mol rieng phan cua nude va rUQu metylic IA 17,5 va 39 cm'S/mo[

.' • I -.

. ,

1,180 x 35,08 = '41,39 ems/mol.

' .. '

....

F •

. ..

Gidi

v = nN V N + nR• V R

, .

. ' nN = 60 /18 = 3,334 mol

•