Vn-Student.

Com

v

___________.~___........__.,.......,....... ----- __ ... _ ~ __ - 1.-_-- ~I"'" .- _. • _ -- •• _ ___.. __ .._ 'I.I'W'TV.. I ._ ... ~_......._. ~

.... -4 .. zyzzzzc .... -=yz , • P.o. I .... - "1'.-- . .. -.. ===+=-.--.,... ~~. --,t':~ I 111.1 •• +..... .. ......... 4 ~ -----r- "1'-.. r--:

. r.... }.. . I· I .J.~ 1 ....... ".,: I I p.

. . .' . FILL rz._ ~, . . "". '. . .,'. '. :::. ;"~:j'~

_ V-fr - .,

.

. . H.401 H

...

.

TRINH THANH DOAN - NGUY~N DANG QUANG - DUON.G~VlN TU~

. . .

Chu bien: HOANG TRONG Y~M .

•

•

'.

- ..

, . ,.,

HOA HOC H

•

co

. TAp 'l

•

. ~

~ .

. _

Gido trinh cho cae truimg dqi hQc

+

, ...

tJ01}vv bPi

.,

•

....

NHA XUAT BAN KHOA HQC VA Kf THU!T

..

--- ----------- --. -------:------;--_._------

..

41 - 33.;~ 1 KHKT

..

....... _- - -- - - - ---._-- ___, ..... -..-.-_

. ...

,

.. .. : ...... -

.... • .. 1

..

-..

. . ........

..... ,

,

. .

- ,

:' .

•

,:

•

... , ."..",

LOINOIOAU

..

. - '

C6 the n6i, phan Ion cac thanh qua trong h6a hoc hllu eel d~u

gar" lien vdi $\1 -phat' trian ella Iy thuygt hoa hoc n6i chung va Iy

. .

, thuyet noa hoc hau co n6i rieng.

N~u nhu trtldc day h6a hoc hllu co chi" 18 rnQt mon hoc, mot Irnh

•• I •

vue mang tinh tiep nhan, thl ngay nay cAn chuy~n men h9C nay

thanh m9t mOn hoc mang tfnh suy dl~n. :,'.:~' ,

. Xuat phat tll quan di~m do, cac tac gia cua bO 88Ch nay da de

~

C@P den nhllng quy lu~t co banco lien quan den h6a hoc hau co,

vOi mang muon chuyen tar toi ban doc hlQng kh$n thuc sau hon,

gan gUi vdi thue te han. -

....

69 "H6a Hoc Htlu COli nay gam 4 tap, vdi nQi dung nbu sau:

. T~p I nau IAn n'hang khai ni~m, nhtlng quy lu@t co ban cua hcla , hoc ht1u co nhU Iy thuygt v~ lien ket, cac hieu ang, khai ni~m v"B

- -

IUQng tU ht.1u co, tac nhan va cac loal phan lIng hau co v» ..

. Tlf pnan Iy thuyet nay ap d\mg vao phan crulc hllu co de du

. .

doan leal phan ((ng, kha nang phan lIng, hlJOng phan ang, cache

phan ling htlu co. · .

T@p II va III trlnh bay cac chLJc hal. co baa gam cac hQp chat , h()u co mach hci, cac .hop, chat rulu co mach vong (ke cit di vong).

Trang hai t~p II va III neu len phudng phap di'eu che. trnh chat Iy, h6a ella cac .chuc, co the cua phan ling ht1u co, d~c bi~t ItJu·y ·

~

d~n cac phan ling hliu co tao nen cac san ph~m h6a hoc '(ht1u Cd)

phuc vu cho nen kinh ttf qude dan.

..

. .

Oac tac gia cJa bLf6C dAu ap dVng nhang khaj niem, nht1ng quy

'.

3

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

luat co 'ban v'S Iy thuygt' htlu co d~ cho ngUdi doc suy luan dllOe hu6ng phan ling, 51) tuonq tacgilla cac ch§t trong phan ling htlu co,

Trang tap IV trinh bay cac phuonq pnap vat Iy d~ xac djnh cau true cac hop chat hilu co, X8C dlnh cac chat trong h6n hop cac - hOP chilt hllu co. '

Cuon "Hoa hoe hilu co" nay co the dung lam tal Ii~u hoc tap, tham khao cho sinh vien, nghh~n CUu sinh nqanh hoa, cac nqanh co lien quan den h6a h9C va cac can b9 lam vi$c trong llnh vue

,

ht1u co cang nhU cac tanh vue h6a hoc khac,

Chung toi mong nhan dL1QC va xin chan thanh cam on nhung y

kien d6ng g6p cua ban doc. '

Chu bien

GS. TS. HoANG TRONG vtM

4

v

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

. .

. - ~._, . - I. . _ . __ . _I

• -. -- _- .... ~r· •• _. n • ,.~ •• ~. __ • -~. ~~~.~. ==:: ..

, '

• ,,"" I, I'~

• -. I' ..

• ',,;. ... -: .. .,. ". 'I

. .

......

'I ",'

I, ~

MUC LUC

. ..

",

Trang

Chuang I.· Mil dall

1 ~1. Dei· tucng ella hoa hoc hiru co

1 ;2 t So IUQc lich sU: phat trien ella hoa hoc htru co

9 9

1.3. Dac diem cua cac hop chat hiru CCf va phan ung hfru co 10

1.4. Phuong phap hQC .~p va nghian ciru man boa hoc htru co 12 ,-

Chuang Il: MOt so khai niem co ban trong hoa hQC huu co 13

2 t 1. Khai niem ve bac cacbon va hoa tri cua g6c hydrocacbon 13

. ,

2.2. Khai niem ve nhom dinh chdc 14

. ."

2.3. Khai niem ve dong dAng 2~4. Khai niem ve dong phan

2.5. Khai niem ve tac nhan phan ung 2.6. Khai niem va CO che phan ling

. ,

Chuang III: Cac phirong phap tach va phan deh eac

, hqp chilt huu co

15 15 22 23

\

25

3tl. Cac phuong phap tach va tinh ch€ cac chat htru CO 25

3~2. Xac dinh thanh phan phan tit cac ,chat hiru co

(xac dinh cong thuc phan tu) 35

3t3. Cac phuong phap xac dinh cau true phan tit hop chat

hiru cc

43

, '

Chuang IV: Axit - bazo v~ dung ~oi

4.1. Axit - bazo ,

4t 1 t 1. Thuyet axit- bazo cua Bronsted

"

4.1.2. Thuyet axit- bazo cua Uxanovit

4.1.3. Thuyet axit- bazo cua Lewis 4.1.4. Cac khai nism khac va axit- bazo

..

66 66 75 76 80

5

4.1.5. Tinh chat axit- bazo cua hydrocacbon

80

.., -

4.1.6. Anh hucng cua cac nh6111 khac nhau len luc

axit- bazo cua cac hop chat htru co

83

~ 4~ 1.7. Axit- bazo va tac dung xuc tac trong hoa h9C hfru co · 86

"

4.1.8. tr ng dung cac thuyet ve axit bazc 87

4.2. Dung moi hiru co 88

4.2r 1. Nhiet do soi 88

. .

4.2.2. Moman luang C\l"C 89

4~2~3. Hang so dien moi 90

4.2.4~ Lien ket hydro 91

4.2.5. Do axit va do bazo 91

•

4~2.6. Do hoa tan cua cac chat 92

~

Chuang v.- Khai niem ve ling dung CO hoc 111Qng tic trong

hoa hoc htru en 94

•

5.1. Tinh chat song cua hat va phucng trinh Schrodinger 95

5.2. Khai niem ve co h9C Iuong ttt cua nguyen tit 107

5.3. Lien ket hoa hoc 110

•

5.4. Nhirng phuong phap co ban cua hoa hoc lucng tli va ting dung cua chung de nghien CUU ly thuyet cac lien

ket hoa hoc 128

•

5.5~ Ket luan 172

~

Chuang VI~t Nhiet dQng hQC va d(Jng hoa hoc htru co 174

641 ~ Vai trb ella nhiet dong hQC va dQng hoc trong boa hoc

hiru cc 174

6.2. Co so cua nhiet d(ing hoc hfiu co 174

6.3. Co sa cua dOng h6a hoc hiru CO 183

Chuang VII: Cac loai hieu ling trong hoa hoc huu CO 196

7.1. Anh .hucng tucng h6 cua cac nguyen tit noi true tiep

voi nhau 196

7.1.1. DO phan cue cua lien ket 196

6

......- •• - --.--..... - ........... __ ........... -- ............... - - -_____.........---- • p. -"" .. - "-- ••• --~. ---:-- ~~~. _ ••• ~~~ •• ,_ ~--~.- •• ,~-~-. -~~, ~. -_.- _.L_~ . --- • .J,.- .. - .. - ... ~ _. -~_. . .. . ~ __ ~ •.. ~.~ p ~--:'"'~

,,- • .1 •

+

.. ..

741.2. DQ kha phan cue

197

.~

- /

7.2. Anh huong tuong he cua cac nguyen tit noi gian tiep nhau 198

7 .2 .1. Hi~u ung cam ung 7 .2 +2. Hieu iing lien hQP

7.2.3. Hieu ung sieu lien hop H

"

198 204 210

~

7.2.4. Hieu ung mezome va electrome

Chuang VIII: Phan loai phan tlng va tac nhan trong hoa hiru co

8.1. Phan loai phantrng

8.2~ Phan loai tac nhan va su hinh thanh cac tac nhan

. + •

8t2·tl t Tac nhan nucleophyl

8.2.2. Tac nhan electrophyl 8.2.3. Tac nhan goc

8.3~ Nhung giai doan co ban cua phan tmg hiru co 8.3.1+ S\1 tan cong nucleophyl

8.3~2. Su tan, cong electrophyl

8.3.3. 8\1 tan cong goe tu do

214 214 219 219 221 222 223 223 .

224

· 226

7

.'

. - ......

~

•

..

"

..

Chuang I·

..

.

M• d~ . '0:·· , au

1..1. 001 TlfONG ellA HOAHQC H(fu'C()

. .

Hoa h9C hitu co Is mOn khoa hoc nghisn euu thanh phan va tinh

. . ... . .

,chit cae hqp cMt euacacbon. ' ..

" "I ", " "

Trang thanh, phh cua eac hen> chin hftit co, ngoai cacbon con Chtla

. . .

nlueu nguyen to khae nhu: H, 0,. N, s, P,. halogen.. Nhung "cacbori ..

. .

dttqc coi 13. nguyen to CO ban cau tao -n~n eac hC1P chat hiru co .

•

1.2. so LL10C LICH so. PHAT TRIEN eVA H6A HQC HOO CO

, . -

TIt thesi xa xua, nguoi ta da bi~t dieu che va: sit dung mot s6 cha~ -

, h(tUCC1 trong dbl s6ng nhu :ii,am (dung dich loang eua axit-axetic),

. .~

~Qt so chat man hilu co, ruou (C2HsOH) ... Thbi ky gil kim thu'_t,

cac nha hoa hoc da ·biet· dieu ch~ mOt 86 chat huu· co nbu ete etylic, ure .. 4

. ,

Vao cuoi the kY XVIII va dau th~ ky XIX ,. cac nha hoa hoc da

. ,

chia't tach dl1qc t~ d"ng, thi$c v$.t nhieu axit hftu co nhu axit oxalic,

axit xitric, axit lactic ... va mC)t s6 bazo hi'1u co (alcaloid). Nam 1806, Ian dau ti@n Berzelius* dB. dung danh tit h6a hoc hllu ·cCJ dt chi nganh hoa hoc nghien cdu cac hcp ch(t co nguon g6c dt)ng, th\tc v(lt~ Thbi diem Day co th~ xem nhu diem m6e danh diiu S1l ra. dCri

.. - . .. ".

eua men hoa hoc hilu co ..

Nam 1815, Berzelius da dua ra thuyet "luc s6ng" , D!l}t luan thuylt duy tim, cho rang cac h9P cha:t hilu co -chl cc th@' tao ra r trong co th~ d.,ng, thuc v~t nhC1 ~tn"t "luc s6ng" d*c bi~t ma ban tay con ngubi khOng th~ di~u che dl1Qc chang trong cac blnh lo, ang

,

~ ~

(.) BerzeJius( 1779-1848) 13. nba bAc hoc nOi ti~ng nglt~i Thuy Dien .

•

...

9

.•

..

v

nghiem nh u d6~ voi cac chat vo co.

Thuyet "luc s6ngn d& thong tri hoa hoc htru co trong nhisu nam,

,

Sau d~ thuyet "!1jC songll dan dan bj danh dd nho cac cong trlnh

tong hop cac chat huu CO t.u cac chit vO cc .

. ...

.

Nam 1824,. Wohler" da\ t<sng hop duoc axit oxalic, mot axit hiru

co dien hlnh, bang each thuy phan dixian 18. mot chat VD C04 NaD1 . 1828, cung chinh Wohler da tong hQP duoc ure (von co trong nuoc tieu dong vat) -tti' amoni xyanat, cung la ID¢t chat va co:

Chinh phat minh nay da lam sup do buc tucng ngan each truce do giua .hca hoc VO eel va hda hoc hiru co ·va lam cho cac nha hda hQC tin rang, co the t\1 tong hop ducc cac chat hiru co trong phong thi nghiem rna khong can co sir tham gia ella mQt "luc song" nao ca.

"-

Tiep thea do, Bectola'" da ~6ng hQP dugc chat beo (1854) va roi

Butlerop'?" dB. tong hop duoc duong glucoza tit formalin (1861).

Cho den nay, hang tri~u chat hiru co dB. duoc tong hop trong cac phong thi nghiem va trong cong nghlep, Khong nhung con nguot da, bat chuoc duoc thief! nhien trong nhisu llnh vue rna con nguoi con sang tao ra dl1QC nhisu vat li~u huu co, nhisu chat hiru co cue ky quan trong, qui gia khong co trong t\i nhien.

Tuy nhien, ten goi "hop chat hiru co" y~n dude duy trl, nhung khong phai vdi nghia nhu trl1ac day la cac chat co nguon goc d<}ng v~t, thuc vat, rna no da mang met nQi dung mci, do la ·cae hop chat

cua cacbon. ·

1.3. HAc DIEl\t1 eUA cAe HOP CHAT HW co vA PHAN UNG HUU co

Cac ~QP chat hiru co rat phong phd ve sO lucng, chung loai; mac

..

. (*). Wohler nha bac hoc Due, (* *). Beet ole n ha bac hoc P ha p.

(***). Butlerop (A.M. EYT~1ePOB) nha bac h9C Nga.

10

...

v

_..... ......... __ - -- - - _.- _... •• ~- - _. _. r- • _ _ ~

. -~

, '

r

dil hoa hoc han co 18. mot monsinh sau de muon hon hoa hoc v6 co

... ....

hang ngan nam, nhung s6 luting chat h au co dB. duoc bi~tcho d~n

. .

nay nhieu gap vai chuc ran 'cac eh~t vO co dA ·hiet. Nguyen nhan cc

·ban ·la do, khac voi 'cae nguyen t9· khac trong bang tuan hoan, cacbonc6 kha nang tao thanhmach 'dai v6 ~ntheo nhieu ·lden each

. .

khae nhau. N6i khac di, ·hi~n tU<;1ng d~ng phan (ttlc 13. cac chat. co

. , .

cung thanh phan phan tit nhung khac nhau ve cau. tao) J..a. cue ,kY-

o

phd bien va dac trung trong hoa hoc hiru co. VI du, nhu co the eo

toi 366.319 chat. co -cau tao khac .nhau nhung co. cimg ·cong thuc phan tit Iii C;OH42.

,-- Ca:u true phan ta cua cac chat hiru co co th~ don gian nhttng 'ding co th4 rat phiic tap va noi chung cac chat huu co IS. v(l{ :chat

- 0

co t<1 chuc cao hon .cac chat vO CC1~ vi~ xac dinh cau true phan til

cua chung 18. nhiem vu nhieukhi rat phuc tap, khd khan, phai dung deil nhieu phuong phap hoa hoc vLa v~t· Ii hien dai,

-

", Neu nhu trong eac chat va co, lien ket ion kha ·pho bi~n thi trong

cac hop chat hiru co, lien ket chit yeu giua cac nguyen tit trong phan ·tit la li~n ke't cQng hoa ~tti. P~c diem Day anh-huang nhisu den ly tinh,

. . . ~ '. . ~ . .

• hoa tinh va d*cbi~t lil kha nang phan ung cuachung.:

•

~ . - .. .

~. . . . .

Cae phan ttng hiru co thualig ,cay ra vai toe dQ'ch~nl; khong tri~t

de va cling thuongtheo J,lhi~ti huang khac nhau, V1 v~y vai tro ella' men nhi~t d~ng hQC, .dQng hoc va xuc me trong h6a hoc h uu· 'co rtlt

.

quan trong, .,

Cac chat htru co dong vai tm cue ky quan trong trong dbi - song

. chung tao Khongnhftng hau het cac thiic an (gluxit, protit, . lipit) , v~t dung hang ngay (xenluloza, sgi . tong h<;SP1 cao su;·~chat deo.i.) Ii cac chat hiru co hoac ~t li~u htru co, ma nhieu chat huu CO con Ii

• • - .... • I • .' • •

I '_ '. •• •

co so cho s\i ~6ng (protit), Nhisn Iieu cho d()ng co dot trong, cho

. .'._ ',... .

nhisu nha may. nhu xang, dau, cling lit nhirng hydrocacbon 'mach

dai, ngan khac nhau, Cac v~t li~u hiru co nhe; khong' bi gi, ti~n su dung; mau . sac da dang dang cang ngay cang thay the cho cack.im

. . . . ' .

. ' loai, hop kim trong nhieu Iinh vue, k~ ca nhirng llnh vue tuong nhu .

khong 'the thieu kim loai nhu ban din, sieu din H t

..

,

11

--_. --------_._._----_ .. --- -----_. __ ._--_._-----_._--- ------_. __ . _ .. _ ... _._---- _ .. -_._---_._---_._---------_._-_._-- -----_.-

....

v

\

Do nhirng d·,c di~m tren Dl8 hoa hoc hiru co dl1QC tach ra nhu met nganh khoa hoc rieng" dbi hoi nhf1ng phirong phap nghien cuu

. . .

va thietb] ngay cang hi~n d~i hen, doi hoi .nhftng nO luc ngay cang

IOn lao cua cac nha hac hoc tren toan the giai" de khong nhirng dan dan bat Ch1.1C1C ducc thisn nhien t6ng hQP nen cac hop chat phuc tap

,

va quan treng trong doi song, rna trong nhieu Ilnh v1!c con vuot xa ca thien nhien,

1.4. PHUONG PHAp HOC T!P vA NGHIEN·CUu MON HOA HOC HUU co

Do nhirng dac di~m ndi tren cua cac hop chat hiru co va phan

.

llng h iru co rna khi hoc t~p, nghien cilu hoa hQC hftu co, chung ta

..

phai chu y quan tti~t cac phuong cham, phuong phap sau:

- Phai h~t sue coi trong Ii thuyst, ke ca cac ly thuy~t co sa tit gi:ii tich toan hoc, dai so tuyen tinh ,giro tich ham, v~t Ii hrong tlt, vat ly thong ke, v~t Iy quang phd cho den nhiet .dOng hoc, de.ng hoc, xiic tac, ca:u tao chat, co chl phan ung ... C6 nhu, v$.y chung ta mci xac lap ducc cau true phan tUt dlj doan duoc kha nang, chieu huong phan ung cua cac hop ch4t hiru co va tim each tien hanh trong dieu ki~n t6i "UU, co hieu suat cao nhat.

- PhAi coi trong thuc hanh, thuc nghiem; nam chac cac ky thuat va cac thao tac thi nghiem, VI hoa hoc v6n la man khoa hoc thuc hanh; viec tien hanh cac thi nghiem va nghien ciiu trong tong hop hiru co va phan tich hiru co lai cang dbi hoi ky nang thuc hanh rat thanh thao mci c6 duoc kat qua t6t.

- Phai coi trong cA de suy luan logic l~n kha nang nho may moe, vi trong men hoc nay co nhirng phan dB. c6 co sO' ly thuy~t chat che, co the suy luan ducc, nhung cling co phan con fbi rae, chua h~ 'thong. Cong thirccac chat hftu cc nhieu khi phdc t~PI ten gQi doi khi cling cong kenh, rae r6i, doi poi pha! van dung ca trl nho nuiy

".

moc.

12

•

:. ,_

..

Chuang II .

Mot .6 khai III co baa'

.' .

trODg boa b90·'ladu· ee

, .,. ....... .... ....#0 ",...r

2.1. KHAI NIEM VE B~C CACBON \TA HOA TRt eVA GOC '

HYDROCA,CBON

•

...

/

2. 1. 1. Thlr bic ella cacbon

..

.

Trong phan tit· hiru co, cac nguyen tu: cacbon khong hoan toan

gi6ng nhau. Vi du trong hQP' chat sau:

+

CH3

•

1 ")1 3 ". · 5

CH3- "C- CH2- CH- CH3

I f

CH3 CH3

..

ta nhan thay rang, nguyen ttl cacbon C 2 lien ket true tiep vai bon nguyen t11 cacbon ben canh, nguyen "tit C3 li~n ·k€t vbi 2 .nguyen til C, nguyen tit C .. lien ket vOi 3 nguyen tit C, con, Cs" va C1 lien ket vai tnQt nguysntir C. Nhu v~y cac nguyen tit cacbon trong hop chat tren "lth6ng hoan .toan gi6ng nhau,

Ng1.iC1i . ta phan bi~t cac b~c cua nguyen tit cacbon sau dAy:

~ Nguyen ta cacbon b~c 1 III nguyen tit cacbon frong phan tu chi li~n k~t true tiep vesi DlQt nguyen tu cacbon khac, vi du nguyen t.ll c, c;

"- Nguyen tit cacbon b~c 2 IA· nguyen h~ r-acbon trong phan tit gan true tiep vai 2 nguyen tit cacbon .khac. VI du (.~ .~.

13

..

-"-' - _ .. - ._-_.

________ • • - • 1.' •• ' •• • •• _._._.

-------_._._- . __ .-_ ...... __ ._---_.- .. -.- ... ---_._ .. -

- N guyen tit cacbon bac 3 Ia nguyen tit cacbon dinh t ruc tiep vdi 3 nguyen tit cacbon khac, vi du C 4'

. ,2. 1.2. Goc hydrocacb.on.v8 h_6a trt cu~ chung

.

• .

,

N€u bo di m~t' hay nh ieu nguyen 'tu hydro trong phan tu

.hydrocacbon :thi phan con l~i ducc goi 'la goc hyd rocacbon. 'I'uy th U9C VaG s6 nguyen tu hydro bo di, nguci ta phan biet g6c hydrocacbon hoa trj. 1" 2, 3, ... ·

Vi du, neu ,?o di mot nguyen ttl hydro (j phan til metan 'CI-l4, thi phan con lai la gee metyl CH3 - hoa tri met , neu b6 di hai nguyen

, .

tit hydro thi phan con lai lit goe metylen CH2= hoa tri hai, khi bo

d~ ba nguyen tit hydro thi duoc g6c rnetyliden CH= h6a tri ba.

Tuong t\i nhu v~y ta co l11Qt so .g6c sau day:

G6c phenyl (hoa tri mot): 06HS -

- G6c vinyl' : CH2 =CH -

- G6c allyl ...

2.2. KHAI N.JEM vI: NOOM llIN'H CHUC

• •

D~ da so cac hQP chat hiru co ·duQc cau tao hi!i hai phan; g6c hydrocacbon va nhom dinh chuc ..

- Goc hydrocacbon 18 phan rna tinh chat hda hoc cua chung trong dai da s6 cac hQP chat hiru co deu tuong t1;l nhau .

. - Nhom dinh chuc la nguyen tit hay nh6m nguyen tit ket hQP vci . g6c hydrocacbon, nhom dinh chuc xac dinh d~c ·tinh hoa hoc co ban etia phan t\1~ N oi mot each khac.. nhom dinh chiic quyet dinh tinh chat hoa hoc mot loai hQP chat co ban cua hiru ca.

Vi du, trong cac hQP chat sau day:

cac nhom CH3 -, CzHs - in goc hydrocacbon. Nhirng g6c nay tuy

14

v

I. _ ..

..

. .......

•

nam trong cac phan tu· khac nhau nhung co tfnh chat tucng t\t

..

nhau. Con .nguyen tit Cl va cacnhcm nguyen tit:'OH, NH2, COOH

la cac nhom dinh chuc. 'I'inh chat cua cac hgp chat tren phan len Ii do cac nh6m dinh chuc nay quyet dinh:

- Nhom OH ~c trung cho alC91 va phenol.

- Nh6mNH2 d~c trung cho cac hQP chat amin, Nd quyE!'t djnh

tinh chat bazc va cac tinh chit khac cua cachcp chilt· amin,

- Nhom eOOH d~c trung cho cac axit hf1u co ..

Khi xet ban cha:t hoa hoc CC1 ban cua ml)t ~ loai hQp ·ch4t nao do, .

..

- .

ta phai xet d~c tinh cua nh6m dinh chitc chua trong loai hop chat .

d6~ , '

2.3. KHAI NIEl\'J vt OONG DANG

•

Nhirng hop chat hfru ca dl1{1c gQi lit d~ng dang vesi nhau 13. .nhimg hop chat co cimg nh6m dinh chuc, cd cau tao hoa hoc tuong t\1 nhau, nhung khac nhau mot hay nhieu nhom metylen (-CH2-).Vi du:

..

CH3-CH2-OH dong ding vui CH3-C_H2-CH2~OH

Cac hop chat dong dang veri ·nhau tao thanh mOt day cac hQP cha:t dang ct!ng goi lit day d~ng dang. V{ du, day dong dAng cua hydrocacbon no gom:

. ~

2.4. KHA.I NltM vs DONG PHAN

, .

•

2.4.1. Dtnh ·nghia

, ' -

Dong phan IS. hien tuong ton ~i .cua cac hop-chat co thanh·phan

phan tit gi6ng nhau, '·nhung do cali tao khac nhau nan co tfnh ch(t . h6a hoc va tfnh chat v~t ly khac nhau.

. . .. -

Nhimg chat co dac diem tren dl1QC goi 18. nhimg hop chat dong phan vai nhau ..

15

v

r

2.4·.21t Phia I loai

•

+

Co cac ·lo~i dong phan sau: - Dong phan cau tao;

- Dong ph an khong gian (con goi IS. dong phan l~p the).

- . +

264.2.1. Dong phan ctiu tao

Dong phan C8U tao .gom cac loai -sau:

"

- Dong phan tao thanh do thay doi mach eacbon. Vi du, hQP chat C 4H8 co ba dong phan:

1 ·1 1 J

·c =c- c- C-

,t 1 1 'I

1 .J I

. c =c- c-

I ~ I -c-

I

J I -c- c-

I I -c -c-

I I

• •• I •• ...

- Dong phan tao thanh do thay doi vi tri ella nhorn dinh chiic

hay lien k€t bQi.

Vi du 1:

..

CH3-CH2-CH20H dong phan vC1i CH·3-CH~CHl

I .

OH

..

Vi du 2:

•

Cl

ba hQP chat nay dong phan vai nhau, ..

•

Vi du 3:

. ,

•

..

CH2=CH-CH2-CH3 dong phan vci CH3-CH=CH-CH3

.

"do thay d6i vi tri lien kat doi,

Dong phan duoc tao thanh khi hQP chat co cung thanh phan,

..

16

+

_ ........ _.._._. _ ... - .. -_. _. - _. __ ....... _... . . ... _.. _..... .. - .- . -_. - - .- .... _ . . .. ..._- - ..... _ ... ----- _ ..

.

.. - .. I

-.'1 . .. -. _~

... I.:

. .. ': . ~~

nhung co nhom dinh chuc khac nhau:

I a

~

CH -CH -OR CH3-CH~-C

3 2 ~ ,

H

l CH3-0-CH3 CH3--C-CH3

U ·

o

Cac hop chat trong nhung cap hQP chat nay IS.. dong phan vdi nhau. Chung cc thanh phan h6a hoc nhu nhau nhung .chiia nhtrng nhdm dinh chuc khac nhau.

.. '-.

2.4.2.2. ~lJong phan l(ip Ihe

Dong phan lap t,h~ gom hai loai: dong phan hinh hoc va dong phan q uang hoc.

- Dong phati hinh. hoc

Hai hQP chat dong phan hinh hoc vci nhau 18. hai hop chat cd cac nguyen tic hay nhdm nguyen tic gi6ng nhau ve ban chat va s6 luong, nhung sap xep khac nhau trong kh6ng giant Loai dong phan nay hay co d cac hop chat noi doi va yang phang, va duoc phan loai thanh dong phan cis va trans. Dong phan cis IS. dong phan cd hai nhom the gi6ng nhau nam cung phia d6i vdi mat phang z (hoac m~t phang yang), con trans IS. dong phan co hai nhom the gi6ng nhau

nam CJ hai phia cheo nhau d6i vdi mat phang 1C. .

Vi du 1:

..

Bu tylen co. hOO de;ng phan cis va trans:

•

DClng phA.n cis

..

DOng ph§n trens

(Hai nhom nguyen tit gidng' nhau nam cling mot phia cua mat phang n).

(Hai nhom nguyen tit giong nhau naIl). V€ hai phia cua

l .

. mat phangzr)

17 -

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

v

N eu cac nguyen ttl: cacbon mang noi d6i cua olephin lien ket voi

oil

bon nhom the khac nhau, thl cis Iii dong ph an co hai nhom the dai

nhat.cong kenh nhat narn cling phia d6i voi 111~t phang 7[, con dong:

phan trans ~ khac phia. ·

Vi du 2:

..

COO!-I

COOTi

COOH

H

H

H

H

H

H

H

H

COOH

Dong phan cis

D6ng phan trens

- Dong phan quang h9C

; ~

a .. .Anh. sang phari C,-!C oa tinli chat eua no

,

Anh sang thuong lit nhtrng song dien tit, do Iii song co cac hat dao

- .

dong thea nhung huang khac nhau, vuong goc voi phuong truyen

song. Neu cho anh sang nay 9ua lang kinh Nicol, thi sau khi qua

". ..

lang kinh do, anh sang thuong se thanh anh sang phan cue, Iii anh

sang dao dQng -theo m¢t phucng nhat dinh, Mat phang vuong gee VCfi phuong dao dOug cua anh sang phan cue goi lil mat phang phan cue ..

•

Tiep tuc dat mot lang kinh Nicol thu hai tren duong di cua anh sang phan eve, thi anh sang phan cue se xuyen qua ducc lang kinh nay, khi lang kinh duoc dat song song vdi lang kinh thu nhat, Nell quay lang kinh thii hai l~ch di mot goc se lam cho anh sang phan cue bi gift lai, kh6ng xuyen qua ducc niia.

b. Cae chat hoat dong quang hoc

,

Cac hop chat heat dong quang h9C (con go! Ia cac hop chat

quang hoat) la nhirng chat co kha nang lam quay mat phang phan cue cua anh sang thea mot g6c a nao do.

18

v

____ .. ---. _.... .. _... __ ... - r'- ----- .- - .. _ I'" .. ~ ........ _._ - __ ._ •• - ..... p p ' • .- --_. • - .. ~

I

.....

/

t ' t ...... ··~ ........

.. ;;44 4"

. + .Anh sang fhudng

t

t · ~

'- Mit phang phr5n c~c

" 'h #'

An song phon cV"c

Long kinh Nicol

d.

Chat

hoat 'luang

Lang kinh Nicol

So do truyen anh sang

j

phan Cl)C qua lang kinh Nico;

khi khong co chAt heat quang

So do truyen anh sang .

,

phan cue qua lang kinh Nicol

khi co chat neat quang

De do g6c quay ella anh sang phan cue, khi cho no di qua chat . quang hoat, ta dung phan C\1c k€.

Co hai loai chat quang ·ho~t:

Chat quay mgt phang phan C1jC cua anh sang sang trai goi Iii chat ta tuyen, khi viet thuong d~t dau (-) truce ten cua chat do. VI d1:1, axit (-) lactic,

Chat quay mat phang phan cue cua anh sang sang phai duoc goi 18. chat hiru tuyen, khi viet thuong dat dau (+) truce ten cua cnat

d". V1 d it ( ) 'I i ..

O. 1 \1, aXl + lac~tC r

Muon co .kha . nang heat dOng quang hoc, cac hop chat h6a hQC phai co nhung d~c diem sau day:

1 ~}

..

---------------"'--

Co cau tao tinh thg bat d6i xung nhu tinh the thach anh, thuy ngan sunfua, natri clorat, kern sunfat. Kha nang quay mat phang phan C\!C cua nhirng chat nay se mat di khi dem hoa tan tinh the.

- Co cau tao phan tit bat d6i xiing Nhung hop chat hiru co co cau tao phan ttl bat d6i xung la nhirng hop chat trong phan tli co chua nguyen tit cacbon bat d6i~' Do la nhirng nguyen tit cacbon co bon hoa tri lien ket \70i bon nguyen ttl hay nhorn nguyen til hoan toan khac nhau, ky hieu Iii C~. Vi du:

b H
I • I
.. -C*-c CH -C*-COOH
a
3
t \
d OH axit lactic Nhimg chat chua nguyen ta" cacbon bat d6i theo cau true tit dien co the co hai each sap xep trong khong gian khac nhau nhu sau:

a

1 I

I

I I l I

I 1

a

b

b

c

c

-

Hai hop chat nay la dong phan quang hoc cua nhau. N guoi ta goi

chung Iii nhfmg chat d6i quang.

....

Hai chat d6i quang 1:3. hai chat co cac nguyen ttl, nhom nguyen tit giong nhau ve ban cha:t va so .luong, nhung sap xep trong khong gian nhu vat va anh cua nhau qua gucng va c6 kha nang lam quay mat phang anh sang phan cue thea hai goc co tri s6 tuyet d6i bang nhau va nguoc chieu nhau.

-.

VI du, axit lactic ton tai duci hai dang dong phan quang hoc

khac nhau:

20

I"'" .r ....

COOH I H-C-OH

I

CH3

COOH I Hooe r

I

1

=; /. I .

OR· I HO

... .

•. 1' •.. t- -..,.

CH :j'H3C

Hooe

I HO-C-H

I .

H3C

H

_.

,~

~H

hay:

. .

Hai dong phan nay khong phai 13. mot hop chat, vi chung kh6ng

•

the chong khit len nhau, gi6ng nhu ban tay phai va ban tay trai

.

kh6ng the chong khit len nhau,

, Nhu v~y, khi co nguyen tic cacbon bat d6i thi phan tit mat tinh CaD d6i va tro thanh bat d6i toan b(i. HQP chat co cau tao bat d6i . (co nguyen ttl cacbon bat d6i) se heat ct¢ng quang ~QC va tc;n tai dudi nhirng dang dong phan ct6i quang. Hai hop chat d6i quang nhau cd gia tri g6c quay mat phang phan cue a bang nhau ve tr] s6 tuy~t dei, nhung nguoc chiau nhau ve dait~

Hai dong phan d6i quang kheng' khac nhau nhieu VEl tinh chat h6a .hoc va Ii hoc, chung chi khac nhau v~ cac di~m sau day:

- Nhirng tinh th~ d~~g phan (+) va (-) ke~ tinh a nhung dang bat d6i khac nhau. .

- Chung lam- quay mat phlng phan cue cua .anh sang m¢t goo

..

.

bAng nhau nhung ngucc chiau nhau.

• Chung khac nhau v~ mOt 86 dnh ch«t 11 hQC nhu vi ngot, dQc

-- . .'

tinh, cac vi sinh v$t cd thg phln huy chit -nAy ma holn ·toan khOng

cd tic dOng dIn ch«t kfa.

- Cd tfnb ch«t hoa h9C gi6ng nhau nhung khac nhau v'A khll nAng tham gi~ phan d~g. viii cac tac nhAn, II nhQng chA:t hoat dOng

~ . ~

quang hQc. -,

. . ...

21

..

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

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

. .

.

2..5. KHAI NI£M vi TAc NIlAN PHAN UNG 4

. . .

2.5.1. Cae ki'u gAy lien k't h6a hQc "trong qua trinh

ph'" ling ~

•

•

~ Khi phan tlng hoa hoc xay ra thl cling xay ra s1:f be giy cac lien

kat ell va hlnh thanh nhirng li~n kat m.m. Vi du:

A-B + C = A-C + B

Trang qua trlnh phan ung nay, lien kat A -!t B bi gay ra va li@n kat mdi A-·C duoc hlnh thanh,

. .

Vi~c be giy .1i~nr ket hoa hoc co th~ ·dian ra thea hai each: - GAy dong ly lien ket A:B, ket qua tao ra hai g6c tlj do:

J *

All B A· + B·-

L;,,. _

I •

- GAy di ly lien lr~t A:B, kat qua tao thanh ion alll va ion duong:

t •

A~: B .. A+ + B-.

I.

.. . ,~

•

hay· A :~ B . • A - + B+

• I

. .

2.5.2. Phin lo,i tic nhin ph'n ling Xet phan l.lng sau:

Z + XY

Lien kat XY co th~ giy ra theo cac each sau:

•
r (1)
x» v
•
• •
•
r . (2)
X .rv
f
I .. '
•• (3)
Xl..:,Y
,
• N en XY gay theo .cach (1) thl de hinh thanh liAn ket XZ tnoi, Z phai 18. tac nhan co du di~n tu (Z:), co nghla lit Z ph:li mang di~n

, .

tieh am hoac chua dfji di~n tli kheng chia. Trong truong hop nay Z

. t· .

ducc goi lit tac nhan nucleophyl N (tac nhan 8.i duong hay Ai nhan),

22

•

•

Neu XY gAy thea each (2) thl Z phai 18. tac nhan thi€u di~n tU:, C9 nghla IS. Z phai mang di~~ tich duong -hay llfp dil}n tit ngoai rung ct'ta no thieu it nhit Dl9t dOi di~n ~a khong chia. Tic nhln nay duoc gQi lit tic nhan electrophyI E (tac nhAn ai di"n tu).

Ntu XY gi.y thea kiGu d~Iig ly (8) va tao thanh cac g6c t\1 do, thl

Z phai lit tao nhan g6c t~ do. D~ 11 nguyen tit hay nhom nguyen t,j I trung hoa va' di~n va ~6 mQt di~n tit Ie.

Nhu v~y, ·tuy thuec vao d~~.:.t{nh:·., cua cac tac nhan ta co th~ co

, .

ba loai me nhan phan dng:

- Tac nhan electrophyl (E), thuong' 18. cae ion duong hoac nhimg

~

phan tu co cac nguyen tit eon chua quy dao tr6ng nhu AlC13; S03'- ...

- Tac nhan nucleophyl (N), thuong lit nhirng anion. Vi du: CI-, CH3 COO -, C2HS a -, NHi... hoac nhung phan til.trung boa chua nguyen tu: cd dOi di~n tu -khong chia (H-O-H, R-O-H, NH3". hoac nhftng phan tu co chua ·d~~n tu x linh dQng nhu:

..

.

> C = C -c, C 6H6 ...

- Tac nhan g6c tl1 do (R). Vi du: Cl··, Br", R· ...

.

· 2.6. KHAI NItM vE CO cut PHAN UNG

Phuong trlnh phan dng chi cho biet trang thai dlli va cu6i cua h~, nhung khOng cho biet qua trlnh phan dng hda hQC xay ra nhu the nao, ndi each khac IS. kheng cho bilt phan ung~ h6a hQC xay ra thea, co ·che nao ..

. .

. Thea quan diem cUa thuyet di~n tit, xet co ch~ phan irng tuc 11

xet qua trlnh gly lien k~t va xet toan b~ cac trang thai cua h~ da duqe hlnh thanh trong qua trlnh phan llng. N gUbi ta phan bi~t hai loai CO ch~ phan ung:

. -:. Loai co ch~ th(i nh4t la Ioai co che' trong do xay ra qua trlnh . gAy di ly car li~n k~t cua phan tit tham gia phan ang va hlnh thanh lien k€i meu ~Cf dO!;"di~n tit chi do mot phan tu dong gOp (cua me

23

--_ .. __ .. _. -_.- --- _ ... _-_.- _._---_._-----_._._--- -----_._---_._----_. __ .. ---_ .. _-- - -------_.,- ._--_._- --_._--_. -----_._._.-

- .

nhan phan ·ung hay cua mot phan tit tham gia phan ung). Cac phan llng xay ra theo co che nay gel la phan ting d] ly hay ion.

Sau day 1ft so do co che 'phan ling di ly;

X: + R:Y )- R:X + Y:

.
lac nhan Phan tLs tharn gia
phan ling· phan ling
hoac:
..
x+ +. R:Y .. R:X + y+

..
Tae nhan Phan tLi tham gia
phan Lrng - phan ung
Vi du: HO- + CH3:CI NOr + C6H5:'H

~~ CH30H __"")I C6HSN02

+

- .

cr

.

+

- Loai co chs thll hai la Ioai co ch€ trong do xAy ra viec gay lien ket thee kieu dong ly, lien ket mrri du~c tao thanh do phan tu tham gia phan tlng va tac nhan phan ung cung gop chung di~n tit. Phan llng xay ra theo co che nay duoc goi la phan dng dong ly hay phan ttng g6c t\i do t

. .

So ,do phAu un~ nh 11 sau =

X· + R:Y

R:X + v:

Vi du:

____..~ H: Cl + CHi

•

I

Chuang I II

Cae pbdoag phip tach vi phan tlcb eae bqp c:ha-t bUa cd

Cac hop chat hitu co .khi mai dieu che ducc hoac tach tit dQ~g thuc vat, thucng a dang h6n. hop khong tinh khiet. Vi v~y" mu6n nghien cUU ehung,IDQ6n phan tich dinh tinh hay dinh lucng chung thi nhiem V\1 truce tien la phai tach chung thanh tung chat rieng biet, a dang tuong doi nguyen chat.

3.1. CAe PHlJONG PHAp TACH VA TINH cut cAe CHAT' Hifu co

3. 1 . 1. P huang phap ket tinh

Phuong phap k~t tinh duoc dung d~ tach va tinh ch~ cac chat

.

huu co ran, .dua tren nguyen tac 18 cac chit khac nhau co dO hila

. .

tan khac nhau trong cung met dung moi. Dung mci thich hQP dl1Qc

lua chon thuong If! dung moi trong do dO hoa tan cua chat ran can

L

tinh che tang kha nhanh thea nhiet dQ. Bang each tao dung dich

baa hoa d nhiet dQ cao (thuong 13. nhiet dQ soi cua dung moi), sau do de nguoi dung dich thu duoc, chat can tinh che se lang xu6ng day blnh (hay day coc), cac tap chat se, a ~ trong dung dich, Bang each ket tinh lai met so Ian trong cung met dung moi, hoac trong cac dung rnoi khac nhau, nguoi ta co the thu diroc tinh the chat can tinh che a dang kha ·tinh khiet. I

CUJ;lg co khi nguoi ta dung mot dung mOi co dl) hoa tan vai ?p chat nhieu hon de loai tap chat khoi chat rAn can tinh che.

25·

,

' ..

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

. .

---_._._--_._ .. __ .. _._-_ .. -

---_. __ . __ .. _- ---_. ---_ .. __ ._---_.

v

+

Dung' moi thucng dung la nucc, alcol etylic,' alcol metylic hay

mQt' alcol thich hop khac, axeton, axit axetic bang ete,

benzen, cloroform, etyl axetat .: hoac d6i khi h6n hop giira chung,

, .

Khi can tach hai hay nhieu chat co' chua trong hon hop vai nhirng' hrcng tuong duong nhau.. nguci ta dung phuong phap ket tinh phan doan.

, ,

Khi da cd chat ran ket tinh, ta can xac dinh nhiet dO nong chay

ella no bang' eng mao quan gan va.i nhi~t ke nhung trong ll1t}t . dung moi co nhiet d(> soi cao, hoac each khOng khi, hoac nhb mot D18.y

•

chuyen dung rai d6i chieu voi hang 86 vi).t If cua chat da cho, d~

biet duoc chat do tinh khiet hoan to an hay chua.

Bang 3 - 1. Nhia dQ soi ciia dung Ino; thong dung va IIOII Ill) P ddng phi gifta chung

..

C'c cilu til' H6n' hqp cling phi
~
T~n dung m8j Nhi&t dO sOi Thanh phan Nhiet dO- s6i
°c .. , h6n h~ ding ph( °c
' th~ tlch, %
Hexan 69,0 73,1 5010
Metano[ 64t65 26,9 .
Heptan .... 98,43 4815 59t1,
Metanal 64,65 51,5 ,
Xyclohexan ' 91t4 69,5 64,9
Etano~ 78j5 30,5
Benzen 80,1 60,5 85,3
Metanol 64t65 39,5
Benzen 80,1 67,6 67,8
Etanol 78,5 32t4
Axeton 56t5 20,0 64,7
Cloroform 61t2 . 80,0
. .
Metyletytxeton ' 79,6 83,0 79t9
Cloroform 61,2 f1,Q
Xyclohexan 81t4 • 63~O
542
..
Metanal B4,65 31~O 26

•

+

3.1.2. Cae phuang philp chung c6't

3.1.2.1. Chung. cat dun gidn

Trong truong hop can tinh che mQt chat· long, tach no ra kh6i tap

. .' .

chat ran -·khong bay hoi, ta chi can ti.an hanh ehung cat dan gian,

nghla III chuyen n6 sang pha hoi trong mot blnh cat co nhanh :rai ngung t\l hoi cua no bang 6ng sinh han vao mot binh hung khac.

3.1.2.2. Chung cal phdn doan

•

Phuong phap chung cat phan doan dung de tach hai hay nhisu chat long co nhiet d(> s6i khac nhau ·ta:n"ldn hoan toan trong nhau, dua tren nguyen tac co 81;l phan b6 khac "nhau ve thanh phancacC~u tit giira pha long va pha hoi d trang thai can bang (0 cirng nhiet dg) ..

... '.

. . '

N eu hai ehB: t long

I r

I

f

j

r

~--------~~-- L __ t

I 2. I

j

I

J

I - . ,

Nhu ta co the d~ A

dang nhan thiy tren hinh 3-1, bang each

lap di lap Iai nbieu

Ian q ua .trlnh bay hoi - ngung t\1 ~ bay hoi .: ngung tu lai.; ta dan dan co' the thu duoc Call, tit A co nhi~t ',dQ s6i thap hon 0 dang gan

. . .

nhu tinh khiet. Y1 v~y ngubi ta dung phuong phap tinh luyen bang

each lap tren blnh ngungmot CQt caoco nhieu dia giiip cn'o viec tai tao qua trlirh bay hoi - , ngirng t1}. tren. Nhovay chat long A d~ bay

-~

khong t uon g tac voi nhau, co th~ bieu

di~n s\t ph 1J th uec cua nhiet do sci cua chat

• •

long va nhi~t dQ

ngung tu ella ~ hoi ph \1 thuoc vao thanh phan h6n hop hai chat dd t.. It::===-t---

" I.

(hlnh 3-1). {

I

. .

}..' 2

·x; X,

Thqnh phon

Htnh 3 .... 1.

..

..

B

._. __ ._ .. -_.-

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

•

v

hoi din dan thoat l~n· tren. i! trang ~hBi ng8.y cang .tinh kh.iet, con. chA:t long B cd nhiet dQ sOi cao hen, ngung t\l tra lai blnh cit. Co th~ dung loai c~t lap day cac ong thuy tinh hay s11 thay cho cl)t da n6i tren va hl~U qua cua cQt ducc tinh bang "s6 dla lY. thuyet" .

.

Trang truong hop co tuong tac yeu gifta hai chat long (solvat hoa .

hay ·to hQP) thl thu dti<;lc hai dang do thi bieu di~n s\t phu thuec nhiet de? soi va ngung t\1 vao thanh phan hdn hQP: mOt dang vai nhiet d() sOi c'da hon hQP dang phi cue tieu (hinh 3- 2a) va mC)t dang

. .

voi nhiet dQ soi cue dai (hlnh 3- 2b).

c

t ) f
t 1
I
t
I
tA
I
I

I
I
I ;
I
~ I 1
j
I
I I
I
A xD Thanh phar, 8 Xo lhanh phan B
.
Hlnh 3 .. 28 .. Hlnh 3 .. 2b ..

Trang truong hop hon hQP dAng phi cd nhiet 4(J sei C\!C tieu. (thap hon hai cau ttt ban dau), cang' len phia trsn cua cQt cat, hon hQP hoi va long cang gan thanh phan cua hon hop dang phi, trong blnh cat secon l;p chat A hay chat B nguyen chat tuy thea ta xuat phat tu" h6n" h.~ co thanh phan phia b~n trw hay ben phAi hlnh 3- 2a. 'I'rong truong, hop h6n hcp dAng phi co nhiet de) soi cue dai, cang len phla tren cua cQt ·cat thi cang giau cau tit A hoac B, con Iai trong· blnh se ~ IS. hon hQP cang gan viii thanh phan cua h6n hop dang phi (hlnb 3- 2b).

3.1.2.3. Chung cat chan kMng (ha)' gidm up)

. ..

Khi can chung c§:t met chat long d~ bj phan huy a nhiet dQ cao,

28

nguoi ta phai dung phucng phap cat chan khong, tile la dung born hut de giam ap suat tren be mat chat long. Vi chat long se soi khi ap suat hoi rieng phan dat den ap suat khi quye n, nen bang phuong phap nay, nguoi ta co the giant duoc nhiet dQ s6i cua no 1119t each dang ke, tranh hien tuong phan huy hay chay no. Nho phucng trlnh Clapayron- Clausius, nguoi ta co the tinh duoc s\i phu thuoc cua ap suat hoi mot chat vao nhiet dQ. Tuy nhien, co the tip dung quyIuat thuc nghiern gan dung nhu sau: Khi ap suat khi quyen tren be mat mot chat long giam di nlQt mra, nhiet dQ soi cua no bi ha thap di khoang 15°C .

.. 1.1.2.4. Cat liJi CUD n then hoi nutic

Ta cung co the tinh che mot chat long khong hoa tan trong nuoc, bang phuong phap cat loi cutin thea hoi- nuoc de ha d~enl sci cua no. Phuong phap nay dua tren nguyen tac: Khi hai hay nhieu chat long kh6ng tron Ian voi nhau nam trong mot hon hQP, ap suat chung p cua chung bang tong ap suat rieng phan PI + P2' nghia 13. no luon Iuon ian hon ap suat hoi rieng phan ella tung cau tii bat ky nao. Do do nhiet dO soi cua hon hop sa thap han nhiet dQ soi cua cau tit soi thap nhat, TY l~ hoi cat sang blnh ngung (ve s6 mol). se bang t}" l~ ap suat hoi rieng phan cua chung 0 nhiet dl) sOi cua ·hon hQP. Nho v~y ta co the tinh toan dl1QC luong nuoc can thie~ de IOi cudn h~t chat can tinh che, Vi du, khi cat loi cudn thea hoi mroc

-.

nitrobenzen (to = 211 "C), a 760 tor ,hOn hop nitrobenzen ~- ~110C soi

,

lJ 99,25°C, 0 nhiet de) nay PH20 = 740 tor, PC6HSN02 = 20 tor. V~y

tY l~ hoi cit sang:

86 nlol H20

-

86 'mol C6HSN02

-

740 20

.

Nghla la, m~6n ,ca:t lOi cuen dugc 123 g C6HSN02 (1 mol) can

37x 18 = 666 g nu{Jc.

. -

·S~u khi dA dung phuong phap-cA:t ·lOi' cu6n theo hcli nltCJc, thullng

ta phM chi't tach cac chA:t - cln~ -tinh ch' ra kh6i ·nt1'-'c bAng mOt.

29

•

---- - ._ .... _--_ .... _ .. _--- _ .. - ... -...,........-- _ .. _ .. _-_. _ .. _._-_. __ . ----_ .. _--- - ._. - _. -_ .. _.- .. _ ... _----_ ... _ ...... _. --- - -- -_.------ -_._---- . __ .-.' --_._. --_ .

•

.

dung mol thich hQP, roi lai tieD hanh cat phan doan de tach dung

moi. Cu6i cung chung lay chat tinh kh et bang binh cat co gAn nhiet ke duoi ap suat thuong hay giam ap, voi sv. kienl tra nhiet ctq cua chat can tinh che.

3.1.3~ PhU'ang, phap thing hoa

M¢t s6 chat nhu iot, long nao ... co kha nang thang hoa (chuycn true tiep tit the ran sang the hoi), I vay nguoi ta co the dung phuong phap thang hoa C1 tip suat thuc ng hoac ap suat thap dg tinh ch€ chung, Phuong phap nay thuong ho phep tinh che' mot luong. nho chat va thu duoc san pham kha tinh khiet.

3.1.4. Phlfang phap chiet

Chiet iii dung mot dung mol thich cp c6 kha nang hoa tan chat dang can tach va tinh che de tach ch t do ra khoi mol truong ran hoac long khac. Thuong nguoi ta dun mot dung moi soi thap va It tan trong nude nhu ete, cloroform de hiet tach chat hiru co tit 11l0i truong nude (cac chat hfru cd can tin che nay thucng tan it trong nuoc hoac d, dang nhu tuong Ian voi uoc) 4 Sau khi lac dung moi vci hen hop chat can tinh che va nuoc chat do se chuyen phan Ion len dung moi va ta co the dung pheu hie't de tach rieng dung dich thu ducc khoi nude.

+

...

Bang each lap lai viec chiet mot s6 an, ta c6 the tach duoc hoan toan chat can tinh che van dung mol a chon, sau do cat loai dung . moi va cat laj" :Ghjt tinh ~hiet (j nhiet Q va ap suat thich hop,

N guoi ta cling thuong chiet mot ch ~t tit hon hop ran bang mot

,

dung 1110i hoac hOn hQP dung moi voi 9t dung cu chuyen dung dac

biet gQi Iii blnh chua Soxhlet. Dung 1110· ducc dun nang, cho bay hoi lien tuc chay vao blnh chua hon hQP an chiet tach (thuong duoc g6i bang giay loc), 0.6 se hoa tan chat an can tinh che va nho mot' 6ng xiphong, dung djch chay x\long b nh cau ben dudi, dung moi nguyen chat lai tiep t\1C ducc cat len. Qua trinh duoc tiep tuc cho den khi 51:1 chiel ,·tach "~dt1<;1c hoan toano Phuong phap nay tiet kiem duoc dung llloi va dat hieu qua tucng 6i cao.

30

_,_

-.

3.1.5. Cae phuong philp sac ky

Phuong phap sac ky ducc Xvet" phat minh ra de tach cac chat bang hap phu til: dau -the ky nay (1903), den nay da tra thanh mot phuong phap tinh che, dinh tinh, dinh lucng rat quan trong trong hca h9C hiru co, duoc phat trien rat manh va ducc sit dung r¢ng rai trong hau het cac phong thi nghiem hien dai.

Nguyen tac chung cua phirong .phap sac ky nhu sau: hon hop chat nghien CUll a pha long (dung dich) hay pha khi duoc cho di qua be mat chat hap phu a pha ran hay pha long kho bay hoi. Do kha nang tuong tac \~C1i pha tlnh khac nhau nan cac chat khac nhau trong hon hop nghien ctiu chuye'n dong' voi van toe khac nhau va dan duoc phan tach ra tung cau tu rieng biet. N gttoi ta phan chia ra thanh cac loai sac ky khac nhau.

,.1,J.5~1. sac k __ v ('pt (silc A1 hap phu) Trang ph uo ng ph ap sac ky cot, nguoi ta dung cac cqt thuy ·tinh hay doi khi bang kim loai,

co klch th tt(i·c thong thuong Iii

15x 1; 25x2; 40x3 hoac 60x4 em; dung cac chat hap P~1:1 a dang b o t , t h uo n g la nh orn oxyt, silicagel, tinh bot, bari sunfat ... h oac mo t chat bat ky kh ac khong tucng tic voi chat nghisn cuu va dung mol. Han hQP chat

,

nghien ciiu ducc hoa tan trong

nlt;.t dung moi tro thich hQP va cho chay qua cot. Cac chat trong hon hqp nghien cuu dan dan

Sinh dtJng dung dich

.... ,.

~,nh hung

•

(*). M~C. Ilaer nhit bac h9C Nga.

31

_ -.--:-.-_. __ . .. . .. _- - ._.-_ _.- _ _.- _ __ .. _._--_ .. _-_._._.- --_ ---- _.- .. __ - _--_. - _ .. - -_ .. _._ .. _ .. _ ----_.- .-.-

- -_ .. _ .. _. __ . _ .. _._-_. _ .. _. . ...

. tach khoi nhau va chung chiem cac vi trl khac nhau tren cQt hap phu, VI Ide dau nguci ta tien hanh tl~n cQt thi nghiem vai cac chat mau, khi chung tach ra tao thanh cac khoanh 1118.U khac nhau tren

•

6ng hap phu nen phucng phap nay ducc goi 18. 'phuong phap sac ky,

F .

Sau do nguoi ta tach rieng tirng chat hoac bang each cat CQt hap phu thanh tung doan ling voi tung chat, hoac lien tuc d~ them dung mei, cac chat se Ian luct duoc rita troi va thoat ra binh hung C1 cac thoi dienl khac nhau.

Co the dung phuong phap nay de tach cac chat' khong co mau, nhung phai dung cac chat chi thi hay thuoc thli thich hop de nhan bie~ khi nao chung bat dliu thoat ra binh hung.

Sac ky gia~y' la l11Qt dang dac biet cua sac ky phan b6 do Consden, Gordon va Martin phat minh narn 1944. Pha tlnh CJ day la nude tham tren giay 19C dac biet (xenluloza tinh khiet). Dung dich chat nghien ctiu ducc cham tren 1119t .dau cua dai giay (each mep giay chirng 2,5 em) va Dloi giot each nhau chimg 2 em Nguoi ta thuong nho dong thbi ca dung dich mau da biet de so sanh. Sau do dau giay lee ducc nhung trong mot. dung rnoi hay hdn hop dung moi thich hop da baa hoa .nuoc. Do luc mao d~n, dung moi se tharn dan len . giay sac ky, keo thea chat nghien ctiu chuye'n dQng len phia tren va tao vet tren giay Ina nguoi ta co the nhan bie't duoc bang mat

. thucng hoac bang chat chi thi. Ty so R, giiia de) dich chuyen cua chat nghien ciru va dung moi duoc gQi 1a hang so sac ky, hang s6 nay la dai lucng quan trong dac trung cho tirng chat .

.

De thu diroc ket qua tach tot han, nguoi ta co the lap lai thao

tac tren voi mot dung rnoi khac va thea chieu thang g6c vdi chieu chay ran truce (sac ky phan b6 hai chisu).

Sac ky giay· thuong dung de dinh tinh cac chat, nhung cung co the dung de dinh Iucng Sd bl) dua vito dQ dam va tiet dien cua vet chat nghien ciiu.

32

•

. ., .. -_.- - --

... -.. . ..

• • -. p ••

... '... - .

. .

,. . r, .,

• I .

... ., ..... ~ . - , ... :. ~ . . . .. .

. '..-

.. ..'

Phuong phap nay .. duoc Izrnailop (113Ma"J1oB).,y~ Schreiber .de

nghi tit nam 1938} :duQc Stanphattrien va hoanthien (1~5Q)". ~pi~n

no co irng dung tat~Qng rai, ,_'.. . '.' . ,: ',",' , ' '.

• : ° • ..' •• •••

. .... . ...

Nguoi ta trang .. mgtJ4p 'mong.chat hap ph\t,(A.lz03, silicagel) Ien .

mot tan} ldnh kfdh thuoc ~'boAng lOx12 em ,P.9~,:20~~O cpl"c}1aru met giot chat _nghl.en ciiu haY- h8n hQP nghien ciiu lenmot :dau, ban (each mep khoang 2 cmi roi chodung moi chay nhu sac ky giay.

• •• .. 0 •

. . ..... . .,..- . ..: . .. ..

Phuong p.:J:iap:,$~c: kj lap')nongthuang cho ,.hi~u; qua .tach

• , 'I • • • • _ •• _ __ • •• ,

cao, thoi gian ng!n, Iuong: chEit:It! thuong duqc dung de dinh ti,P.-h

va tach cac hop-chat thfen-'nhien.Nd cung dl1Qc"cac,nna, hca hoc

••• I ... -

tong: .hopstr dung thuong xuyen de nhanh chong phan . tach cac.chat

. , _... - ..

thu .duQc· trong phan ~tffig~· '. . ' .... .: .: . . ..

t

.. . .. . ..

. .

I • • •

•• _0 ,.'

..

. -.

'. .

.,

.Nhirng .: narngan day sac kY.;khi Iong .(dqi· khi goidon .gian Iasac

ky . khl) diroc :ph_~t' trie.~, n~~~h' .~e" ~p,iCJ ra kh~ '~~~g t{j~, t~~ng phan ti~h- va t~c'h~A~' hop eh§:t 'de' bay hoi. P'h~d~g ,-phap .tbong ~hUC1.ng IS.

- • 0·' •• _.. •

cho vai microlit chat long. phan tlch vao .thiet . bi bay hoi rai dung

dong khimang (thdbng Iii;' heli) re. duon'~p.~r-~~d :'~hurig:'qu~ mot 6ng

. . - ' . . : _. _ .. ..... ..... "r . - .. _ .... . 1- ...... •·• -: . - -. I , .. ' I '.. ••• ..

daFnun'g'nohg nap daYnlQtthat ran' x6p(v.rd~'.g~ch clj.!ii hra tan

r •. .' • ; • i" • ". '" .'... .:- • ". -, .", .». -.,";' : .. , .: ~ - ": .': . :'-.' ~: , ~ .. :: .

nho, nhorn oxyt, silicagel,' than hoat tlnh .. ~.) duoc 'tam bang chat long

. . . .

kho bay hoi nhu dau silicon, polyetylenglycol, cac este soi cao.i. 'Rbi

do xay ra su phan be cac .chat g1i-ia'-phi3:)ong va .pha khi, dong thbi

• • , - • p ',.

... -

11 .......

chi can co su khacnhau nho trong Sl:i phan b6 nay gif1a:/~c"cau tit

trong hon hop cung du de-"phan ta~h hoan toan .:~c chat long trong. h6n'h<;tp,;'vin:'o 'ciuqc lap .fti lap lainhieu Ian trorig 6ng dai, Nguai ta

_., p. . .

.. .

thuong nhan bi€t tung cttat thoat ra a cudi Oilg bang each do su

.' ~ r·· ~

thay d6id¢ dAn nhiet' cua.khl thoatza. Bo do:cua may sac ky khi

long.duoc trinh 'naY-'j} hinh 3:~{ Tuy vi'~c pliaf"hi~n ID.'i?t-pic - tro~gsd ' ....t~ ~ k' khf ".. 1'" d·...... -k" A ...... h h d .,. "'t-. d III h kh· ~ . uu:' sac··· 'y'" 1-. mor-ia ·teu· ten --can,-- n ung c rra: U' -ve·· .. Q"tln '. le·t~'_.

cua mot '~hat:phttdng phap sac ky khff~n rat hiru ich khi llhAn tich

. '.

... -

33

... _. ...

met IUQng nho hOn hop cung nhu,de tach va tinh ch'e' cac chat. Vi

d9 bang phtlong phap nay ta co th~ n ha n biet va tach cac dong phan ella alcol butylic nhu d hlnh 3- 5.

Can nh an m.anh

•

rang, trong ph uo n g phap sac kj, n6i chung ciu true phan tu cua cac hop chat co anh h ttdng Io n den can bang hap phu, cling nhu h~ 86 phan b6 cua chung giita cac pha, do do lien quan chat che den hang so Re' Vi vay ket qua phan tich sac ky cung cho ta thay nhirng thong tin btl .ich

s

Htnh ._~ .. ../, so do' sAc ky (dung detecto dan nhi~t) 1. Bu6ng so sanh cua detectd; 2. Bu8ng do cua

I·' ~

detecto; 3. Kh6a; 4. COt ph!n tich; 5. The tich mau

phSn tlch; 6. Detectd;

ve cau true ella' hop chat.

....

-

-

San qua trlnh tinh che, ta CaD kiem tra ·dQ tinh khiet cua ~QP chit thu duoc 'bang each do nhiet dO nong chay (d6i VC1i chat ran) hoac nhiet d(> soi (d6i voi chat long) hoac do ty kh6i, chi so khuc xa, chup ph6 ...

CH ' I 3

-CH3-C-OH

.CH3

mV

CH" CH-CH-OH

./ 2

CH3

....

. CH~-CH -CH-CH-OH

;, ~ :2 2.

Htnh 3 - 5.

Ihd! gion

34

•

I

........ --

,

MQt chit chi dl1c;tc coi 18. tinh khigt neu qua nhiau IAn tinh ch~, cac hang s6 v~t Ii etta no khong thay d6i~

3.2. xAc DfNH THANJI PHAN PHAN TiT cAe CHAT HUU CO (XAC BINH C6NG THUt PHAN Tln

D~ xac dinh duoc cong thuc phan tit cac chat hUll co, nguai ta

, ' .

ti~n hanh xac dinh cac thanh phan nguyen to va kh6i I uong phan tit

~ .

cua chung,

3.2. 1. Phi" tich nguyen to

Cac chat huu co ngoai cacbon con thuong co hydro, oxy, nita, halogen, luu huynh ... De xac dinh S\1 co mat va ham lucng cua chung, nguol ta sit dung cac phuong phap dinh tinh va dinh 111Qng

rieng.

3 .. 2.1.1. Xac dink cacbon va hydro

811 co mat cua cacbon va hydro trong mQt hop chat thuong dUQc xac dinh bang each dot chay hQP chat do trong oxy, vci xuc tac IS. oxyt dong:

.. . -..

Y. z CxHyOz + (x + 4~ 2" )02

I ••• +-.. .

.

CO2 thoat ra duocnhan biet bang phan ung lam due nuoc voi

~

trong:

. .

Ca(OH)2 + CO2 = CaC03i~ + H20

H20 dUQc nhan biet bang each ngung t\1 tren phan lanh eiia 6ng . dot hay bang CuSO 4 khan.

DG dinh luong cacbon va hydro, nguci ta d6t ·chay m.()t luong can

. ~

chinh xac chat nghien CUu bang dong oxy co m~t CuD trong ong

thach anh, roi hap th9- hoi nude thoat ra bang perclorat magie (MgCIO 4); CO2 hap thu bang amiang tam xut (NaOH). Cac chat htIp thu nay d~ng trong cac ong chu U va khoi 11.t<;tng cua chung dUQc

35

f

•

can chinh ixac truce ,Via sau khi thi nghiem k~t thue., Hieu so :kh6i Iuong gif1a hai Ian can cho ta bie't kh6i lucng H20 va CO2 bi hap thu,

•

Neu trong thanh phan chat 'nghien ciru .co halogen, luu huynh, nito, chung co the tao nen cac oxyt cua nita, cua luu huynh, halogen hay axit halogenhydric va chung co the anh huang den ket qua can cac 6ng hap thu. De loai trir cluing, trong Dng nung d ph an

" ..

• • .' • •• I •

cuoi, nguoi ta 'phai dung cac sci bac de gii1 halogen' va oxyt luu

huynh, dung P 205 de phan huy cac oxyt nita.

3.2.142. Xtic dinh nito

De xac dinh su co mat cua ni to trong hQP' chat nghien .ctru, ta co th€ dot nang Dla.U ·'thu· -viii natri kim loai, nita cung cacbon -tron~g' Yllau ·.thu se.·chuyen thanh NaCN; hoa tan 'san pham tao thanh trong nucc cat, 19C lay dung dich; them Ian IUQt cac ion Fe2+) Fe3+, axit h6a sa tao thanh ket tua mau xanh:

•

6CN- + Fe2+

•

4Fe3+ . + 3[Fe(CN) 6]4-

.

___.:.. Fe'4[Fe(C'N)r)3 J,

•

rnau xanh

,

D€ dinh lucng nita, nguci 'ta thuong dung phuong phap Dumas

hoac Kjeldahl.

Nguyen ly cua phuong phap Dumas 13. oxy hoa hQP chat htru co bang CuO r~i loi cuon san pham bang mot dong CO2 tinh khiet, Nito trong chat hiru co se chuydn thanh N 2 tlj do. Ta do the thu N 2 ehoat ra bang .met buret up nguoc trong chau chua dung dich KOH d~m dac, H20 se ngung tu-trong dung dich; CO2 hoan toan bi hap thu hoi KGH; Nz thoat.len dll(1c va ta c6 the do th~ tlch cuano mot each d~ dang t

Phuong phap Kjeldahl tuy khong phd bien bang phuong phap' Duinas , song trong nhisu tntbng hop cling - r~lt - tit?n lei, no cho phep

36

v

\

xac dinh nhanh ham IUQng nita trong Inau thu. Bang each VQ co

,

h6a hop chat nghien ctiu khi nung nang trong H2S04 dac c6 xuc tac

selen (khi- can co the them .chat oxy hoa), ta chuyen nita thanh 111U6i. amon sunfat, sau do kiem hda dung dich thu dircc roi loi cuon r NH3 thea hoi nuoc sang met binh khac va chuan dQ luong NH3 tao thanh ..

3.2. / ... 1. Xtic dinh halogen

8\1 co mat cua halogen trong hop chat huu CO duoc xac dinh bang each tanl mau chat vao mot soi day dong roi dot, neu hop chat co chua halogen se tao ra ngqn Ilia mau xanh luc,

Nguci ta dinh luong halogen bang each oxy hoa mAu chat trong binh chua oxy nguyen chat, co xuc tac Pt, khi do se tao ra axit halogen hydric, hap thu bang dung dich RN03 va ~au d6 xac dinh bang phan ung vdi nitrat bac:

AgN03 + HX

Bang each so de) due hoac chuan de) luong Ag" du, nguci ta tinh ducc ham IUQng halogen trong mau chat nghien cuu.

3.2 .. 1.4. Xdc dinh luu hUl'nh

r .,

Khi dun chay hop chat hun co vdi natri kim loai, luu huynh se chuyeri thanh Na2S, sau do ta co the d~ dang nhan biet duoc bang each phan ung tao ket tua PbS hay Ag2S:

PbS ~ + 2NaN03

De dinh luong .luu huynh, nguo! ta oxy hoa IilB.U chat htru co bang HN03 hoc kh6i trong ang han kin Cs 200 "+ 300°C, sau viti gib luu huynh trong mau chat se chuydn hoa thanh H2S04, ta c6 the dinh Iuong bang phan ung vdi Baelz, roi xac dinh luq~g BaSO"~ ~ bang phucng phap trong Iuong:

.' . .

•

.. . ..• 1. __ •

• - • • ••• _ • I ._._

II I •• • _ •

. - . .... _

• • II.·· •• • •

. - - .. ,

-_._. __ ... _ .....

•

..

3.2.1.5_ Kdc djn·h cdc nguyin t! ·kh4c

..

,

Ngoai cac ,nguyen to ·ke tren, ,trohg tn.(Jt .86 trubng hQP chA:t hftu

co cd th~ con chua P, Si, m()t· 56 kim loai kh:ic ....

Ta Cling oxy 110a hop chit hftu co bang RN03 bOc kh6i trong 6ng han kin h* nung chAy nd voi han hop NaN03 va Na2C03' Cac nguyen to ndi tren se chuyt$ n h6a thanh cac hQP $at vO co tuong tlng (thuong vai hoa trj duong cao nhat), sau do ta dinh hrong chung bang eac phuong phap VQ co thong thuong.

3.2.1.6. Xdc dink oX'}

Ham luong oxy trong cac chat huu co thuong dl1QC xac dinh IIlQt each gian tjep, tllc la ta lay kh6i luong mAll dem dot tru di tdng khci IttQng cac nguyen t6 khac vira xac dinh thea cac phudng phap

. .

tren, hoac l~y 100% tnt di hgp phan ella cac nguyen to khac, '

Ta cung co the xac dinh trtrc tiep bang each chuyen oxy trong hop chat hiru co thanh CO r()i oxy hoa bang 12°5:

..

Chuan d<) luong 12, CO2 duqc gi8i phong ra hoac chuan de? lucng 1205 du, ta tinh duqc luong CO hlnh thanh,

T6m. lai, nho nhimg CaD phan tlch che tao c\ic ky chfnh xac, nho nhfrng thi~t biphan deb ngay cang hoan thien, nguci ta co th~ tien hanh phan tich vi IU:Qng hoac ban vi hrong, viti nhtrng mau ch~t rat nho (vai mg) ciing du cho ta ket qua dang tin c~y~ Tit nhimg nam

, .

60, nguoi ta da phat hien va sit. dung ca eac phuong phap sieu vi

IttQng, chi can can miu chat (1!~n can di~n ta t1:i dQng), con cac san phdm d6t chay dtiQc xac dinh bang nhimg thi~t bi tinh vi t~n co sit do dQ dan nhiet etia cac chfi:t khi nhCl b(> ph at hi"n detecto. V(ji

I '

•

phuong phap nay, nguoi ta cd the X8.C dinh dbng thbi C, H, N hoan

toan t\t dQng trong vong 10 phut, luong miu chi can khoang 1 mg.

~ 38

•

. .

3.2.2.. Thiet tlp cong- thLlC- t6ng quat eua hep chit

•

Sau khi xac djn.h thanh phan khoi IUQng (hoac thanh phan % kh6i Iucng) cua tung nguyen to' trong chit nghien ctt·u, bang each ehia cho nguyen tit Iucng cua cac nguyen t6 tuong dng, ta sa tim dliQc ty Ii? giita sO nguyen tit tUng nguyen to trong phan tu, til deS thi€t I~p duoc cOng thuc t6ng, quat cua chat da eIr.o: dUC1i dang

(CxI\OzNt)n·

..

Vi du, dot chay 1,5 mgmot chat: A tao thanh 0:,,9 mg H20; 1,76 mg . CO2 va 0,224 ml N 2 (quy ve dieu ki~n tieu chuGn). Ta tinh khoi lucng tung nguyen t6 trong Dl3U chat nhu sau:

•

0,0009 . 0t0009

0,9 DIg H20 == ptg =:-: x 2 = 0,000'1 g H ==

18 18 . .

=0,1 mgH

O~00176 0,00176 .

1,76 mg CO2 z - ptg == x 12 = O,OOO4a g C ,.=

44 44

•

~ 0,48 mg C '

9,224 0,224

0,224 ml N 2 ::::: ptg :::; x 28 = 0,28 mg N

22,400 22,400

LU:Qng oxy: nto = 1,5 - (0,48 + 0,1 + 0,28) == 0,64 mg

..

Ta co:

. O,~8 0, 1. 0,64 0,28

va x : y : z : t = 12 : 1 : 16 : 14 = 2 : 5 : 2 : 1

V~y cong thllc tang quat cua cha:t nghien cuu la (C2HS02N)n'

De xac dinh n ta phai xac cnnh kh6i lUQng phan tit chat dB. cho hoac

, .

dOi khikhong, thuc hi~n dUQc trong di~u ki~n do thi phai bien luan,

39

•

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

,

3.2.3. Xac dlnh khoi 11Iq'ng phan tLf cua mot hop chat

D~ tim duoc cong thirc nguyen (cong thuc phan tit) cua 1119t hop chat, ta phai xac dinh kh6i IUQng phan tit, hay noi chinh xac han '.i3. xac dinh phan tli gaul cua chat nghien CU:u~ Co nhieu phuong phap

xac dinh phan tu Iuong. : .. " .: ,

,

, .

a. Neu nl8.U chat nghien ciiu Iii chat long d@ bay hoi, ta cho -b~y

hoi d nhiet de) thich hop, do the tich hoi d dieu kien dci roi :tinh

. ,

phan tu IUQng cua no theo phucng trlnh:

nt

pV = nRT = RT

M

ntRT

..

. . .

lptgM = _pV

trong do:

p - ap suat;

V - the~ tich hoi chat nghien ciiu; ni .. kh6i lucng chat cho bay hoi; T - nhiet dQ tuyet ddi;

R - hang so khi,

h. Neu do ·dttqc t5r kh6i hoi cua chat da cho d6i voi 111¢t chat khi nao do, ta co the tinh dUQC phan ttl gam cua no Il1Qt each, d@ dang.

VI du, hoi chat A nang gap 25 Ian H2 thi phan tit luong cua-no

. .

phai Iii M = 25 x 2 = 50.

." .. ....

,.

c. Dua VaG dinh luat Raoult

• • 4

- .

Dung dich 1119t chat kh6 bay hoi trong mot dung moi nao _~6 Iuon ..

.. .'. r <. ,/ .', .

co nhiet ct¢ soi cao han, nhiet dQ dong dac thap han so voi dung l110i

nguyen chat va de? tang dienl sci hay tit?' ha dienl ket .. tinh luon. . .tY.;l~

." _'" .,1 I I ••

• ... • ... ..' I

t .. . . . 'I

• .~_ ~ ~ I~ I ~: •• J.: ,f' ~ .. '~. .. ,:. I.' : L_' r • ', :.

tlt = KG

,. .

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

... . ~ .:" . .. .. ' -_ .. . ... .

- . . .",'

I .. • .. • "I. ....

I ~ ," ~ s ; , i· •

40 .

K.. h~ s6 tSr l~, duoc goi la hang .sf) 11ghi~111 sci hay nghiem lanh, d~c trung cho tirng Ioai dung moi;

C .: nang dO mol/l hay. ptg/lOOO g dung 1110i.

Bang each do nnic tang nhiet de) soi (phucng phap nghiem soi) hoac miic ha dielll k€t tinh (phucng phap nghiem lanh) cua dung dich chat nghien cuu trong dung D10i thich hop, ta de dang xac dinh ducc nang d9 chat tan va do do xac dinh duoc phan tit gam cua chung,

N guoi ta hay. dung carnpho lam dung moi, VI hang s6 nghiem lanh cua no kha cao (khi hoa tan l11Qt phan tl1 gam chat tan trong 1000 g campho,. dielll dong d~c ha di 6.t = 37,7°C).

d. Cac phttC1ng phap khac

.

Bang each tuong t1:1, nguoi ta cling co the do ap suat tham thau

cua dung dich chat tan, do dQ nhot cua dung dich hoac bang phuong phap kh6i phd, tu do ·xac dinh duoc kh6i IU<;1ng phan tu chat da cho. Neu biet ra so nhom chirc trong mQt phan tit chat nghien ciru, bang

•

each xac dinh nhorn chuc cung cho phep xac dinh phan ttl: luong cua

chung.

Vi du, '0,92 g met alcol don chuc tac dung voi met luong duo Na cho 0,224 1ft H2 (dktc) thlphan tit lucng cua aleol phai 13.:

0,92

----=46

0,224 x 2 22,4 .

3.2.4. Thilt Itp c6ng thue nguyen cua mOt hOOp 'chit

Sau khi X8.c dinh duqc cOng thti'ct~ng quat cua chat nghien cuu "

...

va kh6i l~Qng phAn tit cua no, tao d~ dang tint ra duoc trj 86 eua n

va do do thift l~p dttQc ceng thtlc nguyen cua hop chtit ~ -,

Vi du, dA l~p dttQc cOng thuc tdng quat cua ch§t A d1Joi dang

4·1 .

-- --- .. - ------ _._---- ----- ----_ .. _-------- . - . __ .----.----- ._------- ----- _. --_ .... __ .. _----_. -- ---_. -- - ~- - -- ._----_ ... _._-- -- ... _.-

. - .

v

. .,

..

. .. . .

(C2HS02N)n nhu d VI du tren, dong thai bang motf.rong cac phucng

,

phap vira neu ta X8C dinh d1JQc phan tu: luong cua chat A la 75, ta

tinh duoc:

..

...

(2 x 12 + 5 x·l + 2 x 16 + 1 x 14)n = 75

75n =.75

=> n = 1

V~y cong thuc nguyen cua A. pha! 18. C2Hs02NI

. Tuy nhien, nhieu khi trong dieu kien thuc nghiem khong cho phep ta thuc hien tat ca cac buoc tren, co nghia Ia phai giai· bai

• - I •

toan tim cong thuc nguyen khi s6 phuong trlnh toan _hQC lap dugc It

han s6 an so, trong truong hQP nay ta phai bien luan. Phuong phap bi~n luan phai dua VaG dac diem cua hop chat ~a cho de xac dinh

. .

tr] s6 n. trong cong thuc tong quat, hoac dua vao cac bat phuong

trlnh phan anh mdi tuong quan giua s6 nguyen tit+ cua cac nguyen to co ban.

Vi du, mot hydrocacbon co ty kh6i d6i vd.i hydro 18. 21. Hay tim

. I . •

cong thdc cua no.

Ta co khdi 111Qng phan til lit 21 x 2 = 42. Neu gQi cong' thtic cua

hydrocacbon do la CxlIy,. ta co: .

•

Suy ra: hay:

12x + y = 42 12x < 42

x < 3,5

M~t khac vi CxHy la hydrocacbonv rien s6 nguyen ttl: H trong phan tit khong vuot qua 2x + 2, nghla Iii:

ys2x+2

42 - 12x :S 2x + 2 ·40 s 14x

2,8 ~ x

42

.

K€t hop voi l~p ·lu~n tren, ta co 2,8 :S x < 3,5 rna x chi tiep

nhan gia tri nguyen, vay x = 3, suy ra y = 6.

Chat da cho co cong thuc C3H6.

3.3. cxc PHUONG PHAp xAc DIN" CAU TRue PHAN TU

•

~ .....

HOP CHAT HLJU co

•

Cac hop chat huu co thong thuong co nhieu dong phan khac nhau. Tinh chat cua chung khong nhirng phu thuoc vao thanh phan phan ttl Dl3. ca vao c:iu tao phan ti1 cua chung (thtl t1:i lien ket, vi tri va kieu nhom chuc). Vi vay, sau khi da xac dinh cong thiic phan ttt nhu tren, can xac dinh ccng thuc cau tao cua no. Tharn chi trong nhieu truong hop, sau khi da tach duoc chat tinh khiet, nguci ta tien hanh phan tich quang pho de du doan ban chat va cau tao hQP chat da cho ngay truce khi thuc hien cac phan tich hoa hoc khac.

De xac dinh cau true phan tit, nguoi ta co .the dung ca phuong phap v~t ly va hoa hoc, cac phuong phap vat ly ngay cang duoc su dung rong rai hon va dong vai tro quan trong han.

· 3.3.1. Cac phllang phap vit IV phin tfch cau true ci c ch't h Cru ca

Trang .cac phuong phap v~t ly, truac tien phai noi d~n phuong phap Quang pb6 h(p th\l phan ttl. Dd IS. ·phuong phap v$.t ly huu hi~u nha:t, vi chi can met lUQng nha "chit, trong mQt thbi gian ngan, nhung lai cho mO~ lucng thOng tin len v~ ca:u true phan tit.

Cd thi ndi tAt ci cac dii s6ng di~n tit voi cac bUCfC song khac nhau, ttt song 'c\Jc ng4n (ROentgen) dA'n song tUdng d6i ..1al·(song vO tuyG'n) d!u cd t~1 sit d\lng trong cae d,ng Quang phd khac nhau d'

~.' .

phan deh c«u tr6c cac 'cMt huu co, M6i loal co llng d\lng rlAng, ",

trong pham vi nh4t' dhi:h va ndi chung chung h6 trq, b6 sUl)g lin cho nhau.

48

•

•

v

N guyen tac ch ung cua quang ph~ hap thu 18. khi bi kich thich hoi biic xa dien tir, phan tit cac chat se hap thu nang lucng lucng ttt voi buoc song thich hop de chuyen sang trang thai kich thich co nang luong cao han. Su hap thu nay co tinh chat chon loc, phu thuoc vao dij.c dienl cau true cac phan ttl vni tung loai lien ket, tung loai nhom chuc.; Vi vay, phan tich anh quang ph6 chup duoc cho ta

.

nhung thong tin nhat dinh ve cau true phan t11, ve s,,! cd mat cua

cac loai lien ket hay nhdrn chuc nhat dinh.

. .

Anh sang tu nguon sang (hay song di~n tit thich hQP) ducc di qua lang kinh de tach pho. Birc xa dan sac di qua ca cuvet chua chat nghien ciiu va cuvet bo chinh (khong chua chat nghien ciru hoac chi chua dung moi tinh khiet) rei .vao h¢ phan tiep nhan deso sanh cucng d¢ hue xa sau.khi qua hai cuvet. Cong viec duoc l~p Iai

. .

lien .t\1C vdi met buoc song moi. Ket qua do dac sau khi qua bq phan

. .

khuech dai, ducc tu dong ghi lai tren bo phan ghi thanh ducng cong

hap thu (ph6 hap thu) dac trung cho tung loai chat. .

•

So do chung etta may quang phd hap thu ducc trlnh bay d

hlnh 3- 6- ·Cae dai phd di~n tit va cac kit~u kich thich phan tit xem d bang" 3- 2.

BO phan tact) phei Nguon anh sang

Cuvet do

... --~

.. I

be chmh

.

tiep . nhan

.

BO phan Ghi kf!t.

khuech d~i qua

Cuvet

·86 ph~n

I ."\. ...

Hinh 3 - 6. Sd dB chung ella may quang ph6 hap thu

"

44

....

+

v

..

Bang 3 • 2. Cai ddi phd difn -til l~Q cackilll· kich thich-phdn tii

..
•
BLlCe· s6ng A, 86 s6ng, ern .. 1 . Ten' Vln9 ph6 ... . , .~ ,. - I ..
Kieu ·klch thich : ..
. _. ...
AO -
_ .. .
-
50 I Tia Roentgen- fl· ,.
• Klch···thteh electron Idp trong .
~103 2.1)0 T~ ngo~ xa I I
I Klch thlch - electron a
4 I
4~103 5.1J~ rai ngo~ gin. r I
Klch thlch eiectron :r
. .
~
8.103 Z 5.10 4 V~ng nhll thiy If·
Klcl} thieh electron ;t he tiAn h~.
. , - -
2,5.104 \25.164 .Hb~g ngo$i g., Oao dOng phin tli .
-
5.1)5 4~103 , HOng .. ngo$i trung ..
Dao dOng phAn tll •
5.106 2.1)2 H6ng ngo~J xa "
.. Oao dOng ph&n tlJ
,
3.1010 20~ Vi s6ng Chuy," dOng quay·
,
0,33.10 .. 2 S6ng ·ngin radio ..
. .

3.3.1.1. Phuong phdp phd hong ngo{li

S\t ha:p thu bile x~ hong ngoal gAn va trung blnh co li~n quan

.. . .

den dao ~C)ng, ctia cac nguyen til hay nhom nguyen tit trong phan

. -

tit~

Trong phep gln dung. b~c .nhat, tan s6 dao dODg co ban cua mt}t phan tit phu thuec vao kh6i lucng m1, m2 cua cac nguyen tu hay

. .

nhom nguyen tit va Iuc lien kat giila ehung: .

1 k

v=-

.2Jr' M

CJ eliy:

. k • . hang so luc;

. M - khoi luong rUt gon:

. 1 1 1

-= +-

M m} nt2

MQt phan tit co N nguyen tit n6i chung cd 3N- ~c tu do) trong

- ,

d6 co ba b~ lit chuyl;n. d4)ng tinh tien, con I~i IS. cae bac t1;t do d~c

trung cho dao dQng va quay cua phan tit. Cac ph An tit cd c(u true

, . .

thing co 3N-5 ~c tlj do, con khong thing thl co 3N-6 b~c tlj do

. .

45

___ . .. __ __ .. _ __ . . _. _ .. - _ .. _ .. - .. __ '1'"-_ .. - - _.,, -- _. __ __ . __ .-------- ',_, --_ _ ------ -- --------.-----_ .. --.-. --:--------_.--- .

-

danh cho dao dQng. Cac dao d-Qng co th~ lil: ·

- ,.

~ . ...

- Dao dt}ng hoa tr]: lam thaydoi khoang each gif1a cac nguyen til

va theo huong' true lien kE!t ..

. '

• I • .. ...

. - Dao dQng ,bie:n - dang: lam thay di$i gQC hoa tri, eon khoang each

nguyen tu kheng d.6ia -

I '.. I •

Thucng dao d9ng hoa tri hap thu nang luong Ibn hen (<1 buoc

song ngan hon) dao dQng bien dang, Tuy nhisn, phd hong ngoai chi

. .

xuat hi~n vi1i nhirng duo-dong lam thay dt5i' momen luang cue cua

-

phan tit. Nhirng dao d()ng' hoa tr] d6i ·xllng a cac phan ta d6i xiing

khong co phd ~~ng. ngoai. •

•

Bang 3 - 3. Mot so tan so /ufp t/~i hong ngoai d4c trung

.Li@n kat Lo~i h~ chit

. s6 s6ng cm'" ClJdng dO h4p thv
2850 - 2960 rnanh .

3010 - 3100 '\
trung banh
-3300 manh
+
600 - 1500 ",(
yeu
1620 .. 1680 thay dOt
2100 ~ 2260 _ thay dcSi
, 2200 - 2300 . thay dOi
•
1000 - 1300 manh ~
1720 .. 1740 manh
•
• • .
.
1705 • 1725 •• manh
•
• , C-H alkan

-O-H alcol, phenol

l1li

Ji6n kAt hydro trong alec',

phena -O-H Q(

liin kAt hydro trang axit am bac, nhA t

=C-H

-

== C-H

-C-C, -C==C-

.

-CEC-

-C=:N-

-C-O-

)c·=O

-O-H

_-O-H

. -NH2 -N-H

46

aiken va aren

,

alkil

alkan atken alkin nitrin

atcot ete, axit, este

. aide hit -C-H

n '0

t

x-eton -C-C-C- ,

, U

·0

, 0- ,

axil, este -C

'OH(R)

amin ba~ hai

..

.

,

,

3590 - 3650

thay d6i

... I . J

manh

4

thay d6i ..

3200 - ·3400 . 2500 ~ 3000

.

3300. ~ 3500 pic kep,.

3300 - 3500 pic ddn

• .............. r'I .. l •• _.... I" I -Ir..... .'

,

trung pnh

,

trung bl1h

•

. ~

•

•

Can cd vao nhimg tln 86 hip ·th1}.· ._~c trung; ta ~O the nhan bitt

dl1QC Sl"/:· ·CO Dl*t coo cac nhdm nguyen tit hay li~n ke~ d~ trttng

•

trong phan ttY. D~ng thi1i cac hi~u dng cua cac nhorn khac cung anh

huong lam dich chuy'n tan s6 dJc trung d6 trong in~t pham .vi nhat dinh. Can cd vao dO dich chuyen ta cling rtit ra dttqc nhitngket lu~n nh~t dinh v~ ~e di~m C«u trUe phan tit. Can ctl vaophd hhng ngoai, ta cung nh:~n bi~t du~c dQ tinh khi.§'t cua mt>t hQP_ ch't

(khOng c6 lin nhirng dAf"~b,l:p thu 1$}. "

..., ".

Ta cung co. th~ phan tlch d!n~ htQng nho phd hbng ngoai bang

each ap d1:lng dinh lu~t Lamber- Beer". Tuy nhisn, -khi d6 din anh sang hoan to an don sac (Vi 'du, tia laze), hoac so sinh vbi dUCfng

cong chuan. "~'.." " ·

3.3.1.2. Phrrung phdp phi Raman

..

..

Phd Raman con goi Ii ph6 khuech tan to hQP, ,cung cho phep xac dinh tan .s6 dao d<)ng va quay cua phan ttl, d~ng thbj .nd 11 phuong

, , .

. '..

phap nghien cdu btl sung tot' 00.0 ph6 hbng ngoai, ~iing dao dQng

boa tri d6i xling khong cho vach ria ttfi ria fru<Jen" "

h§:p thu hbng ngoai t1}l' l~ hien Mou

rO trong phd Raman 'va nguoc

lai co tln s6 dao dQng khong - co

trong phIS Raman thi l,i co

. -

t.rong phd hr,ng ngoai. Vi du,

dao dt)·ng hoa tri ella Iien kat

•

C=C trong CC12=CC12 hay C2H4

khong c6 vach ha:p th\1 roo net trong phd h7lng ngoai, nhung, lal cd cue dai htlp· th\1 ra:t manh

.'

trong ph6 Raman,

Thilt bi .chup ph6 Ran. ~ kha don gian (hlnh 3· 7) .

qua

Iia Ion xa

•

Khe

Khe

I h h '""')' Kin p 0

Hlnh 3 - 7

..

~ I '

(a) Theo' djnh lu~t Lamber-Beer, 19 (-f) =~:A.' l...1 =:= EA' trong do El_ia d¢ tit (hay m~t

d¢ quang), ty I':, vdi nhng d~ C (mol/I) va bf day ldp h~p UH,i I; t). Ia hAng s6 .

..

47

~

.- -_ ... _-

-- ._. __ .. _---- . --- --_._._ .... - .... __ . _. _ ....

+

v

)

, ~

Cho bite ~x~ don sac·- (den thtiy ngan hoac tia laze) ~i qua mau, rbi

thu va .phan tich pho cua anh sang khuech ·tan thea phuong thang-, gdc VC1i phuong truyen 'qua etla tia ban diu ..

PhD Raman phat sinh ra do co, s\i "chiem doat" chap nhoang (tuong tac) cac photon nhe cua tia tesi boi phan tu chat mAu va sau do nhuong _cho phan tu m~t phan nang IU:Qng cua mlnh de kich thich cac chuydn dong dao dQng trong phan tlt, photon do lai duoc

,

hue xa tro lai thanh anh sang khuech tan, co nang luong va tan s6

thap hon tia tar. Ngucc lai, cd nhirng photon kh:ic khi tuong tac vdi

. .

cac phan tit dang a trang thai kich thfch lai nhan duoc phan nang

luong do khi phan tu tro lai trang thai cc ban va diroc hue xa ra vlfi tan s6 cao han ban dau. Chinh vi vay pho Hanlan luon co cac vach hap thu be sung sap xep d6i xtrng nhau 0 phia tren va phia duci vach chinh iing vdi tan 56 tia tni. Chenh J~ch tan so L\v giita vach chinh va cac vach phu dng vci mire nang Iuong dao dQng va quay trong pho hong ngoai.

Bang. each ··so sanh phd hongngoai va pho Raman cung giup cho chung ta biet dttQc tinh d6i xirng cua phan tu. Phan tit 'khong d6i ·xung thl moi vach hap thu trong phd hong ngoai phai tucng llng vdi phd Raman. Nguoc lai, phd dao dQng cua uhungIien ket d6i xung trong cac phan ttl d6i xirng chi- co vach hap thu a pho Raman" ..

. .

-'

3ot3.1.3.. Phd electron'

Qua trlnh hap thu anh sang CJ viing ta ngoai va vung anh sang thay diroc dAn den thay d6i mac nang IU<;1ng di~n ttl trong phan tu.

Trong phan tu, cac electron cd the chiern cac quy dao (orbital) khac nhau, qui dao lien kat kg hi~u la G, qui dao phan lien ~et ky hieu la 0*; qUI dao 1r phan lien kat la x" va rmic khong lien ket 13. n,

~

Cae orbital C1 co a mol lien ket don va lien k€t bQi, trong khi orbital

. ' .

x chi co d lien ket b~Qi, orbital khong lien ket n do cac c~p electron

~

( .) Raman la n ha bac hoc An DQ

48·

khong chia cua di to (nhu 0, N) trong phan tu chiem gi~. Khi bj kich thich boi anh sang co nang 111Qng cao, co the xay ra is\! hap thu photon de thuc hien cac buoc nhay cua electron n ~ x"; n -+ Jt*, n ~ o", a -)t a*, nhu so do 0 hinh 3- 8.

"" Ji*
-
...
,
if
n-(J
O-D#- ,
n -$
r
-, o-Ji*
tf .
Ji -J[
-
.
n
r
-
- phon lien kif

khong lien k~f

•

HlfJ/' 3 ... 8. S6 dB bii?!u di~n tr~ng thai electron trong phin tll

, to ...

va cac bLfdC chuysn electron trong phsn ttl

Cac bUQC chuyen a _. o" can nang llic;lng kich thlch cao nhat vi no hap thu trotig vung tit ngoai chat). khOng a v >50000' em": S\t hA:p thu anh sang trong vitng tit ngoai gan va vitng ,kh! ki~n chung to trong phan tit" c6 cac trang thai electron x va n (co lien k~t bOi

. "-

va cd cac ,*p di~n ttl khOng chla). Khi cd hi~u ttng liAn hop, viln'g

.... .. . . .... .

h!p thu luOn dich chuy~n ~~ phla - btt6c song dai hen, d~ng thbi

. . . .... - .

cUC1ng dO hlp thu tAng l~n. Vi du: "

H2C=CH2 ; Amax = 162 nm ; Emax = 10.~ (1620 A)

..

CH2=CH-CH=CH2 '; Amax = 217 11m ; emax = :21000 ·

GH2=CH-CH=CH-CH=CH2;lmax = 258 nm; emax =-:35000"

" .

. 49

:

____ •••••• •• __ - •• - •• _. •• _ ••• - - ••• • __ •• II •• ,. _-- -- - -_ .. _ ••• --- -- - - - -- - •• __ ••• _--._- ------.---. -_._. _. __ • _ •••• _. -

, .

v

. ~

Vi vay, phan tich phd di~n tit cho ta nhirng thong tin q6.y bau VE!

l

cau true di~n tit cua phan tit, 'Sl:! c6 mat cua cac nhom chualien ket

h9i, cua cap dien til khong chia, he Iien~ hop,

Tuy nhien, can thay rang ph6 di~n ti1 thuong co vimg hip th\l tu (khong co cac pic nhon), do sl!' chuydn di~n tit tit trang thai nang luong eel ban E 1 sang trang thai kich thich E2 luon kern thea s\i chuyen hoa ca cac mtic nang lucng dao d9ng va quay cua chung, khien vung hap thu bi ma rong ..

3.~.1·~4. Phd vi sting

..

,

..

-

Neu kich thich phan til bang song vo tuyen (co nang luong tuong

d6i nho) d vung vi song, thl hau nhu no chi lam thay doi miic nang 111Cing quay trong phan tit quanh cac true qulin tinh khac nhau. Vi

,

v~y phd vi s6ng eo th{; coi 13. ph6 quay thuan ttiy, no cho ta nhirng

thong tin quy gia ve dt} dai lien kat, g6c lien ket, voi dQ chinh xac cao t N goai ra, phd vi song con cho ta bi~t S\i ton tai cua dong vi cua DlQt nguyen. tit trong phan ttl. Vi du ph5 quay cua metylen clorua co hai day hap thu ung vci hai dong vi 35CI va 37Cl.

.Tuy nhien, vi thie't hi phuc tap, viec .giai pho tuong d6i kho khan nen ph6 Vi song khong duoc thong d ung,

"

3.3 .. 1~5. Phuong phap phd cpng huimg tit hat nhan

, ,Day la dang quang phd cue ky thuan lei de nhan biet va phan tich cau true cac hQP chill hiru co. Nguyen ly eu'a loai ph6 nay rat dan gian ~ Hat nhan cua mot so nguyen tit co momen tit, khi nam

• L ~

trong tit truong no dinh huong theo phuong cua tit truong va thea

hai chieu ngucc nhau. Giua hai huong nay co s1j chenh l~ch rmic

to

Dang hrong. Trang pho ceng huong t'u hat nhan, ta xac dinh nang

IUQng can thi~t d€ thay doi huang cua momen tit hat nhan,

Cac nguyen ttt co momen tu 'h~t nhan IS. cac nguyen ttt c6 kh6i hrcng hat nhan bieu thi bangso Ie:. HI, el3, 017, :r19, p31 ... hoac kh6i IUQng hat nhan chan nhung nguyen ·tit s6 (s6 proton trong ~t

. .

..

50

, .

... • .. _.... ... ...... • - _ ...... _.... ............ • • :----- .. _ ------.... __ •• __ I"__~'_-' __ .. -- ... .I __ • __ - .. ._ _ __ ... ~ .- ""'1..- ... _. - - - .1'. _. --..&." ... - .. _ ....... -_ ... __........._... ~ I ......... "I ...._

nhan) Ie 5BIO, 7NI4 ... Cac hat nhan ki~u 6912, 8016, 16832 khong cd ttl tlnh va khOng cho tin hieu trong pho tit hat nhan, Do nhieu nguyen nhan khac nhau ma phd cQng huang tlt hat nhAn cua HI, F19va p31 dt(qc sit dung r¢ng rai nhat trong hda hiru co ..

. ,

Cac hat nhan nguyen ttt noi tren khi t\C quay quanh mlnh n6~ thl

•

co momen spin I = ± 1/2 t' Dll0i tac dung cua tu truang bsn ngoai

H vin huong z, mornen spin nay chi cd th€ sap xep trung vci huong cua tit tr.uC1~ (Iz = + 1/2) hoac ngucc vdi h.u:an~tu truong (Iz = -1/2), huang thuan lei nhat v~ nang IUQng phai IS. hucng tit truong. Hieu s6 nang luong AE gitia hai trang thai nayphai ty l~ vcicucng dQ tit truong H, me dung len h~t nhan:

tlE = yhH 2n

o dA.y:

h ~ hang s6 Planck;

y - b~ s6 ty 1~ d~c trung cho tung hat nhan (HI, el3, N15, ... ), vai proton y = 26.750t

May phat blic x, ..,_._. __ ----I V 6 tuygn

Ttl trtJCJng ctJong d.e rnanh H·,

HJnh 3 - 9.

.' • • I

Khi ta cho bdc XIJ, di~n t11 cd nAng hlQng ~ = ~v: t~ong·t'c vlJi .

I •

miu nghiAn cuu, sA xAy ra s\i h(p th\l cOng huang, din t8i 9\1

51·

•

...

...

I

..

----------- T- -.----.-- - _.. . . - -_ _. - ---1. --- .. - -_ _._-_. _. --------.-- _. --- _._._-- _._- _ _. __ .. - .. - .. - . -- .. _ .. _ .. --_. -_ _ .. __ ._- _. ---- ----- ---- .. -- .. ---- -_. __ - --_.

• •

v

chuye'n hoa cac trang thai-no! tren khi:

..

. yhH

M = hv = tuc IA··

2n

v =

yH 2n:

Neu,?tii:lng d9 tit truong la 1,0000 ersted thi tl.E = 2.84.10-19 erg, nghia lit rat nho, ung'vdi tan sO vcua sOng vo tuyen.

Nguui ta cho mdu nghien

ctru vao mgt eng nh o d~t gitra cucn day va d?t trong tu trucug H giiia hai C\!C nam cham manh (hinh 3- 9),

. '

cho dong d ien xoay chiau

ch~y qua cUQn day de t~o nen truong di~n tit cd tan so

,

vo tuyen v + Nhu vay co the

co dinh H, thay d6i v cho den tan so ung v{ji h~ thirc tren se ~ay ra stj hap thu cong huong hoac nguoc lai, Tren tbuc te nguci ta giu: ~o dinh v, thay doi cuong dQ tit t~bng H thuan ti~n' han. 'I'ai H = Ho ung vrri ceng thiic v = yH/2n'se xay ra su hap thu cong huang buc xa di~n tit va lam thay doi cuong dQ dong dien chay qua cuon day dan; su thay doi do duoc khuech dai va ghi lai tren mot ampe k€ tu

• r •

ghi thanh nhirng pic hap thu kha hep, goi Is phd ct}ng huang tlt hat

·~···i = -1/2 .

-----~,..,_---. z.

lz = +1/2

nhan,

Phd ducc sit dung nhiau nhat v4n IS. phd ceng huang tit proton, . do hydro co mat hau nhu trong moi chat hiru co, va dong theri

..

proton co dQ nhay dac bi~t vC1i phuong phap nay. Phd ceng hudng tit

proton cho ta nhirng thong tin co ban sau day:

- S6 tin hieu cho biet co baa nhieu kieu proton. khac nhau trong

..

phan ttt.

- Vi trf tin hieu cho biet nhirng thOng tin ve· "vong vay dien tit" baa quanh tn6i loai proton .

•

..

52

. ..

. .

- Cuong dQ tfn hieu clio biet s6 proton thuoc pl6i loai .

. - Su tach tin hieu thanh met so pic cho nhung thong tin ve cac proton. IAn .c~n khac bao q uanh proton nghien ciru. _

, Co ba yeu to co ban trong nghien ctiu phd cong huong' tj1. hat

nhan:

, .

- chuyen dich hoa hQC;

- tucng tac spin - spin;

- cac qua trlnh dQng.hQ~ (van t6c phan iing) ..

a. Szt chuyin dich. hoa h9C

TIt cong th uc tren, co the di den ket 1 uan 1ft moi hat nhan cua cung In9t dong vi, chang han proton, Iuon luon cho cung mot pic trong phd cQng huang tit hat nhan. Tuy nhien, VI cac hat nhan nguyen tu trong phan ttf bi cac di~n tit bao quanh, cac di~n tli nay do S\1 chuyen dQng cua chung cling ·t~o nen cac tu ·trtiCfng rieng nguoc chisu vdi huong cua tu trucng ben ngoai, chung gay nen hieu

.

ung chan lam giam me dung cua tit truong ben ngoai len proton,

con .goi Ia hieu iing .chan nghich tit .. Vi v~y tin hieu hap thu cong huong nang luong di~n til xu;it hien muon hen, a tu tntbng·H ben ngoai manh hon, duo bu lai hi~.u ung chan do. Moi kie'u proton trong

, I

phan tit co moi truong electron bao quanh khac nhau, do, do hi hieu

•

irng chan. khac nhau va cho pic hap thu voi cac gia tri khac nhau cua cuong dQ tit tttiClng H~

S\1 khac nhau cua cuong dQ tit truong lam xuat hi~n tin hi~u h~p

,

th\l cua cac hat nhan cung ~Qt dang (chang han proton), nhung

"_ trong moi truong khac nhau duoc goi Iii Slj chuydn dich hoa hoc.

Thucng nguci ta lay tin hieu ha:p thu cua proton trong tetrametyl

. _ ,

. .

silan Si(CH3)4 lam chuan de so sanh, vi chat nay co tin hit?u hap

thu cong huang manh va hep trong Iinh vue ma rit It proton ki~u

. . .

khac hap thu (hlnh 3- 10) t

•

53 .,

..

--_ .. --- . __ .- - ..... _--------_. __ . __ ._-......,...

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

811 dich chuydn h6a hQC co th~ bi~u .thj bang Hz (hec), so vdi tetrametyl sHan.:no s\1 di~h· chuyen nAy ty l~ thuan vOi tan 86 lam vi~c cua may quang phd, nghla Ia. vach nam a 100 Hz tlng vC1i tan 85 lam vi~c lit 60' MHz va se nam a :167 Hz. ling vai tan 86 cong tac 13. 100 MHz. Vi vay de thuan .tien cho viec so sanh tr] s6 cua s\i

..

chuy~n dich hda hoc, nguoi ta dung- don vi gQi Iii phan tri~u (ppm);

gia tr] nay thu ducc bang each chia d(l chuydn dich hoa hoc tinh

" .

theo Hz ,eho taD 1~6 lam vi~c cua may quang ph6~

I 100

I o

t 400

I 300

, 2DO

I

£lYOng !ich phon

c ac pic c9ng hU'dng ~

. t

. --------- " ---- ----------._-_"---_._. _ _,)

j~ J

2 pro Ion ~

___ - ~r __ -_ ..._ ~-j I _,....- .• ~H2

.,j~ j r V"

1 proton ~.

3 proton

I

I

j

I

I

I

I

f

8.0

6,0

4,0

. .

Hlnh 3 - 10. Ph6 cOng hlIdng tll hat nhin ella etanol

Vi d \1, trong tr1.tiYng hqp' tren ta co:

-

100 Hz 6

60.106 Hz' 10 ppm = 1,67 ppm

so VID Si(CH3)4' Nhu v$.y tb SiS lain vi~c lit 100 MHz thl dQ dich chuyg n ciing tuab.g tlJ:

167 Hz

---6-- 106 ppm = 1,67 ppm 100'.10 Hz

Dan vi' nay khong phu thuQc thn s6 quang phd nita.

54

"

•

-,

..

b. Tuong Me spin - spin.

. .

Nhu tren ta thay,- m5i tin hi~u CQng huong cUB. mot loai proton thuc t~ Iii Ill(lt nhom vach, do ke-t qua cUa tuong tao spin - spin.

~. .

Cac vach nay thuong' each d~u nhau va khoang each giita chung

khong phu thuoc vao tln s6 v cua biic xa va cuong dQ tit truong, d6 Ie. tuong tac spin' -. spin -b~ nh§:t. M6i vach nay con .co th~ ti~p tuc tach ra do ket qua cua tuong me spin .. spin ~c hai, S:-;t tach b~c hai nay phu thuoc v, khi tang v, no c6 khuynh huong' bi tri~t ti~~.

, Bangphuong phap dong 'vi, nguo! ta da chiing minh dU(fc rang,

,.

S\t tach spin - spin phat sinh do tuong tac tit etta mot nhom proton -

Day vai ·nh6m khac.:

Vi du.. trong hop chat kieu CH3-CH2-X, tin hi~u proton nh6m CHz tach thanh 4 pic do tuong tac spin - spin vdi proton nh6m CH3. Thay dan nguyen tu: H a nhom CH3 bang de uteri, c6 momen tit nho han rO ret, se lam: giant so pic trong nhom nay xueng 3, 2, 1

(hinh 3-11). . . . ~ .

..

...

X-CH _culf\·

2 rw-.2

..

..

•

Hlnh 3 - 11 ..

.

Trong truong hQP' X-CH2-CD3' tLl hi~u cOng huang eua nhdm

CH2 chi con mot vach, vi cac proton co dQ dich chuy~n hoa hcc nhu nhau, kheng' tach v~ch hip th\1 kh6i nhau. VI v~y d6i viii cac hqp

.

55

_ •• _ ••• _ - • - _ •• "." - II __ .. __ ._ .. ... - __ • .. • .... - ._ • __ •• - _. - - II .. ',' •• _ - --- - - --- -----. - - --- ---- -_ .. - ---- - -- •• _ - ---- '----'--. __ ,

chat chi chua mot kigu proton nhuHj, CH4, CZH6, va (CH3)4Si~ chi quan sat thiiy mot vach ccng huang (hlnh 3-11).

Gi:i tri dac trttng cua hang so tuong tac spin - spin cua mot so hop chat co cho trong bang 3- 4.

Bang 3 - 4. Gia tri ddc trung cua hang so tuong uic spin - spin coo mot s6' ho p chdt

;'

Manh h~p chat

+

j, Hz

j, Hz

........ /
H C=C-C~C •
-, C/o /' I I <, 10 .. 13
12 - 1S H H
/ 'H .
H . H
I /
'C / 1 - 3
=c 0,35 • 2 -y-y-
/ 'H
It H OR - ~CH-CH~ 2 .. 9 - jaa = 9 - 13
H
•
jac = 2 - 4
'C=e/ H· icc = 2~7 - 4
.
/ , 6 - 14
·H H . H . •
- 'C=C/
11 - 18 ~A JAB = 7 - 10
/ ,
H a-He jAC == 2 - 3
-H iAO < 1,5
-C-C=C-H r C
- 2-3 HO
1
H
...
'C/o HA JAB = 7,5 .. 8
'C=C/ " 4 - 10 HeOHe jAC = 1t4 - 2
H
/' "- ' .~
is c = 52 - 5,5 ... '
H ~N H
: C
, - . iCD = os
'C~ .
__ H:oHA JAB = 3 • 4
C=C / .
O.~ '. 2 jAC = ·0,6 - 1
/ . He: .
H , . ~. lao = 1~ - 2
- -

•

56

v

N6i chung, neu mot proton hoac met nhom proton tuong ducng tuong tac vai n proton· tuong duong kieu· khac thl tin hieu se tach thanh n+ 1 vach. Khoang each giira cac vach gin hha:t cua chum

~

vach IS. tuyet d6i bang nhau, de? Ian ella .khoang each nay, tinh bang

Hz, dtrcc gQi la hang so tuong tac spin - spin j . Nhom vach nay

,

luon sap xep d6i xirng vci tam di~m de lam rndc do chuyen dich hoa

hoc .

•

Khac voi su dich chuye'n hoa hoc, hang so tuong Me spin - spin j khong phu thuoc cuong de> ttl trucng ben ngoai Ho. Vi vay, bang. each do trong cac truong co cuong dq khac nhau, co th~ phan bi~t duoc cac chum vach 18. nhung tin hieu dQc lap do chuyeri dich hoa

.,

h9C hay lit chum vach do tucng me spin - spin.

Tuong tac spin - spin duoc lan truyen qua cac lien ket hoa hoc, vi v~y dai lucng j phu thuoc vao s6 li~n ket n6i gifta hai nhan tuong tac va vito ban chat cua chiing. Qua nei ba, tuong me spin - spin Ian truyen hiru hieu hen n6i d6i va qua noi d6i manh hen qua n6i don. ·Cae proton trans d n6i doi co j Ian hon proton cis. Tuong tac spin - spin axian - axian Ian hon axian - equatorian va equatoriati

• •

- equatorian.

3.3.1.6. Phuong phdp phd kho; luong

Vi~c dng dung phd kh6i Iuong de nghien cuu cac hop chit hfru co dua tren StJ, ban phs cac hQP chat nay bang chum electron cd nang :

. .

Iucng trung blnh, trong chan khong r()i· nghien ciiu cac phan tit va

cac manh tich di~n ducc tao thanh (ch 1.\ yeu IS. nghisn cdu cac

..

cation) cii~g r«t th6ng dung .

•

Khi hi bAn pha, phA.n ~u chA:t nghien cdu (0 thl. hoi) hoac bi ma:t

di~n tit _ngoli cung ho*c bi phi·va thAnh tttng manh. Cae ion duong du,",c tAng t6c ~" m.Ot .. bi~n tich ditn Alll, lQt qua khe hep va tb

• I • "I

tr\tb~g r , D~· ~ac .dung cda -t.lI ~ruCrng, cae ion nay. chu)4n dOng trOn

.' • I'. • • •• '. •

vbi. baD· kinh r ph 1}. th u~e vao kh6i' l1Jqrig m, d:ifn thl U eua trubng

, - , . _. ., . . .

. . ~ ~. .

gia t~c. va cubng dQ· ttt· tntbn, H cda nam cham:

...

, ..

07:

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

v

,

r =.

2n1.U «n

•

-

.--"

. ,

.. Vai U va H khong dcSi, thl r chi ph" thuoc V8.0 mle. Bang each

, .

thay d5i tu. truong' hay di~n tit truong; ta co the thay d6i ban kinh

qlly dao chuyen dOng cua cac ion va. huong vao khe cac ion cd k.h6.i lucng khac nhau,

Nguci ta co th~ xiy dung do thi v~ S\1 phu t huoc Day. Neu . ghi

dong ion ~ bia IS. ham s6· cua tht3"

f

t

~ "'guo;' electron

Ban lich .aien om

•

Namchdm

Mal; chat

toe, ta cd pho kh6i lucng trong

r • do the hieu

•

· la ~~i IUQng

do so kh di I \1c;1ng va dong ion Iii. d~i IUQng

do cttong dq cac ion khac nhau. Pho kh6i hrcng ciing CO ·th~ ghi

dt1Qc bang 'each gift nguyen U va H, cho cac ion co kh6i hrong khac nhau da dtCQc phan gi3.i d(5ng thC1i d~p len phim anh (khdi phd kY) .

89 phdn . fiep nhqn ion

Khe

h ie u

..

•

gla

...

, Hlnh 3 -- 12. Sd dO mAy khel pho

Cirong' dO cac ion dl1QC xac dinh qua di) den cua phim ..

Noi chung pho kh6i .luong du:gc ghi lai dudi dang phd vach hay bang, trong do cuong dO cac vach duoc do ·bang phan train so vdi dlnh co cttang dQ cao nhat (gQi 18. dinh co sO'). Dlnh ion phan til

•

•

58

•

thuong la dlnh cao nhat, tuong duong voi kh6i luong phan til cua hop chat khao sat.

j

Phd kh6i luong khong nhirng cho phep xac dinh chinh xac phan

ttl hrcng, ma can c~ vao cac manh phan ttl tao thanh, ta cung suy ra d11<;1C cau true cua phan ttc~ Xac suat tao thanh manh phu thuoc vao cuong dQ cac lien keto tuong ung trong . phan tit cling nhu

'.

vito kha nang ben hoa cac manh tao thanh nho cac hieu tlng khac

nhau. Cac manh co d¢ ben Ian se uu tien tao thanh, cac lien ket yeu nhat de hi ddt ~nhat. Co nhung manh co k.hoi IUQng dac trung gQi IS. "manh chla khoa" , chung cho phep phan tlch cac phd kh6i 111Qng de dang.

. '

So do nguyen if may kh6i phd xem (I hlnh 3-12.

3.~1.1.7. Phd nhiiu x~ ROentgen

Loai phd .nay dung de nghien cuu cau true cac hop chat co cau tao tinh the: Khi cho chum tia ROentgen doi qua tinh the thu duoc

. \ - .

anh nhi~u xa va cac eve dai llng v(ii cong thuc: 4-

nA. = 2d sin8

n - siS .nguy~n; A - bu6c s6ng;

d - khoang each giita cac m$t phang cua each tit; (J - gdc phan x,.

Do ~d6 nghil\n cuu anh nhieu x~· cho tao cac thOng tin v~ c(u true. tWJng 111lsi tinh th~· cua hqp chft nghiAn cttu,. dang: hinhhoc va C«u hlnh khOng gian ella phAn-tit, 'kh6ing cachgiua cac nguy&n tit

.

N ioli' nhi~u x, tiB Roentgen, trong m¢t s~ t.ntbng bQp~ ngulJl ta

con dilng ca nhi~u x,'eiection,nhiiu xa. neutrqn~!ch1ing ciing cho ta

. ..

nhung' thOng tin q uy bau'v~ c«u' trUe khOng. giBn cua 'phAn ttt 'va:

tlnh ·thi. .. \ -, : . . .,

59

•

•

--- ._-- - -- __ ----.--. • _. - - _- ._ _-- ,., --_._ -."-._-- _ ••••• __ ._-- , ._ _ - ------- - -- ._- -_ •• ----- -------_ __ .. _ • __ •• __ • -_II ._. __ •

'II

3.3.1.8. Phd c6ng hllung· thuan tit electron

Nguyen tac Ii thuyet cua loai phd nay cung gi6ng nhu phd c"ng huang tir hat nhan, chi khac d cho phd quye"t dinh bdi momen spin - cua electron chii khOng phai ella hat nhan va do do no dung de nghien cuu va phat hien cac hop chat chua cac ··electron khong C$p dOi co momen spin rieng, dtiesi tic dung cua tit tru~ng momen nay cfing dinh huang thea hai chieu: cung chieu va nguoc chieu vC1i ti:t truong ben ngoai. Khihap thu bite xa (vi song) chung cung chuydn tu- DlUC nang Iucng thap .sang DlUC nang lucng cao. Chi khi co

.. .

nhitng buc xa co nang IUQng dung vai nang luong can thiet do thl

moi xay ra 91:1 hap thu cong hudng nang hrong va nguoi ta ghi dU:Qc

.

. ·pho tuong iing, gQi IS. php cQng hucng thuan tit electron. Ph6 nay

. .

.: .cho phep ta nghien ctiu su cc D1~t va nong d<) electron Ie trong tnAu +

chat nhat dinh, thucng de nghien cuu chat ban dan,. chat mau, mOt

so chat cd hoat tinh sinh hoc .. t .-

.. ..

3.3.2. Nghie'n CLrU mOt s6 hing so vtt Iy quan trQng

. .

Dong thai. vci vi~c nghien cuu quang pho cac hQP chat hiru co,

vi~c xac dinh m<)t s6 hang s6 v~t Ij quan trong cung cho ta nhung thOng tin ve dQ tinh ls.hiet cua met chat, ve cA:u true nQi tai phan ttt cua 'chung, v~ nang 49 cua "chat nghien ctiu trong dung dich ..

3.3~2.1. Diem nong chd)' 'fiC

Di~m n6ng chay (hay' nhit?t dQ nong chay) IA hang so vat ly quan trong' giup ta nhan biet m¢t ch~t ran tinh khiet hoac d¢ tinh khiet

•

ella chat ran sau khi tinh ch~t ·Neu sau khi ket tinh Iai DlQt so lan, diem nong chay vAn kh6ng thay d6i thl ch.at do da tinh khiet. ~On

.

hop hai ch&;t khac nhau thuong co nhiet dQ nong chiy thap hon

tung chat rieng bi~t. Trong mQt day dong dang" nhiet dQ nong chay thuong tang dan theo phan ttl. hrong; trlt mQt so truong hQp d~c biet, chung tang theo hlnh rang cua, Phan ttt cang d6i xirng, dieDl

•

nong chay cang cao.

60

•

~1.J.2.2. Diem so; IJ

Diem sci Iii nhiet de) tai do tip suat hoi baa hoa cua chat long bang ap suat khi quyen.· Vi v~y dienl sci la hang s6 vat ly quan trong dac trung cho mot chat long tinh khiet. Trong nloi day dong d:ing, dignl soi cling tang dan thea phan tit luong. Su 'phan nhanh

.

mach cacbon thucng lam giarn di~m sci. Nguoc lai, neu trong phan

tit co nhirng nhom chuc ihnl tang luc lien ket gif1a cac phan tit (cac .nhorn phan C\1'C, d~c biet IS. cac nhdm tao lien kat hydro) se Ian} tang manh diem soi.

3.3.2.3. Tjt kho i d

TY kh6i cua mot chat long 18. ty s6 kh6i luong cua no va kh6i IUQng cua nuac cat vci cung the tich, S\1 so sanh nay co the d cimg nhiet dO hoac nhiet dQ khac nhau, Nguci ta thuong so sanh voi khei I ucng cua nude a nhiet dt). 40 13 nhiet dQ CJ do' nuoc co ty kh6i Ian nhat (1 g/ml), Vi du, d~() cua chatA co nghla IA kh6i luong cua chat A do 0' nhiet dQ 20()C so vdi kh6i luong cua cung the tich nude CI 4°C.

Nguol ta nhan thay rang, cac chat chua oxy co ty kh6i cao han hydrocacbon goe; hydrocacbon thorn co ty kh6i cao hen hydrocacbon

, '

khong vong co cung s6 nguyen tit cacbon trong phan ttl.

3.3.2.4~' Chi so khuc xa n

•

Chi 56 khuc xa etta met chat long 13. ty so giua tqc dQ anh sang di trong chan khong va trong chat long do t Chi so khuc xa duoc do nho khuc xa ke, thucng do CJ nhiet d9 xac dinh. Khi tang nhiet dq, chi s6 khuc xa gianI, dong thbi chi s6 khuc xa cung phu thuoc ca buoc song anh sang don sac duoc dung, Vi v~y, ta phai ghi ra chi so khuc xa do f:J nhiet dQ nao, vdi anh sang co bUQC song nao.

VI du, axeton co nbo = 1,3591, tuc IA chi so khuc xa cua axeton do CJ 20(}C, voi anh sang vang ella natri (vach D).

~

Chi s6 khuc xa cung IS. hang s6 dac trung cho- mot chat long tinh khiet.

61

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

-' .----_ .. - - . --- _ ...... - . '--" - ._. _ ..... _. .._. -- - -- - - .... _ ... _- . __ .. _ .. -_._ .. _--- .. - --- -- ...... . - ..... _. _... . - .- ... --_ .. _ .. - _._. ::. _ .... _-- .. __ ... _- . "

..

•

DQ khuc xa phan ~it, R diroc tinh theo ceng thuc:

...

M n2 - '1 R=-

d · n2 + I

~ , ,

vdi M Ia khoi lucng 'pha .. n tit chat nghien cuu, d Ia ty kh6i cua chat

. .......... . .

do, n la chi 86 khuc xa cua no.

..

DQ khuc xa phan tit 18. hang so v~t Ii d~c trung cho tn5i chat tinh khiet. D~ng thai R cung co "cong' tfnh" , nghla lit co' the, tinh t~n CO sa tong cac dQ khuc xa nguyen tu. Khi do s\i khac nhau gifta If thuyet va thuc nghiem cho ta nhirng thong tin v~ d~c -trung lien ket giira cac nguyen'tU: trong phan tU: va th(( t\t lien ,k~t gifra chung.

3.3.2.6. Parachor P , Parachor cung lit hang 96 ·cqng tinh, ducc tinh theo cong thtic:

. to

·M.'

P 1~'

= -----~y

d long -' .dhdi

.

Trang do y 11 SUc cang be mat cua chat long. N~u bor qua kh6i

IttQng riAng ella hoi ta co; . "

•

M

p ::::;: . 1'1/4

d long

3.3.2~7.' Momen luimg cue J.l

, '

Lien k~t hda hQC gi\ta hai nguyen tu co d9 am di~n khac nhau bi

•• I •

phan cue. VI v~y, phan tit cae chat chua lisn .. ket phan cue nay va

khong doi xirng nhau sa cd momen luang cue:

p = e.l

I~

I

trong do e lit di~n tich, l 18. khoang each giua hai ,trQng tam di~n

tich dirong va Am. Don vi do momen htoug' cue 18 Debye; '1 D = i d.v.t.d. (dan ~ tinh« dien)')(~cm.iO~.L8~

... .. " .

. . - ..

62

•

•

v

r

Momen IUClng cue co th~ tinh tu hang so di~n mei e theo cong thuc:

•

2

E - 1 M 4 f..l

e + 2 x d =. 3 .n:N l (a + 3kT)

N L - hang s6 Lodshmidt;

E - dQ kha phan cue;

k .. hang 56 Boltzmann; T - nhiet do Kelvin.

, .

..

M01l1en luang cue cua nhieu hQP chat de bay hoi co the xac dinh dua vao quang ph6 quay (pho . vi song) cua chung duai tac dung

s

s

..

. Htnh 3 - 13.

cu a dien t r uo n g ben n goa i. 41 Phuong phap nay thuong cho ket qua chlnh xac cao hon phuong phap hang so di-?D mef E.

Dua vao tr] s6 cua momen luang C\1C, ta co th~ hlnh dung cau true khong gian cua phan tit, goc lien ket, tinh doi xung .. ~ Vi du, hQP chat (hinh 3- 13) co ~ =' 1,5D, chung to phan til khong nam trAn cung mOt m*t phAng, Dl8 g4p thea true S· S· nhu trangsach rod nita chirng.

3.3.2.8. fJp quay c~c rieng [a]

Cae hqp ·ch«t hilu cc chda nguyAn tit cacbon bit d6i xirng thuong co hoat tlnh Quang hQC, chung quay ml).t ph!ng phAn cue eua anh sang di mOt goe at GcSc quay a ph\1 thuQc VBO bin ch«t ch«t nghlAn cdu, vlo n~ng ·dQ (hay tY kh6i nfu IS. chAt ·nguyAn ch(t), nhi~t dO ,va b~ dly cUs. lCrp ch«t nghiAn -cllu mil. 'nh sing phAn c\tc truyln qua.

. .

_ Ngubi ta-diJih nghla dO.quay c\fc ri~ng C1ia Dl(Jt ch't 1& gdc quay __

a cua 4nh sang dOli sAC· (thubng dung. v,ch vang D cUt phdlnat~·'·oo A ,-:i= 5898 A) di - qua --lltp dung dlch b' day' i dm, n~ng dO 1 glml._

+

63

•

\

--- ---------_._---- -_. ----_. __ .. _._-- .. _------ --- -_ .. _- _._._---- .-- - ------ _._---_ ... _---_. _._-_._--_._----------

v

hoac

•

(l.100 [a]5° ~ --l.e

20 . a.IOO' (a]o =-l.d

•

d6i vai dung dich

d6i voi chat tinh khiet

trong do c la nang dQ do bang gam chat hoa tan trang·100 ml dung dich, -

•

-

Nhu v~y dO quay cue rieng trd nen hang so d~c trung cho met chat,

. ~

khOng phu thuoc nong dQ ella no nua. Tuy nhien, 'trong truong hop

dung dich, ~dQ quay cue co the phu thuoc cit vao ban chat dung mol, vi vay nguoi ta chu thich cl dung moi duoc dung. Vi du d- campho co:

[a]~O = +44,26° (etanol, c = 10)

..

D<> quay cue rieng khong nhtrng giup ta .nhan biet mot ch·a:t quang hoat, rna con cho phep ta xac dinh ca nong dQ cua chat quang hoat co dQ quay C\!C on dinh, VI du dl1dng k€ cho phep xac dinh no'ng dQ d1.1C1ng dua vao gee quay a .

....

. 3.3.2~9. Cdc hling so khtic

N goai cac hang s6 v~t 1i va hoa hoc quan trong noi tren, nguo! ta con xac dinh hang loat cac hang s6 khac nhu nhiet dot chay, _ d(> tit cam, hang s6 sac ky va di~n di. ~ ~ VI d \1, bang each do dO tit cam cua hop chat co can bang tautome xeto- enol, ngttm. ta xac dinh duoc nang dO m6i dang tai vi tri can bang. Phuong ph:ip nguyen ta, danh

~

diu cling giup chung ta xac l~p duoc vi trl nhom chile trong mach

v~ cc ch€ phan ttng~

3.3.3 .. Ca.c, phtlang phap h6a h9C xae dinh ciu true

•

Trong phan tren ta da nghien ciiu cac phuong phap hoa hoc xac

dinh thanh phan phan ttl cua cac chat hiru co (dinh tinh va dinh luong cac nguyen.t'O' hoa hoc cotrong thanh phan cac hop chat).

64

, .~

Phuong phap hoa hoc cung dong gop met phan trong viec xac

dinh ca:u true phan tit nhir: ~

- Xac dinh su co mat cua cac nhom clnic trong phan t\i chat

.

nghien cuu. ~

,

- Phan tich dinh Iucng nh6m chuc nham xac dinh so nh6m. chuc trong mot phan .ttl: hay nong dQ cua chat nghien ciiu trong mOt dung dich, doi khi xac dinh duoc c8: phan tu luong ·eua chung nhc dinh IUQng nh6m. chirc tieu bi~u ella chat ,dOt

- Phan giai chat da cho thanh cac hop phan, xac dinh cau true

. .

tung hop phan de _tu do xacdinh ca:u true phan t~ ·to~n b¢, chang

han th uy phan este t

- N~u <lieu ki~n cho phep, ngttoi ta tien ·hanh, nt6ng· hop g~p ga", chap noi cac bQ phan da biet bang con duong rieng dG ·co phan tu

.

da cho ma ta con nghi ngo c6hg~thuc cau tao cua no. Neu chung. c~

hang so v~t Ii va tlnh chat gi6ng nhau, chirng to"\cOng t,hllc ducc gia

. . _

dinh Iii hoan toan dung dan~

N ghien ciiu chi tiet cac phuong phap phan tlch hoa hoc duoc trlnh .bay a cac sach chuyen em ve phan tich htru .co. Phuong phap ttSng hop va chuy~n hoa cua cac cha:t huu co se. duoc m.inh hoa _f!

phan chiic. ~

..

~ _

Nhln chung, phuong phap hoa hoc ngay cang nhuong' bucc cho

cac phuong phap v~t Iy hien d~i~ Tuy nhien, trong mOt. s6 truong hop, phuong phap .hoa hoc khong the· thieu duoc d~ gop phan xac

. , _

l~p cong thirc dung dan cua chit· nghien ciru.

..

. .

•

65

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

. .

Chuang IV

.

. Axit • bazG vi dung BIoi

4.1 AXIT - BAZO

•

T'rudc kia nguoi ta thuo n g dung khai n iem axit- baz o cua

Arhenius. Theo Arhenius, axit la nhirng chat khi 'tan trong mrcc cho ion H+,~con bazo la nhirng chat khi tan trong nude cho anion OH- .. ' Quan diem nay giai thlch dude nhieu phan t1ng tien hanh trong moi t ruong nude .. Nhung dan dan sau nay nguoi ta tim ra nhfeu

. .

axit- bazo khac nhau, trong do co nhirng axit- bazo khong cho ion H+ va OH- ~ Vi vay, nguoi ta da phat trien va tong quat hoa hen nira. Sau day, chung ta Ian lUQt xet m9t s6 khai niem ve axit- bazo thuong hay dung trong hoa h9C hiru ca.

4. 1. 1. Thuyefaxit - baza cua Bronsted

Thea Bronsted, axit la nhimg chat co kha nang cho . proton con bazo 13. nh irng chat c6 khlL nang kat hop vdi proton. Axit thea Bronsted g(}m. ba loai:

Axit 1a nhirng phan tit trung hoa:

He} :. H+ + CI-

H2SO 4 ~.., H+ + HS04"

L

CH3COOH -----3lI-)o H+ + CH3COO-

C6HSOH 'CH3N02

Axit 18. cac anion:

H~ + C6HsO-

01'

H+ + [CH2N02J-

~-)o H+ + COi2 · .., H+ +8042

66

, • r _. ••

- \

Axit 18. cae cation:

. CH3

+ /

~~ H .+ N-CH

" 3 C~

. ,

Al(H20}l~~

H+ + [Al(H 0) om+2 2 5

..

C2H5

. 'O+-H /

CZH5

. Nhung anion Cl ", HS04" , CH3COO-, C6HsO- ... cling nhu cac cation- [Al(H20)sOH]+2, phan tit trung hoa (CH3)3N dUQc 140. ra do slj. tach H+ cia axit ducc gqi 11 bazo li~n hop,

..~ 4

Tuong tu nhu v~y, bazo thea Bronsted c6 ba Ioai:

..

Bazo lit cac phan til trung hoa:

..

NH3+H+ ~·NH:

C6HSNH2 + H+ .----~ C6HsNHj

..

Baza Ii cac anion:

OH-+ H+

CH30- +.H+ Baza 11 cac cation: ~

NH2-NH; + H+

•

~~ H20 _.~ CH30H

Nhirng cation NHt, C6HSNH; ... hay phan t~ trung boe H2v, CH30H... du«;,c tao .r"a do bazo kit hQp vai ion H+ duoc gQi i.a axit lien hQP~

. ,

Nhtt vty ta co th~ nol, phan ung giua axit va bazo thuc chat .

. .

+

.... __ ._

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

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

v

,

.)

S\1 chuydn proton ttl axit sang bazo. Vi d1J.: ' .

..

H 0+ + OH- ... H2O . + H2O
"E
3
II
H2O + H- 4! OH- + H'

2
H2SO4 H2O ) HSO- H 0+
+ +
€ .
4 3
HeaOH + HCO- ) HCOO- H2C03
+
<
3 -
H2O + H 0- .., OH- + H~O+
E II
2 _)
,
axit + bazo ,.. bazo lien hQP + axit lien hop

~ Qua day ta thay, nude cling nhu nhieu chat khac co chua nhom hydroxyl, tuy thea chat tac dung vdi no ma the hien tinh axit hay bazo.

Thea Bronsted, nhiing axit rat manh phai c6 nhirng bazo lien

. '. .

hQP rat yeu va nguoc lai, nhfrng bazo rat manh phai co nhirng axit

~

lien hop rat y~u:

4.1.1.1. Phuong phdp xac 'dinh luc axii-baza

Muon xac dinh luc axit- bazo ngl1C1i ta thuong lay mroc lam tieu

• •

. ~

chuan so sanh.

a .. D6i uoi axit

Hang so can bang bieu thi hoi phuong trlnh:

HA + H20 -E ,. H30+ + A-

[A -] ,[H30+]

Ka = -------

[RA]

trong d6 ta xem nong dt)cua n1.tdc thuc te khong dcfi va bang 55,5

•

mol/l nen be qua. ·

D~t: -lg Ka = pKa

" Nl§'u pKa cua chat cang nho thl tfnh axit c~a no cang manh, IlgliQc lai pKa ,cang !bn thl t£n~ axit cang y€u (bang 4-1).

...

~ .

68

Bang 4-1. TTl so gall dung pK a cua mQt SO axil a proton

,
Ten 90i Cong thCic - Lien k6t ion h6a pKa
Metan CH3-H C-H 58
.
Toruen·· C6H5-CH2~H n 37
Phenylaxetylen C H -C~·C-H 21
fj !5 . :
Axetyfaxeton (CH3CO)2CH-H H 9
Amoniac NH --H N-H 36
2
Anilin C H -NH-H I~ 27
6 5
Cation pyridin CsHsN+ -H ~I 5,17
,
Cation anilin CSH5N+H2-H II 4j58
• CH3-0-H O-H
Metanal 16
,
Phenol CSH50H .. 9,95
Axit axetic CHaCOOH II 4~75
Axit tritlcaxetic FgG-COOH !I ~ -0,25
Axit nitric ' HN03 u -1,37
I" . ~

h. DO. i rtf; baza

Hang ~6 can bang bazo duoc bieu thi nhu sau:

NH3 + HOH • ~ NH: + OH-

[NH;l.[OH']

Kb = -----

[NH3)

D~t -lg s; = pK"

Tucng tu nhu tren pKb cang nh6 thl tinh bazo cang Ian va ngucc lai, pKb eang Ion, tfnh bazo cang, yeu.

c. SI! ·lien It; giiia KQ va Kb ~

VCli n·~(fc cO hang ~ can bAng nhu sau:

'+ It ..... -

~'= [H30+).(OH"] =

, a ' , 1~20]

• ""oJ"

_._. _. -- -_._---_. -- _. -------- -- . _._--- ._ .. _- ----_.- ------ .. _- ---_.- - _. _. - -_ .. - -- --_.- .. _ .. __ . __ ._ .. _- . -- -- -- - .- ----_.- ._- ._-- _ ..... _._-_._- _ ... _-- -- ._._-_._ .. __ ....

•

V~y tich nong' dO:

[H30+].[OH-) = K = Ka[H20] = 1,8.10-16, 55)5 = 1.10-14

~

V,y K =[H30+].[OH-] = 10-14

D~t -lgK = pK = 14

Bay giil ta xet den mOt cap axit- bazo lien hop:

..

H 0+ + A- 3

HA

+ H20 o(;to

, [H30+] . [A-]

Ka = -----

[HA]

....

A~ +. H 0 2

__...,. HA

[HA]~[OH-] [A]

.........

..

Vfj.y Ka.Kb = [H30+].[OH-] -= K = 10-14

Qua day ta tha:y, deb hang so Ka.Kb cua in<)t cap axit- bazo lien hop nao day luon luon bang 10-14, V~y ml)t axit cang manh thl'baz(J

cua no cang yeu- Vi du, mot axit co Ka = JO·s thl bazo lien hQP cita no c6 Kb = 10-1'4: 10-5 ;:: 10-9

pKa = 5, pKb= 9

. .

Bang 4-2. Gia tri pKa' pK b ella mOl so axit-bazo lien no p a zo«:

•

. -
.. Axit Bazo ~1i8n h"P. pKa - pKb
H 0+ H2O . -\1 15t6
3 ..
-
HOOC-COOH HOOC-COO- .. . 1,2 12,8
HCOOH . HCOO- 4.2' 9,8
.
.. t
CH3COOH CH3COO~ . 4,75 9,25
NH + NHa 9,5 4,5
4 -
CHS-NH3 + CHa-NH2 10,8 3,2
(CHa)2N1-12 + (CHa)2Nf( 10,9 3,1
. . ~ .. •
H2O OH- 15,5 -1t9
• ."!::.. 70

•

. '.. ..

I ,

J.- _. •• .... • •

1 •• .. •

- .,

.. .. .. .

•• • -. I II

r ! -

r

" -

.

, , '

- '

..

~' r;: '-

+ 1 I.. ••• 1 •• • _

Nhu tr~n ta th«y, chlnh H20 co thl 11 axit hoac bazo nsn trong

dung dich nltl1c trj 86 pKa rft kho xaic dinh; 'th~lstlg ngttlJi ta phAi

,

xac dinh trong dung mOi kheng phan c\tc nhu bezen, hexan ...

..., '

. Tr,ng thai can blng trong cac trubng hQp trlnh bay d trAn ph\l thuQc vic d¢ ,b~n tuong d61 ella nh6'ng- phlrit~cua~;ci hai vg

phuong trlnh: ' , .. ~-

!IF = -R11nK~ veri axit phan ly" trong 'ri116c:

. ..

.

M = 2,30S-RTpK

•

.

- - AF- S1I thay ddi nAng IUQng khi chuydn ttt h(1p ch«t ban-dlu

.

dA'n ch«t cudi gQi IS. s\t bi~n thiAn 'nang 111(Jng t\t do;

. '

K - hAng 96 can bang;

, ,

T· tl.hi~t dO tuyft d6i;<

, '

R -~ bAng '86 khf,-

• 1 • 1 ..

4.1.1.~. NO~g d6 Iw(lt dpng va,.~ sII ho(Jt 46

•

Nhu chung ta da bi~t, trl1C1ng hc;Jp khl It t-ttong' hay - dung djch-1j

tUCJng ngUai ta thubng dung khai n_i~m' nbng ,ao; cOn trong ~'ung

, ,

dlch th\tc hay khf thuc thl moi phut1ng trinh- me' ti tr,ng thai cAn

-, '_ - ,,. .

bAng _ ctia dung dich ly t\i~ng hay kh{ ly ttld!1g d)u .co th~ ap dvng

- . ,

cho dung dich thuc, miin 11 thay~ khai tii~tn nbng' d~' bang .. 'n~ng "dt). I

hilu hil)u, con g9i 18 .n~l1g ct~ hOlJ..t: dQng hay lio(lt dQ.

_ -

If'

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

Nhu v*y giua dung dich th\tc va 1y' t~Cfng' cd ml)t, sv khac bi~t.

, -

nt1 d~c trung cho S\t khac ,bi~t do, nguCli ta dung h~ 86 host dQ:

..

...

• I ••

.

1 .r r

_. :.. .

a·

fi = ....,__l --

nang dO

, .

. -,

..

...

-. ... 1

. -.... .

, ai~ hO$.tdO·, " . '

. .. . I"

.. - • • • I·

Nong d(» cd thl bilu di~n bal'ig s6 mol/I ~!y phan tu phan Nj,

, .I'

71

.

t

..

- ._-- ---- •• _-_. _ ......... __ •• _- -- _ .... _- ••• -. __ .... - ••• - - •• _-- -_ ... - •••••• ,' .-._ --- • __ .... _ ••• __ ••• __ .- ....... -_. I - .,,.," - ._- •••• --------- ••• ------ •• - .... _ •• _-- _. --_._ •••••

. . ,

.

v

..

nan ta cfing co cac h~ s6 hoat d¢ t. tuong ling:

:nl.j - nang de) bieu thi bang so mol;

Nj - .nongd¢ bieu thi bang phan tit phan;

Cj - nang de) bieu thi bang 86 mol/I ..

Thong thuong nguoi ta dung nang dQ mol/l, ky hi~u Cj. V~y qua do ta co' the dinh nghla:

. .

·'.Ho~t, dQ .cua mot phan tit· hay ion i,:nao dd 13. tich giua nong dQ

. .'

cua phan ttl hay ion dd vci h~ s6 hoat ,de.? Ii :

c. = F.C·

f Ii]

. .

.Ap dung khai niern hoat dQ vao viec tinh hang s6 can bang Ka

nguoi ta thay rang, cac hang s6 xac dinh dua vao nong dQ chi thuan 19i .. ' cho qua trlnh dinh tinh, khi muon dinh luong phai dung kp.a~

, ,

. rt.i~~ hoa t d9 va khi do ta se nhan duoc cac hang 96 can. bang khong

. .

ph'\, thuoc via dung moi.

. ···'<_'·Vf du co mot axit HA~

, . .

1- _ I •

.... ..

, .'

..

, .

'HA

H+

)

I.. I ~

., tht-hang s6 nhiet dQng proton hoa:

al·{+·aA-

. K _. -

.: - .....

a

~ ~H.i~

+ '_

[H ] .fH+·[A l.fA-

-

-

[HAJ.fHA

[H:T-] · [A-I. fH+.fA- · . [HA]~fHA

... ·p6i vdi cac dung dich vO cung loang, h~ so hoat dQ t. = 1 ·.~.1.1.3. Ham asit ho va Ho '.

'Cac hang so phan ly J(a chi ap dung thu~n l<;Ji de do dQ axit trong . cac dung dich loang con vai cac axit d~tn d~c, vi~c ap dung cac hang ·s/fKa d€ tinh luc axit gap nhieu kho khan, do d6 Hammet va Dsrop

72

" 1#0

da dua ra khai niem ve ham nhiet dQng gan dung Ho goi Iii ham axit. Vi du, co mot axit BH+ rna bazo li~n hop cua no trung hoa va " dien:

•

.. ....

tit do ta co:

h() - dq axit.

Dat H == -J.gh ta co:

- 0 0, """

- . "

[B] (+ fS.fH+)

Ho = -lg ho ~ pKa + 19 + =-lg [H ] .

, [BH ] fSH+

- ~

Trang cac dung dich vo cung loang nhu nude, fBlfsH= 1, khi d6 ,

H; == -lg[H+] == pH.

'. Vi v~y ham Ho dung thuan 19i d6i vcsi cacaxit c6 nhngdQ khac nhau. Trong thuc te, da sO cac phan ung xt1c tac hfru co c6 luc XUC tac ty l~ vm ham nhiet 4Qng Ho'

... ,

4.1.1 .. 4. Cdc loai dung ma;

Can cU vao cac tinh chat d~c trung cua cac dung moi trong cac

,

qua trinh tucng tac axit - bazo, nguei ta chia dung moi ra lam hai

loai:

•

a .. Dung moi aproton

.,

Dung moi aproton IS. cac dung moi tro ve" h6a hoc, khong co kha nang cho hoac nhan proton _ nhu benzen, toluen, hexan v~v.~ .. Cac . dung moi loai nay khong co kha nang ion hoa, khong tham gia vao cac qua trlnh tuong tac axit- bazo.

73

...

"~

v

....

b .. Du ng moi proton.

Dung moi proton la cac dung moi co kha nang cho hay nnan proton. Loai nay Iai chia ra:

- Dung moi amphi proton .la cac dung moi vira c6 kha nang cho vita co kha nang nhan proton, nghia Iii d6i voi bazo no dong vai tro axit, va ngubc lai, d6i vdi axit no dong vai tro bazo nhu alcol, xeton, nitryl v.v ...

- Dung moi protogen 18. cac dung moi co kha nang tach proton la chit yeu nhu H2S04, HX~ CH3COOH .H

- Dung moi protophyl IS. cac dung moi co kha nang nhan proton 13. chu yeu, nhu cac amin, pyridin ...

4.1.1.5. SI! anh huung cria cdc }'eu to ben ngoiii den luc axit .. bazo

."

a. Anh huang cua dung moi

Luc axit - bazo cua 1110t chat phu thuoc rat nhieu vao dung moi, C\1 the chung phu thuoc vao:

- Ban chat cua dung moi

Vi du, cimg mot chat nao do nhung trong cac dung moi khac nhau co the ion hoa nhu mqt axit hoac met bazo nhu anilin trong nuoc dong vai tro mQt bazo:

con trong amoniac lai dong vai tro axit:

- . ~

C6HSNH2 + NH3 + C6Hs-NH- + NH;

» Ban chat S\1 phu thuoc nay 13. do 8.i luc cua dung moi vai proton khac nhau.

...

- Phu thuoc vao hang so di~n moi cua dung moi

S\1 phu thuoc giua axit - bazo vao hang so dien moi cua dung

-

moi kh6ng dong nhat doi vci cac loai axit - bazc. VI du, voi cac axit

_ ._ •• .-' __ • ._ 'I,orr--''''.. • ...

. _..

( _

..

. la phan ttc trung hoa hay anion, khi tac dung vai dung moi S se tao

..

ra cac ion trai dau:

A + S A- + S A2-. + S

):

Do do neu hang 86 di~n moi cua dung xnoi tang se lam. glam luc

•

tuong tac giua cac ion va can bang chuyan sang phai ..

.

VlJi cac axit IS. cation nhu:

,

thi hang so di~n moi cua dung moi khong anh h1.idng ti1i luc axit -

. .

bazo, tllc IA khong dich chuyen can bang.

Rieng vai cac axit 13. cation loai A2+, A3+:

A2+ +. S ~ B+ · + SH+

. . .

thl hang so di~n mol cua dung moi tang se lam can bang chuyen

.. .

.

dich ve ben 'trai va cac axit loai nay khi ion hoa cho cac ion cung

da:u.

Ngoai ra, dung moi con anh huang- den,hJc axit - bazc do Itjc ion 'thay d6i.

b . .rinh huang eua nhiet dg - ,

. ..

'I'uong tv nh u cac qua trlnh can bang khac, S\f phan ly cac axit

cling phu thuQc· vao nhi~·t dQ nhung anh huang nay khOng iOn lam .

.

Vi du, axit .axetic trong hon hcp nuoc va glyxerin khi nhi~t dO .thay

ddi khoitng 90°C thl tri sd pKb chi thay d~i 0,14 -dcJn ~.

4.1.2. Thuy't. axit-baza. eua Uxanovit

Theo thuyet nay, axit khong nhirng chi gOlll· nhftng ch1lt chtra _

. '

proton rna gem ca cac chA:t khong chua proton. Thea ling, tat ca cac

phan ung hoa hoc tao thanh mu6i d~u IS. phan t1:ng axit va bazo.

75

•

•

VI du, xet mot so phan ung sau:

+

R:;NH + 1-

+

R,NH + r~ I

CH3

R-NH, + II ~

CH3

Trang ba phan ling nay ta thay ~ chi c6· phan ling (1) ch iia HI 13 mot axit thea Bronsted, con d phan ung (2) va (3), CH31 18. nhimg chat khong chua proton nhung van tao muoi, do do Uxanovit cho rang, CH31 Iii mot axit va eng da dua ra khai niem: axit Iii nhirng . chat co kha nang tach cation trong do co proton. 'I'iep do Uxanovit

•

lai me rong khai niern do va cho rang, axit lit cac chat co kha nang

cong anion trong dd co di~n tU. Vi du, phan ung giira:

Na20 + SiGz .. 2Na+ + SiO~-

R:;N + HI R2NH + CH31

(1) (2)

trong do SiO) Iii axit.

-

hay: 2Na + Clz

trong dd clo 18. axil con natri 18. bazc.

4.1.3. Thuyet axlt-bazc cua Lewis '

Lewis cho rang, neu chi gioi han dinh nghia axit lit cac hQP chat chua hydro thi se khong hieu ducc sau sac cac hien tuong hoa hoc. Vi vay Lewis dA dua ra mot khai niem moi tong quat hon ve

axit- hazel dua vao cau tao electron cua chung.

4.1.3.1. Axil lheo Lewis

Axit iii nhirng chat trong d6 co the l;l ion, nguyen til hay phan tit

co kha nang ket hop voi.d5i dien til: t\1 do cua bazo.

Cac axit theo Lewis co: a) Proton

VI du:

•

76

..

H+ + :NH3

H+ 7f- CH2=CH2

b) Cdc cation

- Phan tlng gifta Li" va metanol:

Li+ + CH3-0-H ...

.-..-.jo NHt

..

----> CH3- +qHz

CH':'O+ -H

- . I

Li

..

- ;phan ung gitra Ag+ va NH3:

,- Ag+' + 21m3 io (H3N:Ag:NH3]+ ·

- - Phan t1ng hydrat hoa ion Al3+:

H H \ / ..

0'

••

..

,. .

H

.\

H-O:

H H '\/ .0 .

•

3+

AI'

,H / :O-H

...

Tfnh axit cua cac cation tang khi: · ·

. .

- di~n tlch duong cua cation tang: Fe+2< Fe+3

. .

- di~n tlch h~t nhAn cua cation tang: Li+ < Be+2 < B+,3

- ban kfnh ion giAm: K+<Na+<Li+ .

•

- . s6 lap electron eua cation giam ~

·C&c lien k~t baa quanh cation tren khong phai IS. li~n ktt cQng

'I • .. •

. hoa tri m.a da s6 13. lien k~t ion- ion, ion- luang. eve. Cac nhom baa

- . .

quanh cac cation dllQC goi ·li ligan. ' ·

. .

D~ bi~t co mQt cation dUQc coi 13. axit Lewis manh, cation nay

. .

thuong tham. gia vao giai doan trung gian cua cac phan t1ng huu co '

nhu:

+

):

•

H

N02

cation nitroni

benzen

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

-- .. _ .. _ _. _._- _ . ..,.. _._ .. __ _. _ .. _ .. _._- -.- - _ _-_ --_ .

+ x'

X H

R - C+ + . II

o

H:

/ ..

. ~C=O + I

R

•

C) Cac hop chat co nguyen. 'tit trung tam cung chua day dil, con chua qiiy doo tr6ng.

Vi du nhu BF 3' AlC13, ...

co Zap di~n tit. ngoai

+

.

Cac hop chat nay co kha nang tac dung vai d6i di~n tit ella bazo

d~ tao ra lap di~n 'tit ngoai cung du 8:

F -F-~ . -
<, J
F-B + F- ~ F~B-F

F/ I
F +

Aicr;

. -4

Truong hop nay tlnh axit .. tang khi:

_ di~n tich cua hat nhan nguyen til trung tam tang (ap dung cho

, .

cac nguyen t6 cung nIi61l1). ,

- dQ am dien ciia cac nguyen t11 . lien k~t voi nguyen' tit trung tam

, ,

tang.

- ban kinh nguyen tit trung tAD1 giam. '

"'

- so lop di~n tit xung quanh nguyen tit trung tam giam. d) Cae nguyen t6 co 6 di~n tit d lop ngoai cung

,

Vi du nhu oxy, hru huynh; eac nguyen to nay co the tuong tac

...

vai bazo de tao ra ldp ngoai citng dti 8 electron ~

••

~> :O:NR3

...

oxyt amin

78

, .

. ~ . - ..

. e) Cac hop chat co, n6i kip -b~ phan. cue

• L

Nhftng hQP chat huu CO chua noi kep bi phan cue de dang tac

. .

dung vai anion (bazo) cho hQP chat mci. ~

o /I.

R-C

-,

H

. ..

'bt. ~-

RCH ~o + CN-

0-

. r

~,. R-C-CN I . '

H'

f) Cae hop cluit ma lop dieti tri ngoai citng eua nguyen tit trung tam. co th'! mo rqng

Vi du, truong hQP nguyen ttl _silic co q uy dao d con· trong co th~

, L

rna rQng lap di~n t11, vi v~y c6 thi xem nhu m<}t axit Lewis

#'
F F, jF 2-
-,
F-Si-F + 2F- ~ F-Si-F

./ / -,
F F F .

Theo Lewis, axit n6i chung co the chia lam hai loai: axit thu

nhat va axit thti hai,

) .

Axit thd nhat la .axit tic dung vm bazo khong can nang 1 ucng

hoat hoa, Axit tht't hai IS. nhiing chat tuong t1;t nhu axit nhung do cau tao cua no kheng the nhan dOi di~n tit cua bazo, Cac axit. loai nay sa dl ket hQP diroc vm bazo 18. do hi~n tuong' nhi~u loan. Vi du:

.

r"'" R-CH = 0

-----,. R - CH - 0-

I

eN

4.1.3.2. Baza theo Lewis

. .

Bazo IS. nh ftng anion hay phan tu, ke cA olefin hay hydrocacbon

thorn co kha nang cho dOi di~n tu khong chia cua mlnh.

Trang cac phan ung giua axit va bazc n6i tren ta thay, axit di vao cho nhieu di~n tii: cua bazo nen goi la, tac nhan electrophyl. Nguoc lai, bazo di vao cho tr6ng electron eua axit nen goi la me nhan nucleophyl.

79

•

. .. __ .. . . . - . - . .. .... - ._.... ... .. - ... - .. _.- .. _ .... _ ... _.- _ ... - _. _... ... .. ... ... .

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

Tuy v~y, 'thu:yet Lewis con nhtroc di~rn lit khong giai thich dttgc · cac axit loai hydroaxit. N~J.1 van dung thea khai niem cua Lewis th! trong phan ttng:

..

CI-H + :NH3

CI:H:NH3

j' ,

•

-

nguyen ttl hydro phai co h6a tri hai, dieu dd mau thuan vcii If

thuyet cau tao chat.

4.1.4. Cae khai niem khac ve axit - baza

..

...

Khi cac ket qua ve thuc nghiem va Ii thuyet ngay cang nhisu, cac gia thuy~t tren khong giai thich dUQc that hoan hao, do d6 co nhisu khai niem ve axit- bazo ti~p tuc ra cU1i. Trang do can chu y khai niem cua David .

•

...

Theo David, viec chuydn proton tit axit sang bazo trong cac phan

~ ,

ung gtira axit- bazc chi IS. giai doan cu6i cung cua cac phan \lng

axit .. bazo, con giai doan da.u tien chinh IS. giai doan tao hop chat phan tit nho n6i cau hydro, sau d6 mdi tao ra muoi bang each chuysn proton. Vi du:

.. •

. ~

HOH

Cc loai phan ung chi dung a giai doan n6i cau hydro:

,

CH30H 0 ... H-O

: '"

CH30H hoac R-C C-R

; . \ ;-

CH30H O-H ... 0

Xuat phat tit quan diem do, ta co dinh nghla: , .

Axit la cac tac nhan nhan electron. Bazo IS. nhung chat cho

•

electron va c6 ai luc vai proton.

4. 1.5. Tinh chat axil • baza cua hydrocacbon

Khi v(in dung cac khai niem axit- baze noi tren vao trong hoa hoc hiru co, nguoi ta thay hydrocacbon ciing co tinh axit- bazo.

80

..

. .~

4.1.5.1. Hydroc~bon ,00 _link axil

, . .

TUdng t\1 nhu cac axit khac, cac nguyen tit hydro trong nhieu

- hydrocacbon c6 th~ thay th6 bang kim Ioai cho hop chit co kim. Vi

diu: - ~

...

+

..

CH=CH + NaCH3

(C6Hs)3CH + :K

•

V~y nhirng hydrocacbon 'n,ay co - tinh azit, cac hop chit co kim

,tren 18. cac hop ~h't ion vi chung 13 cac chat di~n Iy ~

" . .

Ngoai ra, nam 1907, Sorl1gin da tim ra cae' phan ling the nguyen

•

til hydro CU~ cac hydrocacbon nay bang cac nguyen tit kim loai cua

. ~

hQp ch~t Cd kim khac nh 11:

,C6H6 + C2HSNa -,. C6HSNa

...

benzen

•

..

C6HSCH3' - + C2HSNa taluen .

, .

.. ~.

, t

"... _,'

Cac phan ttng nay tuong t\t nhu phan dng axit manh ct4YJaxit

II ' •. -

~ yeu ra khoi mu6i cua no. V~y _ benzen, toluen, etan ,Cting_:fl3-J ~biLng - '

axit. - j .•

- Muon so sanh tlnh axit-'cua nhilng hydro,cacbon--n~~d\'Ck:;~o

, .

nguyen me axit manh dAy axit y~u .ra khoi mu6i ·c~1Il4.ri 1J0 i ~1.··;· <

I • • ..

,.. i" .. .,....,.. ~

Vi d\l; xet mQt so phin tlng sau: ~1D~{rr ~y):}\J .Lf:OC~'.r

'" ., ... - ...

r C'":'i 0' ~ · .... r........ rr h , ,. '" "......" ,,". r

T • .,t.. ~ l. ... ..... ~ t.. ~ _ Jo. I' f.J ~ it u ... " ....

. ~

, I

•

.p

..

, ,

. fluoren·

di~-rIFQ.et~p-{ .. , ') .

. '0. ~ ~

•

~ .

81

v

I

. Qua nhieu phan ling nhu vay, nguoi La sap xep duoc tinh axit

giap1 dan thea thii tv: ·

Fluoren, triphenylmetan, ·dipheny11lletan, toluen, benzen, etan. N goai Ta con sap. xep duoc mot 86 thu tu khac:

- Cac alkylbenzen neu g6c R cang dai thl nguyen ttl: hydro cang kho ,the hoi kim \O~i, do do tinh axit giam,

~ - Naphtalen co tinh axit manh han benzen.

~ .

•

- Axetylen co tinh axit manh hen etylen, va etylen co tmh axit

manh han etan .

..

- Trong axetylen, neu met nguyen til hydro duoc thay the bdi

,

g6c phenyl thl tinh axit tang,

- Trang etylen, neu ta tien hanh thay the 1l19t nguyen tit hydro hay hai d met dau bang cac nh6m CH3 thi tinh axit tang, neu the hai hay b6n nguyen til hydro ~ hOO dau bang hai hay b6n nhom CH3 thl tinh axit giam:

(CH3)2C=CH2 > CH3-CH=CH2 > CH3-CH==CH-CH3 > > (CH3)zC=C(CH3)2

r

4.1.5.2. Hydrocacbon co tink baza

Nhieu hydrocacbon c6 khll nang t:ic dung voi axit tao ra ion

,

eacboni. V~y hydrocacbon cling co tinh bazo nhung chung 18 nhirng

bazo yeu, nen co hai trucng hop xay ra:

ArH + HA ArH + HA

~~ ArH2+ + A- . --- ... ArHtHA

(1) (2)

.

Trubng hQP (1) chi xiy ra khi tac dung voi axit kha manh va co

..

bang so di~~ moi cao nh;r axit HF hay H2S04 khan: ·

,

Trong phan ung nay, n~u them AgF, BF3 thl carrbang chuyen

82

. . .• r- ••

,

-

...

' ..

. .

sang phai tao ra ion, tinh din di~n tang:

. . '" c . .. +. ,

. C6H6 + HF + BF3· " [C6H6H] + .BF;·

Truong hop (2) .xay ra khi tac dung voi cac axit co hang _s6 di~n

.~. .

. .. .

moi khong cao lam nhu. HI, He!.", khi do phan dug se tao phtic ma

, .

khOng tao ion: . . .

. . ~

Dung dich nay neu them AIel) thi H- CI phan cue va .t~o ra ion

• •

cho dung dich din di~n: . • '

•

Qua cac vi du tren ta thay, hydrocacbon co the dong vai trO axit hoac bazo .

•

. .

4.1.6. Anh hlfong eua eae nh6m khac nhau '6" IIIC,

axit - baza cda cae hQ'p chat hiiu CO'

, ..

·4Al.6~1. Truong hVp phiin tit hay . anion c6 hieu·ltng lien h{1p

. .

M()t hC}p chal nao deS sau khi t~ch H+ tao -ra anion mA anion nay

lai co kha. nang lien hop thl no cang ben vting va tlnh axit eua hop chat ~6 tang.

. Vi du, toluen co pKa nho hon "pKa ctla metan, do tiiul 'axit cU~

. ..

toluenlon hon metan; 'P9'i vi sau khi tach ,H+ d~ tao ra anion benzyl

thl anion nay co hi~n tuong cong huong n~n b~n vimg. ' .

)

. .

, - ,

4,,1.6.2. Truirng hlfP phan tit'dura cdc nh6m c6, hi;u; ling cam ung

a. D6i voi cdc nhom. co· hieu ung- ~dm ung am ~

- .. Khi .. trong phan tit chua cac nhom c6 hi~\1 dng c8Dl ung .ilJl· S8

. .

83

........ _--

..

lam tang di~n tich duong a nguyen ttl cacbon cua nhcm cacboxyl

. , .

.lam cho s\t phan C\1c etta lien k~t 0 - H tang l~n, nen dO axit tang.

Vi du, d~ axit ctia axit tricloaxetic Ian han so vai axit axetic

CI ~o-~ ~O-d
-, ~c~ CH3 "'/
CI tE C -c • C
...
/ "~H "~H
' .
CI
axit triclcaxstlc axit, axetic b. D6i uai clic nhom co hieu. ling cam 'Tlng duong

. Khi trong phan tti axit co cac nh6m co hi~u ling cam ung duong se 13.111 giam di~n tich d uong cua nguyen ttl cacbon trong nhom cacb oxy I , lisn ke~ 0 ~ H it bi phan C\!C, do d6 tinh axit giam.

•

VI du, d~ axit ctia axit propionic nho han- so v(ji axit formic.

~O-o ~O-.5

+dl ~,

CH3-CH2-C H-C,. .

\~ ,~

O-H' , -O-H

axit propionic

. axit formic

4.1.6.3. Truimg hqp ,han til chtta cdc nh6m c6 hifu IilJg lien h"p

,

Khi trong phan tit cac hop chit hftu CO co cac nhdm co hi~u ang

+C 813 lam tang .tn$.t·-dt} electron, do do li~n ket O-H it bi phan cue hon, tinh axit gtam so vOi· phan tit khOng chua nhom co hit)u irng +C, VI du, crezol co tlnh axit nho hen phenol hoi vi phan tit ctia no chua CH3 c6 hieu ung +1 va H:

OH

•

crezol

phenol

Nguec lai cac nhdm co hi~u dng =C nhu -N02 se lam giamm;)t

84

....

'III

·cto electron trong phan til~ .li~n k@'t O-H bi phan cl1c nhfsu hon,

..

tlnh axit tang. Vi du, p- nitrophenol cd tinh axit manh hen phenol:

OH

..

.. '

•

.......

j>-ni.trophenot

phenol

. .

4.1.6.4. Lu« axit cia cdc IuJp eMt hitu co con ph~ thu{Jc vtlo

klul nilng solvat h6a· ,

DiSi vffi .cac hQp chal sau khi tach H+ d€ tao ra anion mA anion do co d(l solvat hoa Idn thl hgp chit dQ co tlnh axit cao. Vi du, dQ

,

axitcua butanol hie 3 nbc hen metanol va H20, Mi visau khi tach

H+·. tao ra cac anion C 4H9 - b~ 3, CH30 -, OH~ ~ do y~u t6. khOn~. gian, anion butyl b(ic 3 cong k~nh kho solvat h6a hen so vesi anion CH30- va OH-, vi v~y .

dQ axit cua '. C4H90H bac 3 < eH30H < H20

. Kha nang solvat hoa cua OH- > CH30- > (CH3)3C-O-

. Tl1C1ng t1J nhu v~y, ta cling ,·giai thich diroc tinh, axit ·c~a axit

. ..

. . formic Ian hon .axlt axetic do tac dung chan cda nh6m CH3 trong .

anio~ CH3-COO--, lam cho khl nang solvat hoa anion Day nho hen so vlfi anion H-C-O-

, Ha

o

4.116.~. D9 axit' eac· izvp eMt huu co phl:' thuQc vtlo d9 tim di,ln cUa nguyen tir liin kl,l true tidp yui· hyd_ro

. -

Vi du, axetylen c6 tinh axit msnh hon metan bOi vi nguyen tit

cacbon li~n k«t· vOi hydro trong metan (} t~g thai lai hoa sp 3 co dt)

. .

im di_'n nha hon so vli.i nguyAn til cacbon trong axetylen. CI trang

thai lai boa .~p ~ ..

De. Am di~n nguy@n tit Csp3 = 2,~1 DQ am dl~n nguy~n til' Csp = 2, 75 .

85·

+

, .

Tuong tl:1 nhu vay ta co th~ gUn thich tinh bazo cua pyridin yeu

,

han metylamin, hoi vi nguyen tit nito trong pyridin cd C4p di~n. ttl: khong chia d trang thai lai hoa sp2. .-

Ngoai ra con co cac yeu to khac anh huang den Iuc axit- bazo tao da xet a phan thuyet Bronsted.

4. 1. 7. Axit - baza va tac d l)ng xuc tac trong h6a hoc. h (iu 'CO Trong h6a hoc hiru co nguoi ta thuong dung cac chat xiic tac Iii axit- bazo. Xuc tac bang axit duoo chia lain hai loai:

- proton axit nhu HF, H2S04, HjP04 .

- aproton axit nhu BF 3' AlC13, SnC14 .

Trong cac phan llng hiru co nhu phan ti'ng loai mroc cua aleol; phan iing' axyl h6a; phan ung cracking, phan ling trung hop hoa. ..

II

thl vai tro xiic tac proton va aproton 0 giai dean dau eo tac dung

. .

tach anion) tao ra ion cacboni hoac tao ra phirc mang d~c trung cua ion cacboni, sau do chuydn hda tiep de tao ra san pham phan iing.

Vi du, phan ung alkyl hoa benzen bang RX c6 xuc tac axit aproton AlX3 xay ra nhu sau:

+

RX

Truce tien ROC; +

AlX3

+

tiep do

. ,

Hay phan ung loai H20 cua alcol tao thanh olefin:

R~CH2-CH2-0H

R-CH=CH2

R-CH -CH -0+ -H )

2 2 I

H

RCH=CIl2 + H+

~ .

H+ + R-CHz-CH2-OH

..

---H20 + RCH2 - C+H2 ion cacboni

..

86

v

I

..

..

. Nd~ la xuc tac bazo thl giai dO@.D trung gian se tao ra cacbanion .

•

. .,

vi . du, phan ung aldol hoa cac aldehit tien hanh nhu sau:

. ."

. 0

OH- ;

, CH3-CH-CH2-C

J ' ~,

OH H

"

2CH3-CHO

Trtt6c tiEin OH- + H-CH2-CHO. .. H20 +. (-)CHz-CHO . o

'; .'

tiep d6 CH3-(+)C,< ". (-)CHz-CHO -4» CH3-yH-CH2-CHO

H . O(~)

....

,0

'# CH3-?H-CH2-C" + OR-

OH . H

+

..

4.1.8 lIng d\lng cac thuy" v~axit .. baza

•• • I

Cac khai niem v~ axit- bazo trlnh bay tren d!y dU:Q~ ap dung de:

, ., .

....

a. Gidi thl ch co ·chl cdc phiin. 11ng hicu co nhu: - Phan dng .lo~i n tide.

- Phan dng alkyl hda,

- Phan tlrig cracking. "

- Phan tlng d~ng phan heal

.. Phan ling tritng hQP hoa.;

b. Du doan. chieu. huang ·.~t 86 phdn zlng hitu co

. Vi du, aldehil:, xeton dUQc xem nhu nhitng axit Lewis d~ bi phan cue, . do do' trong cac phan ung k@'t hQP se biet duoc chieu hudng

. .

phan dng: ".

. ..

, O~+6 0 ...

~-<

H

...

...

c. Gidi thlch mot 86 phdn ung ~zla hydrocacbon

" "

Hydrocacbon ed the dong V8:i tro axit nhu u.etylen, do d6 gi!i

thich dl1QC C3.q phan 'ling, thay the; nguyen tu hydro trong axetylen

hang cac kim loai N a, Ag, Cu... . ~

•

CH=CH + AgN03

Age =CAg

hoac giai thich cac phan ling hydrocacbon tac dung vesi axit manh tao ora ion cacboni nhu:

..

ArH

L

+ HA

..

-

trong d6 hydrocacbon them dong vai trO mot bazo.

Ngoai ra cac thuyet ve axit- bazo con co nhieu ting dung khac trong hca hoc hiru cc, ta se Ian luot xet a phan chiic cu the.

4.2 DUNG MOl HOO co

Dungmoi hiru co co tac dung quan trong ,trong nhieu phan ung.

Tuy nhisn cho den nay, chua co Ii thuyet chi dao ch~ vi~c dung dung moi vi cac hien tuong hoa hoc xiy ra gif1a dung moi va cac chit phan llng rat phuc tap, Nhung qua kinh nghiem thuc te va dua vao met s6 d~c die'rn ·cua dung m6i CO" the sl:1 doan bang Ij luan ve Yin de anh huang cua dung mOi den qua trlnh phan ttl:lg~

•

Mu6n xet den van· de nay, nguoi ta phai xet tinh chat Ij h9C va

.

hda hoc cua dung moi. '

4.2.1. NhiAt do sOi

• •

,.

Nhiet dQ soi tang khi trong IU:Qng phan tit tang. 8\1 tang nay co th~ Ibn bat thirong khi phan tit· dung mOi co lisn ket hydro, th! du,

~ . .

trueng hop nuec, aleol, glycol, ~

Khi dung dung moi cho m.Ot phan tlng nao thl phai xet den nhi~t

'. '

d¢ can cho phan ung do ma chon dung moi cd nhi~t d() sOi thich

hop, Thi du, phan tlng khirxeton bang hydrazin va NaOH phAi th1!C

! -

hien trong 6ng han kin (dam. baa nhiet dQ eao) nhungcd th~ thuc

88

..

•

•

hien a ap suit khl quy~n khi dung dung m.Oi co nhiet dO soi cao nhu

, .

. .

di- hay trietylenglycol.

4.2.2. Momen luang eue

Sv phan cue cua dung .DlOi d1.tqc d$.c tzung .bang' mom.en l.uOng cue . ella dung mOi.D6i· vbi cac phan til cd tfnh d6i xung, su phan . ct!c cua cac nhom the hay cac phan trong phan til den bit cho nhau

, . .

nen fA =0. VI du:

. .

,

CH3-(CH2)n -CH3

#=0

Cl

I CI-C-Cl ~l

CI u=O

~

•

tetraclorua cacbon

Dc) phan c1jc ella cac hop chat co the dung lam dung' D10i tang theo day sau:

C6H1..i

L

CCl4 «.CH3COOH < Hce13 < (C2H5)20

•

-

0,83 1,15 1,68

-I

...,. J~_ = a

•

~ 1< CH3COCH3 < HCONH2 -c ~

NH2

2,70 3,37 3,99

1,81 1,90 2,20

...

Kha nang so 1 vat hoa cua dung mol IS. kha nang cua dung mci ket hop vai chat hoa tan; kha nang Day 18 ham so cua dO pha.n C\1c.

DQ phan ·eve cang Ian thl lien ket tao thanh giita dung mei va cac phan til khac lA lien kE!'t ph6i trl, neu d¢ phan C\1c khong Ibn thi se xAy ra hi~n ttiqng phan cue manh hen trong phan til ..

Nhung momen 11.tC1ng eve khong ph!i la yeu t6 duy nhat anh

. .

. ,

huang den kha Dang phan cue cac chat hoa tan rna CO~ phai xet den

y~u to chan kheng gian ella dung moi hay chat hoa tan .

. Anh hl1ong. cua S1;I phan cue dung moi cd the lam thay doi co chE! cua phan ung, th! du trong phan unp' thR,v the C':ftn xuilt halogen)

..

89

-_ .. -. ----_._.- -.-' --_._--- .- _.- ._.. - - _ _.- _.- _ - .. - -- -_ .. - - _. _ .. _... ..- _. . _...... . .. _ --_ .. _._--_ - _ - - .. _------ ._ .. -- - - -- _. - _.- - .

r

. '... ~. . -'

. . .' . . . - .'

neu dung dung m6i khac .nhau thl co th~ xay ra co ch€ SNI hoac

-, SN2 (xem C1} the phan dAn xu~t halogen mach thang)~ dong thdi cling anh h lli1ng den co ehe' cua phan ung tach loai 'E I; E2·

4.2.,3. HAng s6 di," , m6i

Ngoai cI,t) phan cue da trinh bay a tren, cac dung moi con co tinh chat quan trong niia, do la h~ng s6 di~n mOi E.

St,t hut giiia hai dien tich tac dung ql' qz cua hai phan tit d khoang each d voi hang sp dien moi E dl1QC xac dinh bang phuong trinh Caulomb: -

f = q}q2 ed2

Hai t r] so giita ,ll va E: lien quan vdi nhau bang cong thtlc

L

Clausius- Mosotti, mac du hai gia tri nay khOng phai luon Juan thay

,

d6i cung chien, rihung thuong dung D10i cd de> phan cue Ian thl co

hang s6 di~n moi Ian.

S\i phan hang dung 11101 thea hang s6 dien moi co the sap d$t

< < CC14 <: CS2 «C2H5)~O <CHeI3 <CH3COOC2Hs

£=2,02 2,08 2,24· 2,64 4,34 4',81 6,02

, ~ . .

<CH3COOH < , I < CH3COCH3 < CzHsOH < H20 < HCONH2

~ . .

.. ~

6,15

12,30

20,70

24,30 .

81,00

110

De cd duoc s\1 ion hoa de dang doi hoi dung moi co hang so di~n

, .

. ...

moi cao, .tuy nhien di~u kiE}n nay khong phai luon Iuon dung. Thong

thuong y~u to quyet dinh cho su ion hoa Iii S\i solvat h6a.

Thi d1;1, axit xyanhydric co hang so dien moi rat cao (s = 116)

~

nhung khong the dung lam dung moi cho cac loai muoi, trong khi

do nuec c6 E = 81nhung no IS. dung mol t6t cho cac muei.

90

.S\t ion hda d~ dang alkyl halogenua (RX.) .phu thuec vao hang s6 di~n moi nhung phu _thu9~_-_lan.:d6i -~vbi. Iti:o~~n lda~g -,c\tc _~f j/ _ Irtang eye dam bao slj ,ben .virng cac ion tao 'th~nh:do: J~~f.; quasolvathoa.

• • I • 'I • •

• : - I

. .

Nang Iuong solvat hoa IOn ,khoang 70 den 90 keal/mol (0 dang

v ,

ion) trong khi dd mudi ion hoa phan _ tif CJ th~ khi thi can khoang

. . .

200 kc al 1m 01 I Do do da s6 phin ling ion thuc 'hi~n dugc .180 nho dung

. . .

moi, M u6n thl$c hi~n dUQc phan llng ion a th~ khf, can phai cung

cap nang' lucng Ian.

4.2.4. Li6n kit hydro

_

Lien kat hydro lam tang kha nang hoa tan cua cae chat tan vesi

dung mel, Khi cd lien ket hydro 'giua chat hoa tan v~ dung tnOi thl lam tang kha Dang solvat hoa, L do do hcp chat do d~ dang' hoa tan,

Thi du, nuoc hca tan' tot alcoI izopropylic trong khi do nttl1c hoa tan it izopropyl bromua.

..

(CHa)2CHOH (CH3}2CHBr

'7

~

DO hOa tan tron_9 n~.

0.24

4.2.5. DC) axil .va dO baza

. + Dung Dloi co tfnh cha:t· axit neu no co kh! nang phan tach

proton, con dung mel.co tfnh bazo neu ·no co kha nang nhan proton, hay kha Dang ket hop VCsi hop chat axit. 'I'inh axit cua dung moi con

I ... • ...... I .I .

the hien khi no co kha nang- ket hop vdi bazo Bronsted hay bazo

Lewis),

'. Rat nhieu dung moi co tinh . chat luang tinh: vita mang tinh chat axit, vita mang tfnh cp.(t bazo,

Tinh chat cua dung DlOi anh huong tr\tc tiep den kha nang ph an ung. Nhieu dunk mOi co d6i cti~n til khong chia tham d1J m~t s6 phan ung bang each kat hop yoi tic nhan ai di~ tii:~

91

_ _

Nhi'tng dung moi cdkha nang solvat h6a dOi"khi cling lam thu~n

. .

_ ,

IQi cho tien trlnh phan ling. Thi dll, pbenyletylclorua tao thanh

alcol, ete, este khi co mat ,cua dung ll10i Dude, alcol, axit axetie (phan tlng· cung tien hanh theo thu b~c 1).

Chu Y khi dung dung llloi xac dinh thl phai tlm each I\1a chon tac nhan, tranh tac nhan tao thanh vili dung mel mot hop chat phan ttt b"E!n vf1ng. Thi du, khong the dung ete lam dung m·Oi trong phan iing Friedel- Cratfs vi ete se tac dung vdi nhom clorua:

CzHs CI C2HS CI
:1
'0
..... )0: 1-C1
Al:Cl .
+ ,.
/ • • ••
C2HS CI C2HS CI va khong nen hoa tan natri amidua vao alcol etylic:

sO dl nhu vay 13. vi hydro ctia nh6m hydroxyl trong phan tit aleol co' tinh chat axit (D1~C du rat yeu); con natri amidua co tinh bazo ra:t manh .

•

4.2.6. 06 hoa tan cua eac chit '

•

Thong thuong cac hQP chat co cue hoa tan tOt trong cac dung moi co cue, Thi du, cac axit hiiu co b~c th(p' hoa tan tot trong nude. Con cac chat khong co cue thl hau nhu khong hoa tan trong dung mci phan cue. 'I'hi du, cyclohexan hau nhu khong hoa tan trong

~

nuoc.

, .-

Nhln chung dQ hoa tan ella hop chat hjru co phu thuec vao cac

yen t6 sau:

Truong hop dung mei Ia mroc, hop chat hoa tan phAi co nhom dinh chile lam tang d~ phan cue cia hop chilt, nhom dinh chtrc phai tao thanh lien kat niSi hydro vai nuoc. Thl du, nhirng hydrocacbon khong phan cue khOl}g hoa tan .trong mrdc.

•

~

Khi trong phan tit hydrocacbon co lien k~t doi, lien ket ba, nhan

thorn hay nhom dinh chric halogen thl .khong anh huang nhiau den

92

v

,,.

dq hoa tan, vi co th~ co yell to nay nhttng khong co yeu to khac, Nh6m dinh chirc nhu OH, OR, COOH, NH2) C= N, CONH2, C=O, lam tang kha nang hoa tan cac chat chua nhdm dinh chuc nay.

_ . Cac chat co cung nhom dinh chile nhung tang trong lucng phan tit ella gee hydrocacbon thi kh:l nang hoa tali giam. Thi du, cac aleol co g6c hydrocacbon bang· hoac Ibn hen 5 cacbon hoa tan kern trong

,

mroc,

.

Cac chat co nhieu nhom phan C\1C thi kha nang hoa tan tang so

•

vdi hcp c~at trong do chi co met nh6m phan cue.

Cac dung moi khong cue hoa tan tot cac hQP chat khong phan cue, Thi du, tetraclorua cacbon hoa tan tot cac hydrocacbon, cac este .glyxerit. t •

•

Khi tang goc hydrocacbon trong cac hQP chat phan eve thl tang

kha .nang hoa tan cac chat nay trong dung moi khong cue.

Khi dung dung in6i trong .cac phan ung htru co, phai lua ChQD dung moi hoa tan duoc cac cha:t phan ung vi khi hoa tan se. tao nen su tiep xuc giira cac chat phan img, khien cho phan iing tien hanh d·e dang, Truong hop hoa tan .it thi phan ung' cfi.~g· cd th~ tien hanh duoc, VI S\"i has: tan cac chat phan ung cung. tuan thea nguyen ly

. chuyen dich din bang. Khi chat hoa tan da phan .ung . thi can ba~g

~

hoa 'tan chuyen ve phia hoa tan hQP chat .dd trong dung mol.

Do cac van de da trlnh bay a' tren nan khi .thuc .hien phan iing htru eo, trong dai da so truong hQP ta phai Iua chon dung inoi va

can cd vao: .

;- nhiet dO sOi· cua dung moi.

. . - . mamen h1ang cue, hang so di~n Indi cua d ling moi. ~ tinh axit - bazo cua dung mol.

- dt) hoa tan efta dung mO,Ld6i" vBi cac ··chat phan ting ...

Va:·n de lua chon cho d~n nay .chua co th~ co mot .quy luat chung

. . .

. ro rang, tuy thuoc vao tlnh chat. cua phan ung, tinh chat cua cac

. chat tac dung Ina chon dung mol cho thich hop.

93

. .

-Chudng V

Kbii Di~1D ve ifng d\lng

..

ee hqc ldqng td trong

boa hoc hUu co

•

Do su phat hien ra nhirng tinh chat moi cua anh sang, cua di(!n ttl cung nhu trong chuyen dong etta cac hat vi me khac, cac dinh luat vat Ii hoc co di~n tres nen bat Iuc khong giai thich noi va nhieu khi rnau thuan sau sac vdi thuc ti~n.- Ngay thuyet cau tao nguyen tit etta Bohr mac du da c6 gang dua V8.0 1l19t so dinh de luong tit, do

• •

d6 da giai thich thanh cong nhieu hien tuong va tlnh chit cua

nguyen ttl, tuy v~y ·thuyet Bohr cling de It? nhieu .nhuoc dietn quan

.

trong; no kh6ng the xay dung duoc 1y thuyet dinh IUQng cua cac

nguyen tit co nhieu di~n tit. 'I'ren co sa nhimg nguyen tac hrcng tit

•

h6a kheng the xAy dung' d1JQc Ii thuyet v~ tinh ben virng ella quy

c40 ngay ca trong truong hop nguyen til beli co hai di~n tU:; cling khOng the thiet lap Ij thuyet v~ Ct1C1ng d()~ cua cac vach Quang phd. Cu6i cung, ban than thuyet Bohr cung' chua dung 8\1 td hQP day mau thuan giira cac tien d~ 11.1Qng tit vci nhirng khai niem vat Ii hoc co di~n kho chap nhan duoc, Vi v~Y. can phai co ~Qt Iy thuyet hien

dai han, hoan chinh hen, ·

....

SlJ phat minh ra co hoc IUQng tii la mot thanh tuu tuyet vC1i cua

, .

v~t Ii hoc. Cc hoc Iuong tu 13. Ij thuyet hien dai nhat, tdng quat

nhat, no giup ta di sau vao ban ' chdt cUa cac hien tuong trong the giCfi vi mo nhu s'J thong nhat gifta ban chat song va hat, h~ thdc

,

bat.dinh. 'I'huyet luong tit cungIa ly-thuyet chung duy nhat cua cac

hien tucng di~n tli trong the gioi nguyen tit va phan tit, titc la nhirng hien tuong eCl ban tao nen nhftng qua trinh v~t If va hoa hoc

94

v

..

phuc tap han, n6i rieng ii thuyet nay cung chua dung trong n6 khA nang gi8.i thlch day du tinh chat hoa hoc cua VQ di~n tit cua nguyen

. .

tu va phan tit. Dieu d6 duoc chung minh Mi nhirng thanh tuu cua

. .

hoa hoc hlc;fng ttl. Song song ven pham vi Ian lao cac van de v~t ly,

I • • 'I •

trong thuyet lucng tit cdng thu duqc IAn dAu tien nhf.tng IC1i giSi vE!

. . .

nhirng vin de CO SO cua hoa hoc ly thuy~t nhu ban chat cua lien ketO

. . .. ~

hda hoc, tinh bao hoa hoa tr], Dloi li@n h~ giua tinh chit quang hoc

. .

va hoa hoc veri cau true di~n, ttl cua nguyen til: va phan tit, ban chat

•

hang rao nang I11Qng hoat hoa trong phan ttng luong phan tit, tuong

tac gltra .cac ph An tit VtV.tt H6a hQC hrong tit IS. giai do~n DlCJi cua s\1 phat trien nganh hda hoc IY. thuyet do Butlsrop sang l~p.

- .

~

Tuy nhien, .ch uong nay chi nham giup chung ta budc dau lam ,

quen vCtiL phuong trlnh co ban cua cc hoc lucng tit 18. phuong trlnh Schrodinger va sl!- van dung no d~ tim hieu ciu-' tao nguyen tu, phan tu, ban 'chit cac loai lien ket h6a hoc va cac phuong phap co

~ . .

ban cua CO hoc hrong tit tlnh toan trang thai di~n t~. va kha nang

phan ung cua m<)t s6 phan tit huu co. Do d6, chuong nay chi nham

•

dua ra nhirng co sa diu tiAn cho chung ta di· sau v~ hoa hQC luong

-tit· qua cac sach chuyen de khac, . .

5.1. TINU· CHAT SONG CVA HAT vA PHUONG TRiNH'

.. . '

SCHRO.DINGER

~

5.1.1. Thuyit III«;1ng·. t·1l anh sing

. .

Ly thuyetc6 ~ien quan nlsm qu-a trlnh hac xa Ia su phat ra lien

t\1C cac song di~n tu co tan s6 dao dQng v, ~uoc song A va Ian rruyen vlfi toe dO c. Cac dai lucng v, A, C li~n h~ vai nhau hoi phuong trlnh:

. ...

~.

c = v . .A

(5-1)

Nguoc voi thuyet Ctl di~ri, Planck gia thigt rang hue xa di~n tit duoc phat xa hay hfi:p thu DlQt each gia:p. doan, timg phan rieng biet ella nang 111Q~g - t~c 18. nhirng IUQng tit anh sang, .nang hrcng e cua

•

. \

95 .

-----

lucng tit tinh thea cong thirc:

..

E ~ ltv

(5- 2)

, ...

trong dO h la hang s6 Planck, bang 6,62.10-~' erg.s

Tiep thea cluing ta se sit dung tan 56 vong (I) va hang so h; no lien h~ vdi c, h va y thea cong thtic:

~

11 ·;1 =-

2"1"

_Nhtt vay cong thuc (5- 2) co the viet duoi dang:

(5- 3)

•

£ =hsa

Sau do Einstein da phat trien nhirng gia thiet cua Planck thanh thuyet lucng tu anh sang. Thea Einstein, S\! Ian tru)"en cua biic xa duoc xem nhu dong chuye n dQng cua cac IUQng ttl bay vai toe dq anh sang c, gQi'la nhirng photon. S6 photon trong mot don vi the tich quyet dinh cuong de} ella buc xa. Thanh tuu Ian lao cua thuyet luorig tit v€ buc xa khien cho n6 duoc pho bien rcng rai IS. kha nang giai thich ducc dung dan hien tucrig quang dien rna thuyet song di~n tit khong giai thich duoc day du va dung dan .

. ,.

De giai thich .hien tuong quang ap, nguci ta phai gia thiet rang

lucng ttl anh sang, photon, dong thci vci nang lucng con co ca dong IUQng p. Hucng cua vectc p trirng vdi hudng Ian truysn cua song anh sang, con dO Ion cua no duoc xac dinh boi tan s6 OJ thea cong thuc:

p .......

(5- 4)

c

Ta co the lap duoc bieu thuc nay bang each dong nhat hai each tinh nang 111Qng:

tit do

E = Ii w va E = nic2 = pc fz w = pc

lieu

suy ra p =

c

A.W Mat khac, vi c = AV = 2i

-

-

c A.

,96

•

Thay vao (5· 4) ta cd;·

.: 21r, It,

l? =. A -

•

(5- 4')

, .

Phat hi~n cua Compton (1923) va 811 tang ella budc song tia Roentgen khi tan xa chung tren di~n tit va st;i phu thuoc giita ~ va

g6c tan xa 8 da xac nhan dfeu do:

, .

•

. 41th ()

AA. = sin2-

mec 2

Nhtrng nghisn ctiu thuc nghiem eta.' xac nhan hoan toan cong thiic nay. Thea thuy~t luong tit anh sang; co sd cua hien tucng nay

.

lA s\i va cham gifia di~n tit vi photon. Do nhuong' nang lucng cho

di~n tit nen nang IU:Qng cua photon giam xuong ~ theo cong thuc

. .

(5- 2) tan so phai giam xu6ng, cd nghla Ii bttac song tang, len.

Qua day ta thiy, co nhieu hi(!n tttQng xay ra khi tucng tac anh sang vdi cac ch§:t chi eo the giai thich dtlQc bang quan ni~m luong

•

tit, . nhung dl>ng thoi ciing co nbieu hi~n tuqng g8n li~n v{Ji s\t giao

thoa, nhi~u X," va phan cue cua anh sang cd ~h~ giai thieh' dEiy du

.

t~n co sa th~yet. song anh sang, Nhung nghien cttu tiep thea da

chung minh mng tinh chit nhi nguyen song - hat co trong ban chit

, .

ciia 81.1 vat.

... ..

•

, Hai tinh chat song va hat 18. hai ~t d6i lap nhung thQng nhat

.

vdi nhau, 1>0 sung lin cho nhau. Do do phu thuec vito d~ trung ctia

. hi~n tl1Qng ta co th~ dung khai ni~Dl song hoac h~ cua anh sang.

Trang thuy~t Iuong tit hi~n d~,. truong di~n til: co th€ la ttS hQP ctia

, .

khai nism song va hat, mac du VCJi quan ni~Dl cd dian hlnh nhu

dieu d6 IS. mau thu§,n ..

. .:1

5.1.2. Tfnh ch4t s6n9 eua difn tii

Nam 1924 qua nghisn ciiu ly thuyet, L.de Broglie dB. neu len quan di~m va tinh chat -song cua cac -phan ta va do do eta d$t ra

, ....

97

-.- . --- .. _--_. _. __ . - ..... --_, ..... _. _ ..... - -_ ... _ .. _. - . - ... --- ._--- -. __ .. _ .. - - ... - ----- .. - _. - . _._-- . _. -- ._-- .-... _._._- - ._.- _. - - _ .. _-- .... - . -- - ----_. --_._-_. _ ..... - ._ ... _ ... _. _ .. --.- -- .. _--_ ... _.- --- - .-. _ ... - .. - ----_. _. - -

D1Qt trong nhirng yeu to diiu tien xay dung nen thuyet mci la co hoc song (hay co hoc luong til:)" Thea suy luan cua de Broglie, chuydn dong cua 'mot hat vat chat co dQng luong p gan lien vai E:i\l Ian truyen cua mot song don sac co dq dai song tuong ling IS.:

2Jt1i'
A -.
-
.-
.. p (5- 5)

Nhu vay tinh nhi nguyen s6ng - hat, xay ra trong ly thuyet ve

. -

anh sang cung duoc iing dung d6i vai cac phan til cua cac cha-t,

nghia 13. d6i vai nhirng phan tu co kh6i IUQng tlnh,

. .

Nam 1927, Davission va Germer da phat hien 8\1 nhieu xa cua

, .

electron co van toe xac dinh ung voi D1UC nang luong khong Ion

•

tren b~ mat don tinh the. Trang truong hop nay, don tinh th·e 13.'

inQt each tit nhieu xa phang va di~n tu: tan xa uu tien tren mot so hucng nhat dinh tuong ling vi1i su ti~n dean th uyet nhieu xa song. Cac ket qua do luang da hoan toan xac nhan cong thtic (5- 5) cua de Broglie, Cting nam 1927, Thomson (Anh) va Tartacovski (Lien X6· cu) d& thu duoc anh nhieu xa vong troll cua electron khi truyen qua ban kim loai (hlnh 5- 1). .

D6i voi nhfrng electron c6 t6c dq nho, U «. c, thay cong thiic

tinh:

p2 E=- 2nte

vao cong thuc (5-.5) ta co:

2rch

A = (5-6)

V2m~

Neu electron duoc tang toe

•

trong truong di~n tit vdi hieu

the v thi .nang luong electron: se bang:

E = eV.

98

•

Hlnh 5 -. 1

.----

Khi V tinh bang volt, m'e = 9.10-28 g, thay vao cong thuc (5-6) ta

~

co:

A = V 150 ,A v

. Khi V :; 1 volt thi tucng ling A. = 12,2 A ; V = 1 04 volt, tuong

o

ling A = 0,112 A .

(5· 7)

Thay gia tri cua buoc song A vao cong thuc xac dinh vi tri cua cac cue dai nhieu xa d6i veri each tit khong gian:

nA = 2dsincp

trong do d la hang s6 cua each ttt, f{> 13. gdc giua chum tia va mat phang cua each tit. Bang each nay, Thomson va Tartacovski dA chung m.inh h~ thtrc de Broglie hoan toan dung.

Phan b6 cua electron tren man chan khong phu thuoc cuong dq dong khi churn tia co nang Iuong nho do tuong tac giua chung kh6ng dang ke; noi khac, moi electron nhieu xa khong phu thuoc ~o cac electron khac, nghla la tinh chat song la ban chat vOn co

~

cua .mdi dien tit .

•

.

ve' sau cong thuc (5- 5) con dl1QC ki~m nghiem va xac nhan trong

. .

cac hien tucng .lll~i~u xa cua cac phan . tit nang hen nhu nguyen tU:

. . .

va phan tit ..

5.1.3. Ham so s6ng va phllan-g trinh Schrodinger'

BAy gia chung ta chuydn sang thiet l~p phuong trlnh s6ng vdi cac phan tit.

r

M<)t s6ng phang don sac Ian ·truyen theo phuong true Ox co tan

so OJ va bUC1C song A thucng duoc viet duoi dang: .

• r 2..7tx

tf'(x.t) = acos (cut - A ) (5- 8)

21tx

d day a la bien dQ song va bi~u thiic (wt - -r) 18. pha cua song.

99