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Phương Pháp PH H NG Ngo I
Phương Pháp PH H NG Ngo I
Phng php phn tch theo ph hng ngoi l mt trong nhng k thut phn tch
rt hiu qu. Mt trong nhng u im quan trng nht ca phng php ph hng ngoi
vt hn nhng phng php phn tch cu trc khc (nhiu x tia X, cng hng t in
t vv) l phng php ny cung cp thng tin v cu trc phn t nhanh, khng i hi
cc phng php tnh ton phc tp.
2
= 0,8 2,5m
= 50 - 100m
Trong thc t, ph hng ngoi thng c ghi vi trc tung biu din T%, trc
honh biu din s sng vi tr s gim dn ( 4000 400 cm-1).
m1m2 2
ro = ro2 (1)
m1 + m2
m1m2
1
1
1
=
+
hoc
m1 m2
m1 + m2
(2)
h2
8 2 I
J ( J +1)
4
(3)
0
1
0
1
2
2hB
2
6
6hB
3
12
12hB
4
20
20hB
5
30
30hB
Mt s mc nng lng quay thp ca phn t hai nguyn t v cc chuyn dch cho
php c trnh by trong hnh 2a sau:
1
2
(6)
1
2
Trong :
vm - tn s do dao ng t nhin ca phn t.
k - lc lin kt gia hai nguyn t.
- khi lng thu gn ca phn t.
Mt khc khi cc dao ng t thc hin dao ng, di tc dng ca lc hi phc F
th n s c th nng Er:
F =
Er
= kr = k (r ro ) (7)
dr
suy ra:
ER =
1
k (r ro ) 2 + EO
2
(8)
Vi:
Er - th nng ca h ng vi mt s chuyn dch no khi v tr cn bng.
E0 - th nng ca h ng vi v tr cn bng ( tc r = r0), cng l th nng cc tiu
ca h.
Biu thc (8) cn gip ta hnh dung th biu din s ph thuc th nng ca phn
t hai nguyn t trong dao ng iu ho vo khong cch r gia hai nguyn t. l mt
parabol c trc i xng l ng thng ng i qua im cc tiu ca th nng. mi
trng thi dao ng, khong cch r gia hai nguyn t thay i xung quanh gi tr r o t
mt gi tr cc i rmax n mt gi tr cc tiu rmin. hai gi tr gii hn th nng Er ca
h bng nng lng ton phn do dao ng E d. Theo c hc lng t, nng lng ton
phn Ed ch c th nhn mt dy cc gi tr gin on:
v IR = vm
10
1
2c
k
u
(10)
c vn tc ca bc x chn khng.
Biu thc (10) cho thy khi khi lng thu gn khc nhau khng nhiu, s sng ha
tr tng theo hng s lc ha tr :
V c c >V c =c >V c c;
V c =o >V c =c...
Ngc li, khi hng s lc ha tr khc nhau khng nhiu th phn t c khi lng
thu gn nh s hp thu s sng cao hn phn t c khi lng thu gn ln. y chnh l
nguyn nhn lm cho cc vn hp thu do dao ng ha tr ca O-H, N-H, C-H xut hin
khong s sng rt cao trn ph hng ngoi.
Cc vng ph hng ngoi:
Nh ni trn, ph hng ngoi thng c ghi vi trc tung biu din T%, trc
honh biu din s sng vi tr s gim dn (4000 400 cm -1 ) . Theo thi quen, nhiu
ngi vn gi s sng l tn s v thng k hiu V, n v cm-1 biu din chng.
Hu ht cc nhm nguyn t trong hp cht hu c hp thu vng 4000-650 cm-1 .
Vng ph t 4000-1500 cm-1 c gi l vng nhm chc v cha hu ht cc vn hp thu
11
712
594
522
704
2914
1032
1037
1049
726 cm-1
722 cm-1
722 cm-1
724 cm-1
725 cm-1
H3C - CO - CH3
H3C - CO - C2H5
H3C - CO - C4H9
S sng (cm-1 )
2260 2150
>C = C <
1680 - 1620
>C =C C = C <
1.9
1650 - 1600
Arene
1.7
1600 - 1500
1100 - 700
Loi hp cht
CC
CC
Dao ng
Tn s (cm-1)
CH3
VC - H(bx)
D ha tr bt i xng
VC - H(x)
D ha tr i xng
CH3 (tmp)
CH3 (nmp)
>(CH3)2
CH3
1380 (tb)
C(CH3)3
CH3
Ghi ch
1365 (m)
>CH2 thng
VC - H(bx)
D ha tr bt i xng
VC - H(x)
D ha tr i xng
CH2
D bin dng li ko
CH2
745 735
735 725
725 - 720
CH2 vng
CH2
1452 cm-1
18
VC - H
CH vng ba
CH2 - halogen
VC - H
3050 (y)
CC
VC - C
C - C
600 - 500
CO CH3
VC H
Thng rt yu
CHO
VC-H
O CH3 O
CH2 O
VC-H
N CH3
VC-H
O CO CH3
CH3
Cng rt mnh
Dao ng
>C=CH2
V=CH2
CH=CH2
Tn s (cm-1)
=CH2
V=CH2
=CH2
995 - 980
V 915 - 905
>C=CH
Ghi ch
V=CH
=CH
CH(nmp)
RHC=CHR (cis)
CH
R CH=CH2
CH
R2C=CHR
CH
V 940 900
(m)
840 790 (tb)
VC=C(klh)
VC=C(lh)
> C=CH2
VC=C
CH=CH2
C=C
RHC=CHR(cis)
VC=C
C=C
1680 1620
(b)
1625 (tb)
<1665
630cm-1
<1665
630 va 455
RCH=CHR(trans)
VC=C
C=C
>1665
455 - 370
>C=CH v C=C<
VC=C
>1665
Dien v Trien
VC=C
1650(m) v
1600(m)
Dao ng
Tn s(cm-1)
Ghi ch
Aryl H
VCH thm
CH(tmp) thm
CH(nmp ) thm
C=C
(mt nhn
thm)
VC=C
Mch carbon
Nhiu
nhn thm
CH(nmp)thm
Mt nhm th (2 mi)
Hai nhm th ortho (1mi)
Hai nhm th meta (3 mi)
Ba nhm th 1,2,3
Ba nhm th 1,2,4
Ba nhm th 1,3,5
1625 1430
1625 1590, 1590
1575
1575 v 1525 - 1470
900 675 (b)
2 hay 3 mi
D bin dng ngoi mt phng,
tn s thay i theo s H, theo v
tr v s nhm th:
671
770 730 (m)
770 735 (m)
21
Dao ng
Tn s (cm-1)
Ghi ch
CCH
V=CH
CH
VCC
VCC
C th b che bi mi NH hay OH
Hai mi
Alkyne mt nhm th
Alkyne hai nhm th, mi ch do
cng hng Femi, cng cng yu
khi tnh i xng cng cao (khng
xut hin khi ni ba gia mch hoc
gn gia mch)
CC
CC
355 335
510 - 260
960 900
520 495
495 - 480
CCH
CCH
Acetylene
Alkyne th
-CCC
RCCme
RCCEt
D ho tr do mch carbon
D bin dng do mch carbon
D bin dng do mch carbon
Dao
S sng (cm-1)
22
Ghi ch
OH lin kt
hydro (DD m
c)
VOH
OH(tmp)
3640 3630
3625 3620
3620 3610
3460 3450
1410 1260 (m)
OH(nmp)
700 - 600
VOH
OH(tmp)
1500 - 1300
OH lin kt
hydro ni phn t
VOH
H2O kt tinh
VOH
H2O trong DD
H2O m
COH
VOH
VOH
VC-O
Dao ng
S sng(cm-1)
OH
VOH
3620 3590
Ghi ch
DD long, dung mi khng phn
cc
C nhm th rt in t v tr
3650 3600
23
3400 3230
3200 2500
720 600
OH(nmp)
-C-OH
VC-O
1205 1030(m):
1255 1240, 1175
1150, 835 745
1320
1185
1300 - 1200
Dao ng
S sng (cm-1)
Ghi ch
COC
(ether)
VC-O-C(x)
VC-O-C(bx)
1270-1030(m):
1150 1060
1225 1200
1270 1030
1270 1230
1090
1470 - 1230
D ho tr i xng:
Ether thng, no
Ether thng, khng no
Ether vng
Ether thm
Ether benzylic
D ho tr bt i xng, chu nh
hng ca nhm gn trc tip vo
nguyn t oxy
Vvng
1250
COC
(epoxide)
24
CO
(peroxide v
hydroperoxide)
OO
(peroxide v
hydroperoxide)
VC-O v
VC-C(bx)
950 810
VC-H
3060 2990
VC-O
1300 1000
VC-O
900 830
D ho tr bt i xng do s ghp
cp ca lin kt C-O v C-C
Dao ng ho tr C-H ca vng
Dao ng
Tn s (cm-1)
C=O
(cetone thng
no hoc vng
ln hn 5
carbon)
VC=O
Ghi ch
o mu trng thi hi
DD long
Mu lng hay DD m c
Cetone thm(nhiu nhn lin hp)
Cetone - ethylenic
Cetone - halogen
Cetone dihalogen
Orthoquinone
Parequinon (mt hay hai mi hp thu)
Chu nh hng ca nhm alkyl v
tr carbon :
1435 1405
1360 1355
630 629
540 - 510
1610 (m)
C=O(tmp)
C=C
VC=C
(-dicetone)
Aldehyde: Lin kt C=O c tn s dao ng cng nguyn tc vi cetone, nhng cao
hn mt t. Ngoi lin kt C=O, aldehyde cn c lin kt C H (bng 10).
Bng 10: Tn s hp thu c trng ca aldehyde.
Nhm
Dao ng
Tn s(cm-1)
Ghi ch
C=O
VC=O
CH
C=O (nmp)
VC-H
1740-1720 (m)
1715-1695 (m)
1705-1685 (m)
650-580 (m)
Aldehyde no
Aldehyde thm
Aldehyde -ethylenic
Aldehyde thm
Gm hai mi, tn s thay
i theo mch carbon v
nh hng ca nhn
thm:
Benzaldehyde (mt mi),
Aldehyde thm (hai mi)
C=O (tmp)
2900-2860
2830-2810 v
2745-2720
1390
Dao
ng
Tn s (cm-1)
Ghi ch
COOCO
VC=O
26
COC
VC-O
1185-980
1050-1040
1300-1210
Anhydride
ngn.
thng,
mch
Dao ng
Tn s(cm-1)
Ghi ch
CO
VC=O
1725-1700 (m)
1760
Dimer
Monomer (gim khi mch carbon
cng di)
Acid thm hay acid -ethylenic
(acid thm c s kt hp ni phn t
gia nhm COOH v nhm OH v
tr ortho lm gim khong 50cm-1
1715-1680
OH
COO
VOH
-CO-O
3300-2500
675-590
570-545
>C=CHCOOH
Carboxylate COO-: Ion carboxylate c hai vn hp thu do dao ng ha tr i
xng, bt i xng v mt vn do dao ng bin dng (bng 13).
Bng 13: Tn s hp thu c trng ca ion Carboxylate
Nhm
COO-
Dao ng
VC=O(x)
VC=O(bx)
-CO-O
Tn s(cm-1)
Ghi ch
1610-1550(m)
1690
172-1700
1450
760-400
27
Dao ng
Tn s(cm-1)
Ghi ch
CO
VC=O
COC
VC-O
1750-1725(m)
1730-1705(m)
1800-1750
1770-1740
1780-1760
1820
1275-1185 v
1160-1050 (m)
1310-1250 v
1200-1100 (m)
Eter thng, no
Eter thm hay khng no
Aryl v vinyl ester
Ester c nhm rt in t gn vo C-
Lactone nm cnh
Lactone bn cnh
Ester thng (hai mi)
Ester thm hay khng no
Dao ng
CO
VC=O
Tn s(cm-1)
Ghi ch
Acid thng no:
Dao ng
VC=O
VN-H
NH
CONH
(amide bc 2)
O=C-N
Mch carbon
VC=O
VN-H
NH
O=C-N
Mch carbon
CON<
(amide bc 3)
VC=O
O=C-N
CONCO
(imide)
NCON
(urea)
VC=O
CONH
(thioacid v
thioester)
VC=O
VC=O
Tn s(cm-1)
1690
1650
3500-3400
3350-3200
1620-1590
1650-1625
700
1420-1400
1700-1670
1680-1630
3460-3300
3270-3100
1550-1510
1570-1515
700
1305-1200 v
700
1670-1630
700
1710 v 1700
1770 v 1700
1660
1640
1720
1720
Ghi ch
DD
Rn
DD long (hai mi)
DD m c (hai mi)
DD long (mt mi)
DD m c (mt mi)
Mt hoc nhiu mi hp thu
Mt mi
DD
Rn
DD long (mt mi)
DD m c (hai mi)
DD long (mt mi);ch c amide
mch h
DD m c (mt mi)
Mt hoc nhiu mi hp thu
Mt mi
DD v rn
Vng su cnh
Vng nm cnh
RNHCONHR
Vng su cnh
Vng nm cnh
Dao
ng
Tn s(cm-1)
NH2
VNH(bx)
3500 (tb)
29
Ghi ch
DD long
VNH(x)
NH
>NH
VNH
NH
CN
VCN
NH3+ (mui
amine nht)
VNH+
NH+
NH3+
(aminoacid)
VNH+
NH+
>NH2+
(mui amine nh)
-NH4+
(mui
ammonium)
VNH+
NH+
VNH+
NH+
3400 (tb)
3400-3330 (tb) v
3330-3250
1650-1560 (tb)
3350-3310
3310-3300
1580-1490 (y)
1515
1250-1020
1340-1250
1350-1280
1360-1310
3000-2800 (tb)
1600-1575 (m) v
1550-1504 (m)
3130-3030 (tb)
1600(m) v
1500(m)
2700-2250 (tb)
1620-1560 (m)
3300-3100
1435-1428
Dao
ng
Tn s(cm-1)
NH
(ca imine)
C=N(ca imine)
C=N
(amidine)
C N (nitrile)
VNH
34003300 (tb)
VCN
VCN
16901620
1681580
1515
22602250(b)
22302220(b)
VCN
CN
N C
VCN
390-350
580-540
V 430-380
2175-2150
30
Ghi ch
Mi imine
Mi Amidine rn
DD
Nitrile thng, no
Nitrile khng no,
thm(cng bin
carbon, theo h thng
to phc vi kim
C N M )
Nitrile thng, no
Nitrile thm (hai mi)
Isonitrile thng
lin hp hay
i theo mch
ni Pi lin hp,
loi dng
VCN
2225-2210
VCN
VCN
2250-2000
2080-2070
1575(y)
VCN
2300-2230 (m)
VN=O(bx)
VN=O(x)
VN=O(bx)
VN=O(x)
VN=O(bx)
VN=O(x)
VN=O(bx)
VN=O(x)
1560 (m)
1350
1650-1600(m)
1270-1250(m)
1630-1550(m)
1300-1250(m)
1600(m)
1500(m)
1300-1200(m)
970-950(m)
N+O thm
N+O bo
VCN
Isonitrile thm(Isonitrile c mi hp
thu c trng phn bit vi nitrile
1595 cm-1)
Mui dng rn
Mui trong DD
Rt yu hoc khng xut hin v lin
kt-N=N- khng phn cc
Rt mnh
Mnh
P=O
P OH
P O P
P O C
P O C
Dao ng
VP-H
P-H(nmp)
P-H(nmp)
VP=O
VP=O
Tn s(cm-1)
2440-2350(m)
1090-1080
940-909
1150
1190
1299-1250
1040-910
1000-870
1050-970
1260-1160
Ghi ch
Nhn
Tn s(cm-1)
2600-2550 (y)
>S=O
VC=S
VN-H
VC=S
N-H
VS=O
1200-1050
3400
1300-1100 (m)
1550-1460 (m)
1060-1040 (m)
>SO2
VS=O
1370-1310 (m)
1180-1120 (m)
1420-1330 (m)
1200-1145 (m)
Nhm
S H
(ca imine)
>C=S
CS NH
(Thioamide)
SO2 O
Ghi ch
Yu hn VO-H v t b nh hng bi
lin kt hydrogen
3150 cm-1 khi th rn
D ha tr bt i xng
D ha tr i xng
Dao ng
O=C=O
Carbon dioxide
N=C=O
Isocyanate
Tn s(cm-1)
Ghi ch
2349 (m)
2275-2250 (m) Rt mnh; V tr khng b nh hng
bi lin hp
N=N=N
Azit
N=C=N
Carbodilmide
>C=C=O
Cetene
N=C=S
Isothiocyanate
2160-2120 (m)
>C=C=NCeteneimine
C=C=C
Allen
2000 (m)
1950 (tb)
Dao ng
Tn s(cm-1)
C F
VC-F
1400-730:
Ghi ch
Monofluoralkane
32
1100-1000
1350-1120
830-560:
VC-C
C-F
726
649
760-505 (m)
CCl3
VC-Cl
450-250
830-700
CH2 Cl
C Br
CH2
VC-Br
C-Br
1230 (m)
650-485 (m)
300-140
C I
VC-I
CH2 I
CH2 CH2 I
Aryl-halogen
CH2
600-200
610-485
1170 (m)
594 v 503
1270-1100
1096-1089
1078-1074
1057-1034
1073-1068
1073-1065
1042-1028
1061-1057
CF2,CF3
C C Cl
VC-F
VC-Cl (para)
VC-Cl (meta)
VC-Cl (ortho)
VC-Br (para)
VC- Br (meta)
VC- Br (ortho)
VC-I (para)
Mch thng
Hai vn
33
35
V d: Xc nh mt cht dng dung dch.Chn s sng thch hp, cho dung dch
cn o vo cuvt. Ch s o trn my t l vi I. Li cho dung mi nguyn cht vo
Cuvet. Ln ny ch s o c t l vi Io.Theo h thc trn, xc nh c A tng ng
vi nng C. nhng my hin i, gi tr A c tnh v ghi trc tip. T cc nng
khc nhau bit, o cc gi tr A tng ng, v th A - C.Sau vi nng cn xc
nh, cng o A nh trn ri theo th chun m tm C.
b. Phng php ng nn:
C khi gi tr A cho trc tip trn my.Nu hn hp c nhiu thnh phn c cc m
ph xen ph nhau th tm nng ca tng thnh phn phi gii h phng trnh nhiu
n (tng t nh phng php ph in t).
38
V.
Bng phng php ph hng ngoi khng cho bit phn t lng (tr trng hp
c
bit).
- Ni chung ph hng ngoi khng cung cp thng tin v cc v tr tng i ca
cc nhm chc khc nhau trn mt phn t.
Ch ring ph hng ngoi th i khi cha th bit l cht nguyn cht hay cht
hn hp v c trng hp 2 cht c ph hng ngoi ging nhau.
b.
Axt Linolenic:
CH3CH2CH=CHCH2CH=CHCH2CH=CH(CH2)7COOH
Axt Eicosapentaenoic:
CH3CH2CH=CHCH2CH=CHCH2CH=CHCH2CH=CHCH2CH=CH(CH2)3COOH
Axt Docosahesaenoic:
CH3CH2CH=CHCH2CH=CHCH2CH=CHCH2CH=CHCH2CH=CHCH2CH
=CH(CH2)2COOH
5.2
ghi ph FT-IR ca cc mu, chng ta s dng phng php vin nn KBr. Sau
khi to vin nn bng my thy lc th trng mt lp cht bo (c trch ly bng my
Soxhlet) tht mng v u trn b mt vin KBr. Sau ghi ph iu kin: Hnh 1 l
ph FT-IR ghi c ca m c basa.
phn tch nh lng, chng ta chn mi dao ng ha tr bt i xng as (=CHR) s sng ~ 3.000 cm-1 (hnh 1) v dung mi s dng thch hp l CCl 4. Trong m c,
thng axt bo khng no chim hm lng ln l Olenic (C18:1). Do , chng ta chn
cht chun l axt ny dng ng chun.
Cn 49,9 mg Olenic v pha long vi cc lng CCl4 thch hp co cc dung dch
c cc nng tng ng l 9,52 ppm; 15,87 ppm; 31,74 ppm; v 79,36 ppm. Sau cho
tun t cc dung dch vo cuvet (d=0,5 cm) v ghi ph FT-IR phn gii 4 cm-1 v 10
scan (s sca t v dung mi bay hi nhanh). Dng ng chun tng ng vi cc s liu
ny.
Cn 500,6 mg cht bo (c trch bng my Soxhlet) v pha long bng dung mi
CCl4 vi lng thch hp cho nng nm trong vng ng chun. Sau cng cho
dung dch ny vo cuvet nh trn v ghi ph FT-IR vi cng iu kin nh cc dung dch
chun. hnh 2 l ph FT-IR ca cc dung dch chun v mu kho st. Kt qu tnh ton
cho ra hm lng ca tng cc axt bo khng no trong m c basa l 61,01%.
5.3 THO LUN SO SNH:
40
STT Tn axt bo
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
Lnh (40C)
Nng (chin)
0,24
4,39
0,25
22,97
3,50
0,33
9,63
39,94
9,76
0,41
0,47
1,66
0,53
0,72
0,31
0,21
0,32
38,69
61,31
45,22
16,09
0,19
5,91
0,24
30,19
2,27
0,25
8,46
40,01
5,85
0,40
0,29
1,41
0,37
0,40
0,72
0,13
45,53
54,47
43,69
10,78
Lauric
Myristic
Pentadecanoate
Paimitic
Hexadecenoic
Hexadecanoic
Stearic
Oleic
9,11-Octadecadienoic
Linolenic
Eicosanoic
11-Eicosenoic
11,14-Eicosadienoic
Arachidonic
Eicosapentaenoic
Docosanoic
Docosahexaenoic
Tng bo no
Tng bo khng no mt
Tng bo khng no mt ni i
Tng bo khng no nhiu ni i
Soxhlet
(700C/6h)
0,07
4,44
0,13
32,04
1,33
0,14
7,76
41,17
8,03
0,21
0,35
1,80
0,81
0,40
44,93
55,07
44,30
10,77
Kt qu phn tch tng axt bo khng no theo phng php FT-IR l 61,01% l rt
ph hp vi kt qu phn tch theo phng php trch nhit lnh l 61,31%. Trong
khi trch bng phng php Soxhlet nhit 700C l 55,07%. iu ny cho thy c s
thay i tng axit bo khng no theo nhit trch ly.
Kho st s bin i thnh phn axt bo theo nhit trch ly cht bo cho thy
nhit cao lm tng tng hm lng axt bo no t 38,7% n 45,1% v lm gim lng
axt bo khng no t 61,3% xung cn 54,5%. c bit, nhit cao qu lu axt bo
omega-3 nht l DHA loi cn thit cho no b con ngi s hon ton bin mt.
5.4
KT LUN:
VI.
Ngun hng ngoi: Ngun NIR c lm lnh bng khng kh nng lng
cao.
ngh ha hc.
7. Francis