Phn II Cc phng php ph

Chng I: Khi qut v cc phng php ph

I.1.Cc bc x in t
Cc bc x in t bao gm t sng v tuyn n cc bc x Rngen bc
x u c bn cht sng v ht.
*Bn cht sng th hin hin tng nhiu x & giao thoa. Khi truyn trong
khng gian n sinh ra 1 in trng & 1 t trng bin i c cng tn s nhng
c hng vung gc nhau.

E

Thi gian truyn

Hnh II.1 Bc x in t sinh ra 1 in trng E & 1 t trng H vung gc vi nhau
- Khi coi l sng, cc i lng c trng c lin h vi nhau qua cng
thc:
c = . (II.1)
c c
hay ;

Trong : c -Tc truyn sng (tc nh sng)
0
- Chiu di sng (1cm = 10 8 A = 107 nm = 10 4 m)
- S sng trong 1 giy
Chiu di bc sng c o bng cc n v o di, c th l mt (m),
centimet (cm), nanomet (nm), micromet ( m), angtron (A 0)
1m = 100cm = 10 6m = 109nm = 1010A0
Trong quang ph ngi ta cn s dng i lng nghch o l 1 o chiu
di bc sng k hiu l gi l s sng:
1
; n v: cm -1

*Tnh cht ht: Cc bc x in t cn c th xc nh l 1 dng ca cc ht
photon. Cc ht ny mang nng lng. Cc dao ng t ch c th pht ra hoc
hp th nng lng tng n v gin on, tng lng nh nguyn vn gi l
lng t nng lng hay nng lng bc x in t:
c
E h h (II.2)

Trong : E :Nng lng bc x
(1ec = 10 -7J = 2,3884.10 -8 cal = 0,6241.10 12 eV)
h: hng s Plank = 1,054.10 -34Js = 6,59eVs
*Da vo chiu di sng, cc bc x in t c chia thnh cc vng khc nhau
nh: sng v tuyn, sng micro (vi sng), hng ngoi, nh sng nhn thy, t
ngoi, Rnghen, .
Bng II.1.Phn loi cc vng bc x in t

10 10-1 10-4 4. 10-5 10-6 10-8 10-11

(A0) 109 107 104 4. 103 102 1 10-2

(eV) 10-5 10-3 1 4.101 102 104 106
Cc Sng
Hng Nhn T
loi v Vi sng Rnghen Tia
ngoi thy ngoi
sng tuyn

II.2. S tng tc gia vt cht v cc bc x in t

- Khi chiu chm bc x in t vo 1 mi trng vt cht s xy ra hin tng
cc phn t vt cht hp th hay pht x nng lng. Hiu s nng lng m phn
t pht ra hay hp th vo sau khi chiu chm bc x in t: E s bng:
 E = E2-E1 = h (II.3)
Trong : E1v E2 l mc nng lng ca phn t trng thi u v cui
l tn s ca bc x in t b hp th hay pht x ra
Nu E>0 xy ra s hp th nng lng bc x in t
Nu E<0 xy ra s pht x nng lng
- Theo thuyt lng t, cc phn t & cc bc x in t trao i nng lng vi
nhau khng phi bt k & lin tc m c tnh gin on. Cc phn t ch c th
hp th hoc bc x n ln lng t h (n = 1,2,3)
Cc phn t khi hp th nng lng ca bc x in t s gy ra nh ng s
thay i trong cu to phn t nh lm quay hay dao ng cc nguyn t trong
phn t, lm bin dng cc m my in t trong phn t. i vi cc phn t c
momen lng cc 0 th momen ny s b thay i thng qua s quay (momen
quay q ) qua dao ng (momen dao ng e ).

iu ny c m t qua hnh II.2.

a) b)
c)
Hnh II.2 : S thay i a) momen quay
b) momen dao ng
c) momen kch thch in t qua s tng tc vi cc tia
in t
Cc qu trnh ny u i hi mt nng lng xc nh, c tn s ring gi
l tn s quay ( q ), tn s dao ng d , tn s kch thch in t e .
V vy, khi chiu 1 chm bc x in t vi cc tn s khc nhau vo phn
t th n ch hp th c bc x in t c tn s ng bng cc tn s ring ni
trn ( q , d , e ). Do s hp th chn lc ny m khi chiu chm bc x in t
vi gii tn s khc nhau i qua mt mi trng vt cht th sau khi i qua, chm
bc x ny s b mt i mt s bc x c tn s xc nh, ngha l cc tia ny
b phn t hp th.
Chng ta c th xem xt mt cch chi tit nh sau: Eel > Ed > Eqy, tc
mi trng thi electron (c bn hoc kch thch) bao gm mt s trng thi dao
ng khc nhau, n lt n mi trng thi dao ng li bao gm mt s trng
thi quay khc nhau.
Cc bc x c nng lng thp nh sng cc ngn hoc hng ngoi xa ch
lm thay i trng thi quay ca phn t. Do khi nghin cu s hp th bc
x trong vng vi sng hoc vng hng ngoi xa ta x thu c ph quay thun
tu. Ph quay thun tu gm cc vch rt xt gn nhau v cch u nhau, mi
vch c tn s:
E qy
qy
h
Khi phn t hp th bc x vng hng ngoi gn, trng thi dao ng b
kch thch (trng thi electron vn khng thay i), nhng lng t nng lng
tng ng s c tn s:
E dd
dd
h
V Ed >> Eqy nn cng vi s bin thin nng lng dao ng lun c
bin thin nng lng quay. V th ta khng thu c ph dao ng thun tu m
thu c ph dao ng quay, thng vn c gi n gin l ph dao ng
hoc ph hng ngoi. Do kt qu chng cht nhng lng t quay ln nhng
lng t dao ng nn ph hng ngoi ta khng thu c cc vch mnh nh
ph quay m ch thu c cc m vch vi tn s = d + qy.
Cui cng nu phn t hp th cc bc x c nng lng ln hn nh bc
x kh kin hoc bc x t ngoi th nng lng electron ca chng b thay i.
Nu ch c trng thi electron thay i th vch hp th tng ng s c tn s:
E el
el
h
Tuy nhin, ng thi vi s thay i trng thi electron lun lun c c s
thay i trng thi dao ng v trng thi quay nn ta khng thu c cc vch
vi tn s el m thu c cc m vch vi tn s = el + d + qy. Ph thu
c trong trng hp ny c gi l ph hp th electron, hoc gn hn l ph
electron. V ph electron c th hin vng t ngoi v kh kin nn cng c
gi l ph t ngoi kh kin.
Biu din ph hp th phn t:
Ph hng ngoi thng c ghi di dng ng cong s ph thuc ca %
truyn qua vo s sng (hoc bc sng) ca bc x. i vi vng t ngoi v kh
kin cc my ph thng ghi cho ta ng cong s ph thuc ca mt quang
D(A) vo bc sng (hoc s sng). so snh gia cc cht, gia cc cu to
khc nhau ngi ta thng biu din ph t ngoi kh kin di dng s ph
thuc ca h s hp th mol (hoc lg) vo bc sng. vng vi sng, ngi ta
li ghi ph di dng s ph thuc ca cng hp th vo tn s.
II.3. nh lut Lambert-Beer
Khi chiu mt chm tia sng n sc i qua mt mi trng vt cht th sau
khi i qua cng bc x b gi m (do khuych tn hay hp th trong lp mng
vt cht).
Gi s cng ca bc x lc ban u l I 0, chiu qua lp mng vt cht
c chiu chiu dy dx b hp th mt lng l dI. Sau khi i qua lp mng vt
cht, cng bc x cn li l: I 1= I0- dI
I
T s: 1 .100 0 0 T gi l truyn qua
I0
I 0 I1
.100 0 0 A gi l hp th
I1

I0 I1

i lng dI s t l vi chiudxdy ca lp mng, nng e ca dung dch

& bnII.3:
Hnh chtSca tngtn
khuch cht.
hayDo
hpvy
thtamt
c chm
th vit
ti a sng n sc trong lp mng vt ch t
dI
.C.dx (II.4)
'

I
 Trong : C Nng (mol/l)
dx- chiu dy lp mng (cm)
- H s t l ph thuc vo bn cht ca cht nghin cu
Ly tch phn 2 v:
I1
dI
1

I I .C.0 dx
'

I
ln 1 ' .C.d
I0
I
lg 1 .C.d vi 2,3 '
I0
E .C.d (II.5)
*nh lut Lambert Beer:
I
F = lg 1 l mt quang ca dd nghin cu vi nh sng c di sng
I0
l h s tt phn t
C l nng dd
d l chiu dy lp mng (chiu dy Cuvet)
- nh lut Lambert Beer ch ng trong trng hp nh sng n sc.
T phng trnh (II.5) ta nhn thy i vi 1 cht nht nh th gi tr E ch ph
thuc vo nng dd E f c . Do , ta c th lp th E f c di y:
E
271
2,2
2,0 286
1,6 264
1,2
0,8
0,4 C.103

0,25 0,5 0,75 1,00 1,25

Hnh II.4. S ph thuc ca mt quang E vo nng dung dch phenol trong
hexan cc bc sng khc nhau
II.4.Vng quang ph hc
Bc x in t bao gm di ph rt rng. Nhng do gii hn ca cc tia
sng khi i qua cht quang hc nn vng quang ph hc c ng dng ch trong
gii hn t (1000A 0- 100m). Ph thuc vo vic s dng cc vt liu quang hc,
ngi ta phn vng nh sng nh sau:
1-Vng sng 50-1000A0(Vng Laman). Khng th vt liu trong sut
m ch c th s dng cch t. Khng c ngha trong ho hu c.
2- Vng sng 1200-1850A0(Vng Suman). Vt liu quang hc l CaF 2. Cc
tia sng thu nhn c trn knh nh. ng dng nghin cu cc hp cht hu
c.
3- Vng sng 1850-4000A0(Vng t ngoi TB), vt liu quang hc l thch
anh. y chnh l vng quang ph t ngoi. ng dng rng ri nghin cu cc
hp cht hu c. (Ngun sng l n euteri).
4- Vng sng 4000-8000A0(Vng nhn thy), vt liu quang hc l thu
tinh, ngun sng l n in thng (vonfram). Vng ny s dng nghin cu
cc hp cht hu c c mu.
5- Vng 0,8-2m (8000-20000A0)- (Vng hng ngoi gn), vt liu quang
hc c th l thu tinh hoc thch anh. Ngun sng l n thng.
6- Vng sng 2- 40m (20000-40000A0)- Vng hng ngoi c bn. Vt
liu quang hc dng ng thi l: LiF (n6 m), CaF 2(n 9m), NaCl(n
15m),KBr (n27m), CsI (n 40m).Ngun sng dng n Nerst
(85%ZnO 2+15%YO3) (Y- Ytri) C ngha ln nghin cu cc hp cht hu
c.
7- Vng sng 40-200m (400000-2000000A0)- Vng hng ngoi xa. Vt
liu quang hc cch t.
Trong nhng nm gn y c s dng nghin cu cc hp cht hu c.
 CHNG II. Ph hng ngoi v Raman.

II.1 Chuyn ng quay ca phn t - Quang ph quay.

- Cc phn t khi hp th nng lng ca nh sng kch thch nm vng hng
ngoi xa s b quay quanh cc trc cn bng ca chng.
- i vi cc phn t 2 nguyn t nh CO, HCl, NO c khi lng m1 m 2 ,
momen lng cc 0. Gi thit trong qu trnh qua y, khong cch gia 2 phn
t khng thay i. Mu nh vy c gi l mu quay ca 2 qu t hay l mu
Rotato vng chc.
- Cc phn t ca mt cht trng thi kh c th quay xung quanh trng tm ca
n. Nu khi lng nguyn t l m1 & m 2 , khong cch gia tm cc nguyn t l
r th ta trng tm c xc nh.
m1r1 m 2 r2

r1 r2 r m1
m2

Gii h phng trnh ta c: c

r.m 2 r1
r1 (II.6) r2
m1 m 2
r.m1
r2 (II.7) r
m1 m 2 Hnh II.5: S mu phn t gm 2 nguyn t
Theo c hc c in ta c:
Momen qun tnh I ca vt c tnh theo cng thc:
I m i .ri2 (II.8)
i

Trong : m i l khi lng nguyn t

r i l khong cch t tm khi lng n trc quay
- Vi phn t gm 2 nguyn t, momen qun tnh I c xc nh :
I m1 .r12 m 2 .r22 (Thay gi tr r 1, r2 t II.6 & II.7)
 r 2 .m 22 r 2 .m12
I m1 . m .
m1 m 2 2 2
m1 m 2 2
m1 .m 2 m 2 m1 2
I r
m1 m 2 2
m1 .m 2 2
I r .r 2 (II.9)
m1 m 2
m1.m 2
Trong = c gi l khi lng rt gn.
m1 m 2
Cng theo c hc c in, nng lng quay ca mt vt c tnh theo cng thc:
1 (II.10)
E quay I2
2
Trong : I l momen qun tnh
l tc gc.
Theo c hc lng t, bi ton ca s quay phn t gm 2 nguyn t ng nht
vi bi ton ca in t v ht nhn quay quanh tm lc trong nguyn t hidro.
Trong chuyn ng quay ca phn t gm 2 nguyn t c m t bng
phng trnh Schdinger:
2 2 2 2
2 2 2 Eq 0 (II.11)
x 2 y z h
Trong :
: hm sng
x,y,z: to ca cc tiu phn
h: hng s Plank
- T , gii phng trnh trn ta xc nh c nng lng quay ca cc phn t:
h2
E q 2 J J 1 BJJ 1 (II.12)
8 I
(B- Hng s chuyn ng quay c trng cho mi loi phn t)
Trong : J - s lng t quay nhn cc gi tr 0,1,2,3,4.
 Ta nhn thy rng J nhn cc gi tr nguyn, gin on nn nng lng
quay cng nhn cc gi tr gin on, khng lin tc. Gi l c lng t ho.
- Khi hp th nng lng, phn t c th chuyn ln mt mc lng t quay gn
nht, nng lng quay s tng ln:
E E 'q E q (II.13)

Trong :
E 'q - Nng lng quay ca phn t mc cao hn

E q - Nng lng quay ca phn t mc thp hn

E - Hiu s chnh lch gia 2 mc nng lng

*Theo c hc lng t ta c:
c
E h. h..c (II.14) [do c ]

( - S sng ca nh sng m phn t hp th)
* Theo quy tc la chn i vi trng hp quay phn t th hiu s gia 2 bc
nhy nng lng c gi tr 1, tc l J = 1
J2
J1
J = 1 hay J- J =1 (II.15) E J0
v3
Khi , thay (II.15), (II.12) vo (II.13) ta c: J2
J1
J0
v2
h2
E 2 J 1J 1 1 J J 1 J2
J1
8 I J0
v1
J2
h2 h2 J1

E J 1. 2 J 1 (II.16) J0
v0
8 2 I 4 2 I
*Kt hp (II.14) & (II.16) ta c: J2
J1
J0

h2 v3
h..c 2 J 1 J2
J1
4 I J0
v2
J2
h2
J 1
J1
2 J0
v1
4 I.hc J2
J1
J0
2B v0
J 1 (II.17)
hc
* Nh vy momen qun tnh I khng thay i th s chnh lch gia 2 s sng ca
di ph lin nhau trong chuyn ng quay lun hng s.
2B

hc
C ngha l gi tr lun cch u nhau do trn ph s c cc nh hp th
cch u nhau

J 0 1 2 3

2B/hc 4B/hc 6B/hc 8B/hc

* Tuy nhin, trn thc t quang ph quay ca cc phn t ghi c khng phi l
cch u nhau m cng v sau cng st li gn nhau. iu ny thc t l do trong
khi quay, khong cch gia cc nguyn t trong phn t thay i, n s gin ra
hoc p li.
Mu quay nh vy gi l Rotato khng vng chc.
II.2. S dao ng ca phn t Ph dao ng.
ng thi vi chuyn ng quay, cc nguyn t trong phn t cng c th
dao ng, tc l khong cch gia chng tng gim theo chu k nht nh.
* Ta c th hnh dung nh sau: i vi phn t gm 2 nguyn t , khi gi yn mt
nguyn t v ko nguyn t kia ra mt on d r ri b t do, n s dao ng quanh
v tr cn bng vi bin d r khng i. Dao ng ny gi l dao ng t iu
ha. dr dr

r0

Hnh II.6: S s dao ng ca phn t gm hai nguyn t bt i xng

- Trong trng hp ny, phng trnh Schrodinget c dng:
2 8 2
E ddong . 0 (II.18)
x 2 h2
Trong : - Khi lng rt gn
- Hm sng
Edng- Nng lng dao ng
- Gii phng trnh trn ta thu c:
1
E ddong h v
2
Trong : - Tn s dao ng ca cc nguyn t
v - S lng t dao ng, v = 0,1 ,2,3
Khi v = 0 , Ed(v-0) 0, do vy khi phn t khng dao ng n vn cha 1 nng
1
lng nht nh. Nng lng ny gi l nng lng im 0, E 0 h .
2
Vi dao ng iu ho, quy lut la chn v cho php v = 1
Trn thc t, phn t khng dao ng iu ho.
Phng trnh nng lng phi c hiu chn h:
1 1
E d h v x v (II.20)
2 2
Trong : x H s b chnh dao ng khng iu ho.
- ng cong th nng ca dao ng khng iu ho khng cn l ng parabol
nh dao ng iu ho.
Dng iu ho Dng khng iu ho
Ed Ed
4
3 4
3
2 2
1 1
0 0
r r
r0 r0
Hnh II.7: S ng cong th nng ca dao ng i u ho v khng iu ho
- Quy tc la chn i vi phn t dao ng l v = 1, 2Nh vykhi phn t
dao ng c th tip nhn cc bc chuyn nng lng.
v=0 v=1 gi l dao ng c bn
v=0 v=2 gi l dao ng cao mc 1
v=0 v=3 gi l dao ng cao mc 3
v=0 v=n gi l dao ng cao mc (n 1)
II.3. Dao ng quay ca phn t.
- Khi kch thch bi mc nng lng thch hp, c th xy ra qu trnh p hn t b
quay v dao ng ng thi. Nng lng dao ng quay bng tng nng lng
quay v dao ng.
E qd E q E d

h2 1
E qd 2 J J 1 v h (II.21)
8 I 2
- iu kin la chn vi phn t dao ng quay l: J = 1
v = 1,2,3
II.4. Hiu ng Raman.
- Khi chiu 1 chm tia sng vo mt dung dch keo ri qu an st theo hng thng
gc vi tia chiu ban u t a c th nhn thy chm tia khu ch tn.
- Thay th dung dch keo bng dung dch tht, ngi ta cng nhn c cc tia
khuych tn hng thng vung gc vi tia ban u, c tn s 0 bng tn s ca
tia kch thch ban u. Hin tng ny gi l khuych tn Rayleigh.
- Ngoi ra cn nhn c cc tia c tn s nh hn 0-d(vch STOKE) v tia c
tn s ln hn (vch ANTI STOKE) [0+d], c cng yu hn vch 0
- Nhng tia c tn s 0d gi l tia khuych tn Raman
- Nguyn nhn xut hin tia Raman l do tng tc ca tia sng kch thch vi cc
phn t lm bin dng tun hon lp v in t dn n dao ng cc ht nhn
nguyn t vi tn s d .
 REILEIGH

STORES v Anti STORES

Hnh II.8: Cc vch ph Raman
- Nng lng ca tia Raman bng tng hoc hiu nng lng ca cc tia kch
thch ban u v nng lng dao ng.
E Raman E 0 E d h 0 d (II.22)
II.5.Dao ng ring ca phn t.
trn, ta mi ch xem xt cc trng hp phn t c 2 nguyn t. Nhng
trng hp phn t c nhiu nguyn t th s ..
Cc nguyn t trong phn t dao ng theo 3 hng trong khng gian gi l
dao ng ring ca phn t.
S dao ng ring trong phn t c N nguyn t ti a bng 3N- 5 (phn t
thng nh CO2) hoc 3N- 6 (phn t khng thng nh H 2O. Mi dao ng ring
c mt mc nng lng nht nh, tuy nhin c trng hp 2,3 dao ng ring c
cng mc nng lng.
- Ngi ta phn bit dao ng ring lm 2 loi.
* Dao ng ho tr [] thay i chiu di lin kt, khng thay i gc lin
kt.
* Dao ng bin dng [ ] thay i gc lin kt, khng thay i chiu di
lin kt.
- Mi loi dao ng chia lm2 nhm
* i xng: s, s
* bt i xng: a, a
 s , a
V d: CO 2 c 3 nguyn t nn s dao ng ring: 3 3 - 5 = 4
2. s
O C O [ s ]
OCO OCC
[s] [a]
O C O [s]
(-) (+) (-)
(Trn thc t ch c 2 vch 2349 cm -1 v 667 cm -1)
s , a
H2O c 3 nguyn t nn s dao ng ring: 3 3 - 6 = 3
s

3943cm 1 3832cm 1 1648cm 1

[a] [s] [s]
Mi dao ng c th b kch thch bi tia hng ngoi hoc tia Raman hoc bng
c 2 loi tia trn.
- Vi my quang ph hng ngoi, dng ngun sng hng ngoi c th l n
Nerst (85%ZnO 2v 15% Y 2O3).
- Vi my ph Raman, ngun sng c th s dng l tia lase vng nhn thy.
(Kh Ar: 458-528nm; kh Kr:476-799nm; kh He-Ne 632,8nm).
II.6. Mi lin quan gia tn s hp th v cu to phn t.
- Tn s dao ng ca cc nguyn t thuc vo hng s lc ca lin kt v khi
lng ca chng, do cc nh m chc c tn s hp th nm trong vng
5000- 200cm-1
- Ngoi ra, cc yu t dung mi, nng , nhit , trng thi tp hp cng nh
hng n v tr ca cc cc i hp th.
V d: nng dung dch gy nh hng n s thay i v tr ca cc i nh
hp th, c bit vi cht c kh nng to cu lin kt Hidro.
 II.7. Tn s c trng nhm
Theo quan nim dao ng nhm, nhng nhm nguyn t ging nhau trong
cc phn t c cu to khc nhau s c nhng dao ng nh v th hin nhng
khong tn s ging nhau. Nhng tn s ng vi cc dao ng nhm rt c ch
trong vic nhn ra cc nhm nguyn t trong phn t v vy c gi l tn s c
trng nhm. Bng sau dn ra tn s c trng nhm ca mt s nhm nguyn t,
cng vn ph c vit t t nh sau: m (mnh), tb (trung bnh), y (yu),
b (bin i).
Nhm Tn s, cm -1; (cng ) Nhm Tn s, cm -1; (cng )
O-H 3650-3200; (b) C=O 1850-1650; (m)
N-H 3500-2900; (tb) C=C ~1650; (tb-y)
C-H 3300-2700; (m-tb) (C) NO2 1550 (m) v 1350 (m)
S-H ~2550; (tb-y) >SO2 1330 (m) v 1150 (m)

CC ~2200; (y) >S=O 1070-1030; (m)

CN ~2200; (tb) C-O- 1300-1000; (m-tb)

Cc tn s ghi trong bng trn l ng vi dao ng ho tr ca cc nhm.

Dao ng bin dng ca chng thng th hin vng tn s th p hn so vi dao
ng ho tr tng ng. Hnh v di y cho ta thy s phn b tng i cc
vn hp th ng vi cc dao ng ho tr v dao ng bin dng ca mt s nhm
nguyn t thng gp.
4000 3500 3000 2500 2000 1500 1000 500 200
cm-1

O-H C C C=C C-X , M-X (M: KL

N-H CN C=O X=C, N, O, S, Hal)
C-H C=C=C C=N Cc loi dao ng
S-H C=C=N N=O bin dng v cc
NH vn t hp.
II.8. Cu trc phn t v tn s c trng nhm
Tn s c trng nhm ph thuc trc ht vo mi lin kit gia cc
nguyn t trong nhm tc ph thuc vo bn vng ca lin kt v khi lng
ca cc nguyn t tham gia lin kt. i vi dao ng ho tr, s ph thuc
1 k
c biu din bi cng thc: dd (*). Phn cn li ca phn t cng gy
2
nh hng n tn s c trng nhm thng qua cc hiu ng electron, hiu ng
khng gian v lin kt hydro ni phn t.
a) nh hng ca s th ng v
Trong cng thc (*), tn s t l nghch vi khi l ng rt gn tc l cng t l
nghch vi khi lng ca cc nguyn t tham gia lin kt. Khi thay mt nguyn
t bng mt nguyn t ng v khc, bn cht ca lin kt ho hc khng thay i
do hng s lc hu nh khng thay i: k C-H ~ kC-D; kO-H ~ kO-D Tuy nhin khi
khi lng tng th tn s s gim, chng hn:
C-H > C-D ; OH > OD; .
Vic th ng v c th dng kim tra s quy kt cc vn ph hng ngoi.
V d, vn hp th 3314 cm -1 trn ph ClCH 2CCH chnh l vn hp th ca
nhm CH ankin (CH) bi v khi th H bng D ta c vn hp th 2604 cm -1.
b) nh hng ca hiu ng electron
Trong ho hu c, cc hiu ng electron nh hiu ng cm ng (I), hiu ng
lin hp (C) khng nhng gip ta lm sng t nhiu kha cnh v tnh cht ho
hc m cn gip gii thch v tin on s chuyn dch tn s hp th cc cu
to ho hc khc nhau. Khng nn ch i mt mi lin quan n gin gia hiu
ng cm ng hoc hiu ng lin hp vi tn s c trng nhm, trong mi dy
hp cht c th cn xem xt tc ng ca cc hiu ng electron n bn vng
ca lin kt v n th bc ca lin kt trong nhm nguyn t ang xt.
Thng th s lin hp lm gim bc ca lin kt bi v tng bc ca lin kt
n xen gia cc lin kt bi. Do khi cc lin kt bi lin hp vi nhau th tn
s ca chng u gim so vi khi chng v tr khng lin hp, v d:
 Loi hp cht -CC- >C=C< >C=C-C=C< Aren -C-C-

Bc lin kt 3 2 1,9 1,7 1

, cm-1 2150-2260 1620-1680 1600-1650 1500-1600 700-1100

Loi hp cht CH2=CH2 CH3CH=O CH3CH=CHCHO CH3CH=CH=

CH=CHCHO
C=C 1620 - 1618 1615

C=O - 1720 1692 1677

i vi ni i C=C , nhng nhm ht electron lm gim mt electron do

lm yu lin kt i dn ti gim tn s C=C, cn nhng nhm y electron th
ngc li:
Hp cht CH2=CH2 CH3CH=CH2 (CH3)2C=CH2 ROCH=CH 2 CH3ClC=CH 2 Cl2C=CH2

, cm-1 1620 1647 1655 1635 1635 1611

i vi ni i C=O th mi s y electron lm tng cng s phn cc vn

c ca n li lm gim bc lin kt do s dn ti s gim tn s C=O
Hp cht RCOCl RCHO RCOR RCOOR RCONR 2

, cm-1 1815-1790 1740-1720 1725-1750 1750-1730 1690-1650

c) nh hng ca yu t khng gian (sinh vin t tm hiu)

d) nh hng ca lin kt hyro ni phn t
AX H YB
X, Y thng l F, O, N. Y cn phi c t nht mt i electron cha tham gia
lin kt.
Nu c 2 hp phn AX-H v YB u thuc cng mt phn t ta c lin kt
hyro ni phn t. Nu AX -H thuc mt phn t, cn YB thuc phn t khc th
lin kt hyro to ra gi l lin kt hyro lin phn t.
Lin kt hyro c th c xem l lin kt kiu ba trung tm, trong hyro
ng vai tr cu ni. V th lin kt X -H v B-Y u b yu i. Kt qu nghin
cu bng phng php Rnghen xc nhn iu . di lin kt O -H v
C=O trong trng hp c lin kt hyro u tng so vi khi khng c lin kt
hyro.
Chnh v th khi c lin kt hyro th tn s dao ng ho tr ca c 2 nhm
tham gia lin kt u gim i, ngoi ra vn hp th ca nhm X -H thng tri
rng ra (vn t) khng nhn nh trng hp khng to lin kt hyro.
Khc vi dao ng ho tr, lin kt hyro lm kh khn cho dao ng bin
dng ca lin kt X-H v vy lm tng tn s ca dao ng bin dng.
e) nh hng ca trng thi tp hp, lin kt hyro lin phn t
trng thi kh, cc phn t kh xa nh au, chng chuyn ng t do v hu
nh khng tng tc vi nhau. Chnh v vy, nhng s liu thu c t ph IR,
ca cht o th kh l phn nh cc yu t ni phn t, ngha l mi thay i
trn ph u phn nh s thay i v cu trc phn t. Tuy nhi n ph IR ca cht
kh thng c cu trc quay tinh vi i khi lm phc tp cho vic phn tch chng.
iu kin thng, a s cc cht tn ti dng lng hoc rn. V vy, ngi
ta thng ghi ph cc cht th rn, lng hoc trong dung dch.
loi tr nh hng ca cc tng tc mnh gia cc phn t cc cht th
rn hoc th lng tinh khit, ngi ta s dng cc dung dch long vi cc dung
mi tr nh n-hexan, xiclohexan, cacbontetraclorua, cacbon disunfua,
Khi nghin cu ph IR ca cc cht o t rong dung dch cn phi ch ti hai
yu t l nng ca cht tan v bn cht dung mi.
II.9. Cng v hnh dng ca vn ph IR
Khi phn tch ph IR, ngoi vic xem xt v tr (tn s) ca vn ph cn
phi ch ti cng v hnh dng ca vn ph . Ph IR thng c ghi di
dng ng cong s ph thuc gia phn trm truyn qua (100.I/I 0) vo tn s
sng (). i khi ngi ta cn ghi thm c gi tr bc sng (thng tnh ra
micromet). S hp th ca cc nhm nguyn t c th hin vi nhng vn ph
cc s sng xc nh m ta vn quen gi l tn s.
II. 10. My o ph IR
Hnh II.9 trnh by s nguyn l mt my o ph IR (ni gn hn l my
ph hng ngoi) kiu hai chm tia. Ngun bc x (1) pht ra chm tia hng ngoi
vi mi tn s trong vng cn o. Chm tia ny c tch thnh hai phn: i qua
mu (2) v i qua mi trng o (dung mi chng hn, 2) ri n b to n sc
(3). B to n sc tch tng tn s a qua b phn tch gi l detector (4).
Detector s so snh cng h ai chm tia (mt i qua mu v mt ia qua mi
trng o) cho ra nhng tn hiu in c cng t l vi phn bc x b hp
th bi mu. Bt t ghi (5) c ch huy bi tn hiu in do detector cung cp s
ghi li s hp th bc x ca mu.

(2)

(1) (3) (4) 5 (6)

(2)

Hnh II.9: S nguyn l my ph hng ngoi hai chm tia

Nu mu l cht lng hay l dung dch, n c cha trong dng c gi l
cuvet. Cuvet ny c mt ca s cho chm tia hng ngoi ia qua. Ca s ny
lm bng vt liu trong sut vi vng hng ngoi nghin cu. Cc cht lm ca s
thng l NaCl, CaF 2, AgCl, B to n sc (3) trc kia thng dng lng
knh ch to t NaCl, LiF, hoc CaF 2. Ngy nay ngi ta thay bng cch t nhiu
x tng phn gii v d bo qun.
Cc my ph hng ngoi th h mi c ch to theo kiu bin i Furi
(Fourier Transformation Infrared Spectrophometer = FTIR -Spectrophometer).
my o hng ngoi bin i Fourier (hnh II.10) ngi ta khng dng b to n
sc m dng b to giao thoa (giao thoa k) gm t mt gng c nh, gng di
ng v b phn chia chm sng. Bc x hng ngoi sau khi ra khi giao thoa k
s i qua mu ri n detector. Detector ghi nhn s bin i ca cng bc x
theo qung ng d m gng di ng thc hin c ri chuyn thnh tn hiu
in. Khi ta thu c tn hiu di dng hm c a in th V theo qung ng,
V-f(d). Computer s thc hin php bin i Fourier chuyn hm V=f(d) thnh
hm ca cng bc x I theo nghch o qung ng d (tc d -1).
V d-1 chnh l s sng , do thc cht ta c hm s ph thuc ca
cng bc x vo s sng. Bt t ghi s cho ra ph c dng ging nh cc ph
thu c t my ph th h c.
My ph hng ngoi bin i Fourier c u im hn hn my ph hng
ngoi thng. Vic dng giao thoa k cho php lm khe sng rng hn. Do
lng nh sng thu c trn giao thoa k s ln hn nhiu so vi b to n sc
my ph th h c, nh nguyn l hot ng mi, my ph hng ngoi bin i
Fourier gim c nhiu, lm tng tn hiu. Do s dng Computer nn vic o
ph c t ng ho mc cao, ngoi ra ph cn c th c lu tr v i
chiu vi ph ca cc cht c trong th vin ca my.

Piston
Gng B (di ng)

Gng A
(c nh)
Ngun sng
Gng quay

Tia cng hng

Mu

Detector

Phn tch chuyn thnh tn hiu kt s

Computer Tb ghi

Hnh II.10: S nguyn l my ph Fourier th h mi

II.11. Chun b mu
Ngi ta c th o ph cc cht th hi, th lng tinh khit, trong dung
dch hoc trng thi rn.
th hi: hi c a vo mt ng c bit c chiu di khong 10cm, hai
u ng c bt bng tm NaCl.
th lng tinh khit: mt git nh cht lng c p gia hai tm NaCl
phng c mt mng mng b dy 0,01 -1 mm, ta gi l mng lng.
Trong dung dch: Ho tan cht nghin cu vo dung mi thch hp vi nng
1-5%. a dung dch vo cuvet vi b dy 0,1 -1 mm c ca s bng NaCl.
Cuvet th hai ging ht cuvet th nht nhng cha dung mi nguyn cht. Khi
chn dung mi cn lu mt s im sau y. Mi dung mi u hp th bc x
hng ngoi. Nh so snh 2 chm tia i qua dung dch v qua dung mi ngi ta
c th loi c vn hp th ca dung mi. Nhng khi dung mi hp th trn 65%
bc x chiu vo n th khng th thu c ph hp th hng ngoi v khng cn
lng bc x cn thit.
th rn: C 3 cch o, n gin nht l nghin nh 1mg cht nghin cu
vi mt vi git parafin lng (nujol) sau p va thu c gia hai tm NaCl.
Nujol s c tc dng lm gim s tn x nh sng do nhng ht r n gy ra. Trn
ph s c nhng vn ph hp th mnh ca parafin 2850 -2950 v 1350-1450
cm-1. V th kho st s hp th ca cc nhm CH th thay cho parafin lng
ngi ta dng hexaclo butadien.
Mt phng php thun li khc thng c s dng l p vin KBr nh
sau: Nghin nh cht nghin cu vi mt lng KBr ln gp t 10 100 ln ri
nn hn hp trong my nn thnh nhng vin dt. Vin thu c hu nh trong
sut v cc cht trn trong c phn tn ng u. C mt iu bt li l KBr
c tnh ht m, do trn ph thng c vn hp th ca nc m 3450 cm -1.
Dng KBr cng cn lu n kh nng xy ra phn ng trao i cation hoc
anion trong trng hp cc cht nghin cu l mui hoc cc phc cht v c.
II. 12. Hp th hng ngoi ca cc cht hu c
V d 1: Ph IR ca Limonen o th lng tinh khit

A: 3100 cm -1 (y) : =CH2 (CH ca anken u mch: xem Biu 2.1 v bng 2.7)
B: 3040 cm -1 (y) : CH ca anken gia mch (xem Biu 2.1 v bng 2.7)
C: ~2960 cm -1 (m) : CH no (xem Biu 2.1 v bng 2.6)
D: 1640 cm -1 (tb) : C=C (khng phn bit gia hai ni i, xem biu 2.4 vbng 2.14)
E: 1450 cm -1 (m) : CH (CH2, CH3 , xem biu 2.15 v bng 2.6)
F: 1380 cm -1 (tb) : CH3 (dao ng bin dng i xng ca CH3 , xem biu 2.15 v bng 2.6)
G: ~890 cm -1 (m) : CH ca ni i u mch (biu 2.5 v bng 2.7)
H: ~800 cm -1 (tb) : CH ca ni i gia mch (biu 2.5 v bng 2.7)
V d 2: Ph IR ca xeton (o trong CCl 4)

A: 3600 cm -1 (y) OH t do (biu 2.1 v bng 2.8)

B: 3450 cm -1 (tb) OH lin kt hyro yu (biu 2.1 v bng 2.8)
C: 2960 cm -1 (m) CH no (biu 2.1 v bng 2.6)
D: 1700 cm -1 (m) C=O xeton (biu 2.3 v bng 2.13)
E: 1370 v 1390 cm -1 (y) CH ca nhm >C(CH 3)2 (biu 2.5 v bng 2.6)
F: 1040 (tb) C-O ca nhm C-OH (biu 2.5 v bng 2.8)
(C lin kt hyro)
Bi tp 1: Hy quy kt ph IR ca C 6H5CH2CH2CH2CCH (o dng nguyn cht)

Bi tp 2: Hy quy kt ph IR ca p-O2NC6H4CC-COOH (trong KBr)

Bi tp 3: Hy quy kt ph IR ca amit II (trong KBr)
Biu 2.1: Tn s dao ng ho tr ca lin kt n vi hyro
(m: mnh; tb: trung bnh; y: yu; b: bin i)
 Biu 2.2: Tn s dao ng ho tr ca lin kt ba v hai lin kt i lin

2400 2300 2200 2100 2000 1900 cm -1 Nhm Bng

Biu 2.3: Tn s dao ng ho tr ca nhm cacbonyl (tt c cc vn C=O u mnh)
1900 1800 1700 1600 1500 cm -1 Nhm Bng
 Biu 2.4: Tn s dao ng ho tr ca cc lin kt i
(tr C=O v dao ng bin dng ca lin kt N -H)
Biu 2.5: Mt vi vn ph c trng trong vng vn ngn tay
Bng 2.6: Nhm CH no

-Dao ng ho tr nhm CH 2 v CH3 c th l i xng hoc khng i xng:

H H H H
C C C H C H
H H H H
CHkx~2925 CHx~2850 CH ~2960
kx
CH ~2870
x
Dao ng bin dng ca cc nhm CH 2, CH3 c nhiu kiu: bin dng phng, bin
dng khng phng, bin dng kiu con lc, kiu qut, kiu x on ng ch
hn c l cc tn s sau:
H H H H
C C C H C H (-)
H H H H
CH2 li ko CH2 con lc CHkx CHx
~1465 ~720 ~1460 ~1380
Bng 2.7: Nhm CH khng no v CH thm

- Nhm CH khng no v CH thm c th c phn bit vi CH no bi v

thng chng hp th tn s trn 3000 cm -1, cn CH no di 3000 cm -1. Tuy
nhin, do cng nh hn nn hay b che ph bi vn no CH, hoc cc vn NH,
OH c cng ln hn nhiu
 Bng 2.8: Nhm OH ancol v phenol

- nh hng ca lin kt hydro ni phn t v lin phn t n vn OH

- Vn OH lin kt hydro ca ancol, phenol v axit c th bao trm c vng
hp th ca vn CH vt qua cc vn ny ti tn 2500 cm -1
Bng 2.9: Nhm NH ca amin, imin, ion amoni v amit

- Lin kt hydro amit? Khi c lin kt hydro tn s NH amit gim t hn so vi

nhm OH. Cng ca vn NH amin cng thp hn so vi OH .
Bng 2.10: Cc nhm X H khc

Bng 2.11: Cc nhm lin kt ba

- Nhm - CC v - CN khi lin hp vi ni i C=C hoc ni ba C C th tn s

gim i nhng cng tng ln, cn khi lin hp vi nhm C=O th tn s t b
nh hng. Cc nhm >C=C< v - CC - i xng hoc gn i xng thng
khng hot ng trong ph IR.
Bng 2.12: Cc ni i lion

- Cc nhm X=Y=Z thng hp th mnh v cng l h c tng tc mnh

gia cc lin kt tng t nhau lm cho tn s dao ng dx v kdx phn tc xa
hn.
Bng 2.13: Nhm cacbonyl (vn C=O lun l vn mnh)
Bng 2.13: Nhm cacbonyl (tip theo)
Bng 2.13: Nhm cacbonyl (tip theo)
Bng 2.13: Nhm cacbonyl (tip theo)
-

- Cng hp th: nhm cacbonyl axit hp th mnh hn so vi este,

este li mnh hn xeton v andehit. Amit hp th gn vi xeton nhng cng
thay i nhiu hn.
- V tr vn CO: nh hng ca cu to n v tr vn CO c th tm tt:
a) Nhm X trong h RCO-X- cng m in th tn s cng tng.
b) Nhm , khng no h thp tn s t 15 -40 cm-1 tr trng hp amin li
tng tn s thm 15cm -1.
c) S lin hp xa hn v tr , ch gy hiu ng yu
d) Nhng vng c sc cng lm tng ng k tn s phn bit gia cc
vng 4 cnh, 5 cnh v >5 cnh thuc loi xeton, lacton, lactam (vng > 5
cnh hp th tn s ging nh mch h tng t)
e) Lin kt hydro nhm cacbonyl lm gim tn s 40-60 cm-1. Tn s CO
khi o th rn thng thp hn trong dung dch long.
f) Thng c cng tnh khi mt vi yu t cng nh hng n CO
Bng 2.14: Anken

- Cc nhm th y electron lm tng tn s hp th cn cc nhm ht

electron lm gim tn s hp th. Khi anken hon ton i xng th C=C khng
hot ng trn ph IR.
- Trans anken hp th km hn cis anken, nhng du hiu phn bit
chng l tn s CH (dao ng bin dng khng phng bng 2.7).
- nh hng ca kch thc vng n C=C cng ging nh n C=O . Khi
kch c vng gim tn s hp th ca ni i hng ra ngoi vng (exo, ngoi
vng) tng, cng tn s ni i trong vng (ni vng) th gim. Khi sc cng vng
tng th CH tng cht t.
 Bng 2.15: Hp cht thm

Hp th ca cc hp cht thm th hin 5 vng: vng 1600 1500 cm-1 c th

c 2 hoc 3 vn do dao ng ho tr ca cc lin kt C C trong nhn gy nn
(dao ng khung). Nhng vn ny l c trng cho cc nh n thm loi 6 cnh nh
nhn benzen, nhn pyridin. Vng tip theo t 125 950 cm-1 hu nh khng c
gi tr xt on. Vng di 900 cm -1 c cc vn dao ng bin dng ngoi mt
phng ca cc lin kt CH thm ( CH). Vng ny c th gip xt on v s lng
v v tr cc nhm th (bng 2.15). Tuy nhin, v nhng vn CH thm khng phi
l nhng vn duy nht, thm ch cng khng phi l nhng vn mnh nht trong
vng ny, cho nn vic xt on theo bng 2.15 cn phi thn trng. Vng th t
l vng 2000 1600 cm-1. vng ny thng xut hin vn ho m v vn t hp
ca hp cht thm. l cc vn rt yu nn cng t c s dng. Vng 2950
3100 cm -1 c cc vn CH thm cp bng 2.7.
Bng 2.16: Nhm >C=N, -N=N- v -N=O

Bng 2.17: Hp cht cha lu hunh (c a thm c vng nhm chc)

Bng 2.18: Hp cht cha photpho

Bng 2.19: te v dn xut halogen

 Chng III. Ph t ngoi- Ph kh kin.
(Quang ph kch thch in t)

S hp th ca phn t trong vng quang ph t ngoi v kh kin ph

thuc vo cu trc in t ca phn t. S hp th nng lng c lng t ho
v do cc in t b kch thch nhy t qu o c mc nng lng thp ln mc
nng lng tng i cao. Hay ni cch khc, t ocbitan lin kt hoc khng lin
kt ln ocbitan phn lin kt. Bc chuyn ny i hi hp th nng lng t
ngoi E h h c .

Do cu trc in t ca phn t m nng lng kch thch i hi ln hay
nh ng vi cc tia hp th c bc sng ngn ha y di nm trong vng t ngoi
hay kh kin (200-800nm) hoc vng t ngoi xa(<200nm). Cc in t t
ocbitan lin kt nhy ln ocbitan phn lin kt c mc nng lng cao nht, ng
vi =120-200nm.Cc in t v cp in t t do nhy ln ocbitan phn li n kt
c mc nng lng cao hn nm trong vng t ngoi(200-400nm) hay vng kh
kin (400-800nm) tu theo mch lin hp ca phn t.
III.1. Bc chuyn di nng lng.
iu kin bnh thng, cc in t trong phn t nm trng thi c bn.
Khi c nh sng kch thchvi tn s thch hp th cc in t ny s hp th
nng lng v chuyn ln cc trng thi kch thch c mc nng lng cao hn.
Theo c hc lng t, qu o in t ca cc phn t c chia thnh:
- Ocbitan lin kt ,
- Ocbitan phn lin kt *, *
- Ocbitan khng lin kt n
Mc nng lng ca cc ocbitan ny khc nhau. Ocbitan c mc nng lng
thp nht, ocbitan * c mc in t cao nht (Hnh II.1). Cc in t nm
ocbitan , , n gi l cc in t , hay n. in t n chnh l in t khng lin
kt cc d t nh O, S, Nhay cn gi l cp in t t do.
 Hnh II.9: S bc chuyn nng lng ca cc electron trong phn t
Theo c hc lng t, trng thi c bn cc in t c sp y vo cc
ocbitan lin kt , hoc ocbitan n. Khi b kch thch (hp th nng lng), cc
in t s chuyn ln mc nng lng cao hn. Cc in t s chuyn t
ocbitan sang *, in t chuyn t ocbitan sang *, in t n chuyn t
ocbitan n sang *,*
- Cc bc nhy ny gn lin vi bc chuyn nng lng khc nhau. Hiu s
mc nng lng gia 2 ocbitan chnh l nng lng hp th t ngun nh sng
c
kch thch bn ngoi E h h .Bc nhy ln * cn nng lng ln nht

tc l nh sng kch thch c bc sng ngn nht. Bc nhy ln * cn mc
nng lng nh hn nn bc sng di hn. Cc in t t do n c th nhy sang
*, *, ta nhn thy t n sang * cn nng lng nh nht v c bc sng ln hn
c.
Nh vy, chiu di bc sng ca cc cc i hp th s thay i.
*< *< n*<n*
ly v d, ta quan st bc nhy in t ca nhm C = O khi b kch
thch bi nh sng. Nhm C = O c 2 in t v 2 in t * to lin kt i gia
C = O, ng thi nguyn t oxi cn cp in t t do .
Bng II.2. S hp th ca cc hp cht cacbonyl
Bc chuyn di nng lng (nm) Nng lng kch thch (Kcal/mol)
* 120 230
* 100 184
n* 180 162
n* 280 82
Thng thng, trong qu trnh kch thch in t c km theo qu trnh
quay v dao ng ca phn t, do nng lng chung ca h phn t bng tng
nng lng ca cc qu trnh trn.
Et Eq Ed Ee
Trong : E e >> E d >> E q
Do vy, khi ghi ph t ngoi ca cc hp cht dng hi, ta nhn c ph
vi nhiu nh tinh vi c trng cho qu trnh quay v dao ng ca phn t.

Hnh II.10: Ph t ngoi ca CH 3I: (a)-Dng hi ; (b) Dng dung dch

III.2. Nguyn l Franck Condon v cng vch ph.
Ngi ta nhn thy mi bc chuyn in t u tun theo 1 quy lut la
chn ca nguyn l Franck Condon.
Bc chuyn in t t 1 trng thi in t ny sang 1 trng thi in t
khc xy ra rt nhanh (10 -16s), trong khi dao ng ht nhn xy ra chm hn
(10-13s) nn khong cch ht nhn hu nh khng thay i trong khong thi gian
chuyn in t ny.
Theo nguyn l Franck Condon, trong s k ch thch in t xy ra rt
nhanh, bc chuyn in t no din ra trong khi khong cch cc ht nhn khng
thay i s c xc sut ln nht. Ta xt cc trng hp:
a- Khi phn t b kch thch in t, khong cch ht nhn khng i (r = r 0),
ng cong th nng trng thi in t c bn v trng thi in t b kch thch
khng lch nhau vi khong cch r.
Bc chuyn dao ng t v= 0 sang v= 0 c xc sut ln nht. Cc bc
chuyn khc c xc sut nh hn. Xc sut ny gim i cng vi s tng v. Do
vy, trong cu trc dao ng ca ph t ngoi, bc chuyn v= 0 sang v= 0 c
cng ln nht. Cc nh khc c cng nh hn. ng ph c cu trc
bt i xng. (Hnh II.11. a,b)
b- Khi phn t b kch thch in t, khong cch ht nhn tha y i (r < r 0), ng
cong th nng trng thi kch thch b dch chuyn so vi trng thi c bn. Bc
chuyn dao ng t trng thi c bn v= 0 sang v= 0 khng phi mc kch
thch in t c xc sut ln nht. Ngc li, do s chuyn dch ca n g cong
th nng trng thi kch thch in t nn bc chuyn v= 0 ln trng thi dao
ng cao hn (V d v= 2) s c xc sut ln nht (v theo mc chuyn ny s
m bo cho khong cch cc nguyn t khng i).Ngoi ra, xc sut chuyn t
v= 0 cc mc dao ng khc s c xc sut nh hn. (Hnh II.11.c, d)
 Hnh II.11: Bc chuyn in t theo nguyn l Franck -Condon
Theo c hc lng t, khi phn t trng thi dao ng c bn (v=0) th
hm s sng v do mt xc sut c gi tr cc i trung im ca dao
ng, ngha l v tr r=r 0 suy ra v=0 v v=2 l ln nht.
III.3. S lin quan gia nhm mang mu v v tr ca cc i hp th.
T lu, ngi ta nhn thy cc cht c mu l do trong phn t c cha
nhiu nhm ni i ni ba nh C=C, C=O, N=N, C C, NN gi l nhm mang
mu.
Vic nghin cu v quang ph in t ch ra rng cc phn t c cha
cc nhm mang mu c cc i hp th nm v pha sng di hn nhng phn t
khng cha chng. S c mt ca mc h lin hp ca nhiu nhm mang mu trong
phn t lm cc i chuyn dch v pha sng di hn.
 Bng III.3. Mt s gi tr cc i hp th ca cc cht.
Hp cht max(nm) max
CH3OH 183
CH3NH2 213
CH2= CH2 162 10.000
CH3CHO 167
CH3 CH2CH2C CH 172 4.500
CH2= CH- C CH 219 7.600
CH2= CH- CH= CH2 217 20.900
Nh vy, nu nhiu nhm mang mu lin hp vi nhau th mu ca chng
cng m. Cc cht c nhiu nhm lin hp c mu m th cc i hp th
chuyn dch v pha sng di.
c trng cho s thay i v tr cc i hp th trong ph in t ngi
ta nu ra mt s khi nim:
- Chuyn dch batcrom ngha l chuyn dch cc i hp th v pha sng di.
- Chuyn dch hipscroin: chuyn dch cc i hp th v pha sng ngn.
- Hiu ng hipecrom: ngha l lm tng cng hp th.
- Hiu ng hipocrom: ngha l lmgim cng hp th.
C cc kiu lin hp tng ng vi cc di hp th nh di R, K, B,
1) Lin hp *
- Trng hp ny xut hin khi trong hp cht cc ni i lin hp. Cc c c i
chuyn dch mnh v pha sng di v cng hp th tng khi s ni i lin
hp tng.
Bng II.4. Cc i hp th ca polien CH 3(CH=CH) nCH3
n max(nm) max
1 174 24000
2 227 24000
3 275 30200
4 310 76500
5 342 122000
- Nguyn nhn ca s thay i l do s lin hp gia cc lin kt lm thay i
mc nng lng ca cc ocbitan, rt ngn hiu s nng lng ca bc chuyn
in t. Ta c th biu din nh hng ca s lin hp n cc mc nng lng
nh Hnh II.12 (So snh gia etylen & but adien)

Hnh II.12: S biu din nh hng ca s lin hp n cc mc nng lng

Di hp th tng ng vi bc nhy ny l di K. Di K nm v pha sng ngn,
c cng hp th ln(max >10.000).
Di K: - Trong dung mi phn cc polien t nhy cm vi dung mi phn cc
batocrom
phenol (do E kch thch gim v do tng tc lng cc v cc lin
hipecrom
kt Hyro)
- Mch lin hp tng: batocrom, tng.
y ta c th coi ocbitan phn t ca butadien nh t hp ca cc hm
sng phn t ca etylen. trng thi c bn, 2 phn t etylen c hm sng phn
t l 1, 2- trng thi kch thch l 1* , *2 . S t hp ca hm sng ny, ta c 4
hm sng phn t ng vi:
Mc c bn: 1+ 2 v 1- 2
Mc kch thch: 1* *2 v 1* *2
Trn s ta nhn thy bc nhy kch thch in t phn t etylen 1 1* s
ln hn cc bc nhy in t butadien (1- 2) ( 1* *2 ) nhiu, do cc
i hp th max tng [Konjugiert].
 i vi bengen, xut hin ca di hp th ng vi bc chuyn di ca h
thng in t c di B (Bengenoit). Di B c trng cho quang ph ca cc phn
t vng thm & d vng. Di hp th B l di hp th rng vng t n goi gn
230 270nm
khong , c nhiu nh cu trc tinh vi.
230
- Khi c nhm mang mu mi vi nhn thm, di B quan st c vng
sng di hn di K nhng di K li c cng hp th cao hn. (Batocrom,
hipocrom).
V d Styren c di K max =244nm, max =12.000
v di B max =282nm, max =450
- c trng cu trc tinh vi ca di B c th vng mt trong ph ca cc
hp cht thm c nhm th hoc trong dung mi phn cc.
2) Lin hp p.
y l s lin hp ca ni i v cp in t t do cc d t trong lin
kt i C=Z (Z=O, N,S) v C -X (X=Cl, Br,I) tng ng vi bc nhy in
t n* . Di hp th c trng cho bc nhy ny l di R (Radikal).
Ta c th biu din s s lin hp p nh hnh II.13.

Hnh II.13: S mc nng lng ca hp cht cacbonyl cha bo ho -

 - Trong trng hp ny, ta nhn thy mc nng lng ca cc lin kt
C=C v C=O khc nhau nn s tng tc ca chng nh hn, ng th i li c
bc nhy in t ca cc in t t do ca ocbitan n ca d t oxi.
S lin hp ca cc lin kt khng nh hng n mc nng lng ca
ocbitan n nhng bc nhy nng lng ca cc in t n li b thay i v cc
in t n s nhy sang ocbitan * lin hp mi.
Trn s ta nhn thy bc nhy * cacbonyl - ng thi bc
nhy n* rt ngn. Do vy cc i hp th tng ng dn xut vinyl -
cacbonyl chuyn dch v pha sng di hn so vi hp cht c ni i bit lp.
- Nh vy c th nhn xt rng di R c cc i hp th nm sng di hn
di K nhng cng hp th lun nh hn ( =10100)
- Trong dung mi phn cc: hiu ng hipocrom.
- Trong trng hp mch lin hp tng: batocrom, khng tng.
3) Lin hp - .
Nhm th ankyl lin kt gy ra hiu ng siu lin hp, cc in t trong
phn t chuyn dch theo s :

Hiu ng ny lm cc i hp th chuyn dch v pha sng di mt t

Bng II.5
Hp cht max max
CH2= CH2 165 16.000
(CH3)2C= C(CH3)2C 196,5
CH2= CH- CH= CH 2 217 21.000
CH3 CH= CH- CH = CH 2 223 24.000
CH3 CH= CH- CH = CH- CH3 227 24.000
III.4- Cc yu t nh hng n cc i hp th.
1) nh hng ca nhm th.
Khi cc nhm th gn vo c c v tr khc nhau ca phn t, n s lm cho
cc i hp th thay i. S thay i ny ph thuc vo bn cht nhm th v v
tr ca nhm th.
- Nu nhm th khng phi l nhm lin hp CH 3, CH2OH, CH2COOH) th
s nh hng n cc i hp th t.
- Nu nhm th l nhm lin hp (C= CR 2, COOH, OH, NO 2) th nh
hng mch, chuyn dch cc i hp th v pha sng di v tng cng hp
th.
Bng II.6- nh hng ca nhm th n cc i hp th C 6H5X
Di K Di B
Gc th Cht
max max max(nm) max
H Benzen 203 7400 254 205
CH3 Toluen 206 7000 261 225
OH Phenol 211 6200 270 1450
CHO Benzandehit 242 1400 280 1430
NH2 Anilin 230 14000 280 1400

2) nh hng lp th.
Hiu ng lp th nh ng phn cis, trans, tnh ng phng ca phn t c
nh hng n cc i hp th.
* Tnh ng phng.
Ta bit s ko di mch lin hp ca phn t lm cc i hp th chuyn
dch v pha sng di. S lin hp ch c c khi phn t nm trn 1 mt phng.
Khi tnh ng phng mt i th s lin hp b ph v.
 Trn sc ph c th nhn thy khi tnh ng phng mt i, di bc sng
ca cc i hp th thay i t nhng thay i nhiu. C th ly lm thc o
tnh ng phng ca phn t. Ta c th ly axetophenon lm v d:
Bng II.7- nh hng nhm th axetophenon.
Nhm th max(nm) max ,
Khng th 243 13.200 0
2- CH3 242 8700 40
2,6- Dimetyl 240 2.000 67
2,4,6- Trimetyl 242 2.500 68
* ng phn cis, trans.
Cc i hp th ca cc ng phn cis, trans c s khc bit:
- ng phn trans c cng hp th cao hn ng phn cis.
- Cc i hp th ca ng phn trans chuyn dch mt t v pha sng di
so vi ng phn cis.
- ng phn cis c xut hin thm hoc lm tng cng mt cc i
hp th v pha sng ngn.

Hnh II.14: Ph t ngoi ca trans-stiben v cis-stiben, -carotin

3- nh hng ca dung mi.
Dung mi c nh hng n v tr cc i hp th tu theo phn cc ca
chng. nh hng ny khc nhau i vi cc di hp th khc.
Khi tng phn cc dung mi th di K chuyn dch v pha sng di cn
di R chuyn dch v pha sng ngn.
III.5- Ph t ngoi v kh kin ca mt s hp cht hu c
III.5.1- Hp cht cha nhm mang mu bit lp
- Cc hp cht hu c c nhm mang mu bit lp nh C= C, C C, C= N,
C= O,NO2, NH2cho cc bc nhy * nm vng nh hn 190nm ( =104)
v bc nhy n* nm vng nh hn 400nm ( =102).
Bng II.8- Ph t ngoi ca mt s nhm mang mu bit lp
Nhm Hp cht Bc chuyn max Log Dung mi
C= C CH2= CH2 * 162,5 4,2 Heptan

n* 279 1,2
C= O (CH3)2C= O Heptan
* 188 3,3

C= N (CH3)2C=N-OH * 193 3,3 Etanol

C C CH CH * 173 3,8 Dng kh

III.5.2- Hp cht polien (-CH2= CH2-)n

- Hp cht polien cho cht hp th cc i ng vi bc nhy * nm
trong vng 200- 400nm tu theo mch lin hp di hay ngn v s c mt ca cc
nhm th khc nhau trong phn t.
- c im ca bc chuyn * l cng hp th ln. Cu trc khng
gian c nh hng n v tr ca cc i hp th.
 Bng II.9. Hp th cc i ca nhm polien.
Hp cht max (nm) Lg max Hp cht max lg max

CH2= CH- CH= CH 2 217 4,3 237 3,9

CH2= CR- CH= CH 2 220 4,3 247 4,3

RCH= CR- CH= CH 2 223 4,4 CH3-(CH=CH) 3-CH3trans 275 4,5
CH2= CR- CR= CH 2 226 4,3 CH3-(CH=CH) 3-CH4 trans 310 4,9
R- CH= CH- CH= CHR 227 4,4 CH3-(CH=CH) 3-CH5trans 341 5,1
V mt thc nghim, ngi ta a ra cng thc tnh cc i hp th c a
polien theo quy lut Woodward:
 max = 246 (dien cng vng - 0)
+ 5 (1 ni i exo)
+ 15 (3 nhm th)
273 nm
Cholesta-2,4 dien (Thc t: max = 276 nm; max = 10.000)

max = 253 (dien cng vng - 0)

+ 20 (4 nhm th gc)
273 nm
(Thc t: max = 272 nm)

C 4H 9
max = 253 (0)
+ 25 (5 nhm th gc)
+ 60 (2 lin kt i ko di)
+ 15 (3 vng exo)
353 nm
H3CCOO (Thc t: max = 356 nm)
max = 253 (0)
+ 25 (5 nhm th gc)
+ 60 (2 lin kt i ko di)
+ 5 (1 vng exo)
343 nm
H3CCOO
(Thc t: max = 356 nm)

C8H17 max = 253 (0)

+ 20 (4 nhm th gc)
273 nm
(Thc t: max = 275 nm)
III.5.3- Hp cht cha nhm cacbonyl.
Cc hp cht cacbonyl khng bo ho , c mch lin hp trong phn t

H3C max = 215 (0)

+ 30 (1 ni i lin hp)
O
+ 18 (1 nhm th )
H3C
+ 2*18 (2 nhm th )
CH3 CH3
299 nm
(Thc t: max = 296 nm)
 max = 215 (0)
+ 30 (1 ni i lin hp)
+ 12 (ankyl )
O + 18 (ankyl )
+ 5 (1 ni i exo)
280 nm (Thc t: max = 296 nm)
H3C max = 193 (0)
+ 12 (ankyl )
O 205 nm (Thc t: max = 205 nm)
HO
H3C
max = 215 (0)
+ 12 (ankyl )
CH3 227 nm
O
(Thc t: max = 205 nm; 315 )
* n*

Hnh II.15: Ph t ngoi ca trans -penten-3-on-2

III.5.4- H vng thm bengen.
Bengen dng hi ng vi bc chuyn in t * cho hp th :
= 184nm (=46000) ng vi bc chuyn A 1gE2v
= 203nm (= 7400)- di K ng vi bc chuyn A 1g B1v
= 256nm (= 204)- di B ng vi bc chuyn A 1g B2v
Di B Cu trc nh tinh vi, c trng cho vng benzen

Hnh II.16: Ph UV ca benzen dng hi

Khi c mt nhm th, v tr cc i hp th thay i. Nu nhm th l gc
ankyl, cc i chuyn dch t v dng ph t thay i. Nu nhm th lin hp,
(CHO, COOH, OH, NH 2) cc i chuyn dch v pha sng di mt nh tinh
vi.
V d: Ph ca toluen, anilin, benzendehit:
Hnh II.17: Ph t ngoi ca toluen (trong hexan) v anilin (trong dung dch m
photphat pH=8)

Hnh II.18: Ph t ngoi ca benzadehit trong metanol

Bng II.5 : nh hng ca cc nhm th n cc i hp th ca phn t benzen
c nhm th (trong dung mi heptan)

Quy lut tnh cc hydrocacbon vng thm c nhm axyl:

C F
= 0 + Ai
x O

R=H 250 nm
R = Ankyl, vng 246 nm
R = OH, O-ankyl, O-vng 230 nm
 Ai Octo Meta Para
Ankyl 3 3 10
OH, O-ankyl 7 7 25
-O 11 20 78
-Br 2 2 15
-Cl 0 0 10
-NH2 15 15 58
-N(ankyl)2 20 20 85
V d 1:
max = 246 (0)
O CH 3 + 25 (para O-ankyl)
+ 3 (ankyl-O)
274 nm (Thc t: 276 nm)
O
V d 2:
max = 246 (0)
+ 7 (m O-ankyl)
+ 3 (ankyl-O)
O CH3
256 nm (Thc t: 257 nm)
O

V d 3:
O max = 250 nm (0)
CH (Thc t: 257 nm)
III.6. S my ph t ngoi.

(1) (3) (4) (5)

(2)
Hnh II.21: S my ph t ngoi
1- Ngun sng km thit b tch nh sng n sc.
2- Curet ng mu.
3- Thit b quang hc (Lng knh thch anh, gng quay, t bo quang in)
4- B khuych i tn hiu.
5- B ghi.
- Cc my ch to o c vng t ngoi v kh kin (800 - 200nm) ngun
sng cn 2 loi n.
- n Deuteri dng cho vng t ngoi (400- 200nm)
- n nh sng thng cho vng t ngoi kh kin (800 - 400nm)
- V nh sng t ngoi khng qua thu tinh nn cc lng knh v ca s Cu vet u
phi bng thch anh.
C th o mu dng hi hoc dng dung dch ng trong cuvet th ch anh
Dung mi ghi ph t ngoi: CH 3OH, C2H5OH, C5H12, C6H14, Clorofoc,
* Phng php ghi mu.
- Khi o mu dng hi ch cn nh 1 t cht lng vo y Curet, y kn np
hi ho tan trong Cuvet.
* Yu cu dung mi.
- Ho tan mu o vi nng nht nh, ng thi khng c phn ng vi cc
mu o
- Dung mi khng c hp th trong vng cn o ( thng l cc dung mi khng
c ni i trong phn ng).
- Dung mi tht tinh khit (thng phi tinh ch theo phng php ring)
 Chng IV Ph cng hng t Ht nhn

5.1. C s l thuyt v s nguyn l ca my ph cng hng t ht nhn

a) C s l thuyt
Cc ht nhn nguyn t mang in tch dng, t quay quanh mnh v sinh ra
mt dng in vng. Dng in ny to ra mt t trng c momen t . Mt
khc, khi ht nhn quay cng sinh ra momen quay gi l momen spin ht nhn p .
Chng quan h vi nhau theo biu thc:

.p (II.26)
Trong : l hng s t thm c trng cho mi ht nhn.

p
N

i
S

.p

Hnh 5.1: S momen spin ht nhn v momen t

Ht nhn ca mi ng v c c trng bi s lng t spin (I). N lin
quan ti v p theo biu thc:
h
p . I(I 1) (II.27)
2
h
I(I 1) (II.28)
2
1 3
Trong : I= 0, ,1, , 2, tu theo s khi v s th t nh th no.
2 2
, p l gi tr tuyt i ca momen t v momen spin
Cc ht nhn c I 0 c gi l cc ht nhn t. Khi t cc ht nhn t vo
t trng ngoi c cng H 0 th cc momen t ht nhn s xoay theo hng
ng sc ca t trng ngoi. S xoay hng ca cc momen t khng phi bt
k m ch c mt s v tr nht nh trong khng gian gi l s lng t ho c
c trng bi s lng t m, m nhn gi tr -I, -I+1, -I+2 n +I, tc l c (2I+1)
gi tr ca m, hay (2I+1) kh nng nh hng.
- i vi ht nhn 1 H , 13 C ; c I 1 m 1 tc l c 2 kh nng nh
2 2
hng. Mi s nh hng khc nhau ca hnh chiu p trn trc hng t
trng( trc hng t trng ngc vi hng trc z).

Khng c t trng
H0

z z E

H0
1 h
Pz p z

2 2

1 h
z
Pz p 2 2
x

y
Hnh 5.2: Kh nng nh hng ca momen t trong t trng ngoi
h
pz mi. (II.29)
2

Trong : p z l hnh chiu p trn trc z

 h
z .m i (II.30)
2
1 h
Vi ht nhn 1H, 13C (m=1/2) z .
2 2
Tu thuc vo s nh hng, ht nhn s chi m 2 mc nng lng khc nhau:
E = -mi.H0 (II.31)
1 1 h
m E 1 . H 0 [mc thp] (II.32)
2 2 2
1 1 h
m E 2 . H 0 [mc cao] (II.33)
2 2 2
Hiu s gia 2 mc nng lng:
E E 2 E 1 h 0

h
. H 0 h 0
2
1
0 H 0 (II.34)
2
iu kin cng hng: Gi s cc ht nhn c spin I=1/2 c t trong mt t
trng H0 th cc ht nhn s c 2 cch nh hng tc l s phn b hai mc
nng lng. By gi nu ta chiu vo mu sng v tuyn c tn s xc nh th
cc ht nhn mc nng lng thp s hp th nng lng ca sng v tuyn
chuyn ln mc cao. Ngi ta ni lc xy ra cng hng t ht nhn
(Nuclear Magnetic Resonance: NMR). Qu trnh cc ht nhn mc nng lng
cao gii phng phn nng lng hp th c tr v mc nng lng thp gi
l qu trnh hi phc.
1
m (E2)
2
E
E
Vng t
trng 1
m (E1)
C t trng 2
Hnh 5.3: S phn b mc nng lng ca ht n hn c I=1/2 trong t trng ngoi
b) S nguyn l ca my ph cng hng t ht nhn

My pht sng B khuch i

radio sng radio Detector

B khuch m

Thit b o dao
ng hoc b ghi

My to s
qut

Hnh 5.4. S khi ca my ph NMR. ng ng mu c t vung gc vi trc ca

2 cc nam chm. A, ng mu; B, cun pht; C, cc cun qut; D, cun thu; E, nam chm.

B phn chnh ca mt my ph cng hng t ht nhn lin tc l mt

nam chm in hay nam chm siu dn c cng t trng H 0 ng nht, mt
b phn pht tn s sng v tuyn v mt cun t cm nhn tn hiu. Mu c
t trong mt ng thu tinh di 20 cm c ng knh 5 mm v quay lin tc t
trng tc ng ng nht vo mi ch ca mu. Sng v tuyn c pht lin tc
nn thit b ny c gi l my ph cng hng t ht nhn sng lin tc.
Mu ghi dng dung dch. Dung mi thng dng l nhng ch t khng
cha ht nhn t proton nh CCl 4, CDCl3, D2O, CD3OD, CD3COCD3, C6D6,
Ngi ta dng tetrametylsilan (TMS) (CH 3)4Si lm cht chun.
5.2. chuyn dch ho hc
a. nh ngha
Xt s cng hng t proton ( 1H NMR) ca CH 3COC(CH 3)3 vi cht chun
l Tetrametylsilan (TMS).
 600 500 400 300 200 100 0 ,Hz

CH3
C CH 3
CH3

O
TMS
CH3 C

10 9 8 7 6 5 4 3 2 1 0 ,ppm
1
Hnh 5.5. Ph H NMR ca CH 3COC(CH 3)3 vi cht chun TMS
Ba proton ca nhm metyl xeton l tng ng nhau nhng khc vi 9
proton ca nhm tert - butyl ( ng thi cng khc vi 12 proton ca TMS). Trn
hnh ta thy theo chiu tng ca cng t trng, cc proton nhm metyl xeton
(Ha) cho tn hiu cng hng trc, tip theo n cc proton ca nhm tert -butyl
(Hb) v cui cng l cc proton ca cht chun (H TMS). Nh th cc nhm proton
cng hng cc trng m nh yu khc nhau. Nu dng tn s c trng
cho cng t trng th cc proton H a, Hb, HTMS ln lt cng hng cc tn
s a , b , TMS tng ng.
Cc i lng a , b , TMS v do hiu s gia chng khng nhng
ph thuc vo cu to ha hc m cn ph thuc vo tn s lm vic ca my ( 0)
do khng dng c trng cho cc loi proton c. Th nhng t s /0
li khng ph thuc vo my ph m ch ph thuc vo cu to ha hc ca cc
proton.
Ngi ta nh ngha chuyn dch ha hc () nh sau:
TMS X 6
.10 6 .10 (ppm) (II.35)
0 0
b. Cc yu t ni phn t nh hng n chuyn dch ha hc
Hai yu t ni phn t nh hng ln n chuyn dch ha hc (cdhh) l
nh hng ca cc electron bao quanh ht nhn (s ch n ti ch) v nh hng
ca cc electron ca cc nguyn t bn cnh (s chn t xa).
*) S chn ti ch
Trc ht ta hy xt trng hp proton, trong phn t proton t nhiu u
c bao quanh bi electron. Di tc dng ca t trng H 0, electron s chuyn
ng thnh mt dng in quanh proton. Dng in ny pht sinh mt t trng
cm ng m ng sc ca n c v bng cc ng nt t. vng gn ht
nhn, t trng cm ng ny ngc chiu vi t trng H 0, n chng li t trng
sinh ra n v lm cho t trng hiu dng H hd quanh proton gim i so vi H 0.
Nh th electron che chn cho proton. Ngi ta gi l s chn mn
electron ti ch hay ni gn hn l s chn ti ch. V s chn ti ch lm gim
cng t trng tc ng ti ht nhn, do nu ht nhn cng c chn mn
nhiu th cho n i vo cng hng cn phi tng cng t trng. Ni mt
cch khc ht nhn cng c chn mn nhiu th tnh hiu ca n cng dch
chuyn v pha trng mnh.
H tng
e
ng CH3F
+ sc t
trng

CH3Cl

CH3Br
H0 CH3I
Hnh 5.6. T trng cm ng ca dng in m in tng
vng
Hnh 5.7. nh hng ca m in c a
halogen n chhh ca proton nhm metyl.

S chn ti ch ph thuc vo mt electron xung quanh ht nhn ta ang

xt, do n lin quan trc tip n m in ca cc nguyn t hoc nhm
nguyn t nh vi ht nhn . iu ny c chng minh khi xt nh hng ca
cc nguyn t halogen n chuyn dch ha hc c a cc proton nhm metyl
cc metyl halogenua. S tng m in theo trt t I, Br, Cl, F lm gim s chn
mn electron i vi cc proton nhm metyl, lm cho tn hiu ca chng chuyn
v pha trng yu ( tng). Cc nhm ht electron mnh s lm gim s chn
mn electron v do lm tng .
Si c m in nh hn C. V vy cc proton trong TMS, c chn mn
nhiu hn v tn hiu cng hng ca chng dch chuyn v pha trng mnh
hn so vi cc proton ca a s cc hp cht hu c khc. Chnh v t h m ngi
ta chn TMS lm cht chun xc nh chuyn dch ha hc trong 1H NMR
vi dng cho chuyn dch ha hc ca cc proton trong cc hp cht hu
c thng thng u l nhng s dng ( > 0).
S chn mn electron khng nhng ph thuc vo mt electron m cn
ph thuc vo hnh dng v kch thc ca m my electron (tc l ph thuc
vo cc ht nhn khc nhau). Cho nn trong khi chuyn dch ha hc ca
proton thng bin i t 0 n trn 12 ppm th chuyn dch ha hc ca 13C
li bin i ti 240 ppm.
*) S chn t xa
S chn mn gy ra bi cc electron bao quanh proton l mt yu t ng
gp vo chuyn dch ha hc nhng khng phi l yu t chnh. Ta hy xem
chuyn dch ha hc ca proton mt s hp cht di y:
CF3COOH RCH=O C 6H 6 CH2Cl2 H2O H2C=CH2 CH CH C6H12 TMS

12 11 10 9 8 7 6 5 4 3 2 1 0 , ppm
Trng yu Trng mnh
Hnh 5.8. chuyn dch ha hc ca proton mt vi hp cht
Hnh trn cho thy trt t v chuyn dch ha hc khng phi lc no
cng tng ng vi trt t v m in. Chng hn, proton ca benzene cho tn
hiu trng yu hn proton ca ety len v proton ca axetylen mc d m
in ca C sp2 nh hn ca C sp. Thm na tn hiu ca proton ca benzene th hin
trng yu hn so vi proton CH 2Cl2 v H2O mc d mt electron xung
quanh proton cc hp cht ny khng tng ng vi s tha y i v chuyn
dch ha hc nh th.
 Nhng nguyn t hoc nhm nguyn t bn cnh proton, c bit l
nhng nhm khng no, nhm vng thm, hoc cc nguyn t c cha cp
electron khng lin kt c th l ngun gc ca nhng dng in vng mnh hn
v to ra xung quanh proton cc t trng c hiu sut ln hn t trng ca cc
electron ha tr ca chnh proton . Chnh v th nhng nhm nguyn t bn
cnh proton cng c tc dng che chn i vi proton. l s chn t xa. S
chn t xa cn c gi l s chn bt ng hng v hng ny th b chn cn
hng kia th li b phn chn.
Ta hy xt s chn bt ng hng ca vng benzene. Di tc dng ca
trng H0, h 6 electron lin hp kn ca nhn benzene to thnh mt dng in
vng m t trng ca n (t trng cm ng) c biu din bi cc ng sc
nh hnh v: (+)

H0

(-) H
(-)

(+)

Hnh 5.9. S chn bt ng hng gy ra bi dng in gy ra bi dng in

nhn benzene
khu vc gia nhn benzene, k c pha trn v pha di, trng cm n g
ngc chiu vi trng H 0, n lm gim H 0. Khu vc c chn v c k
hiu bng du (+). khu vc ngoi vng benzene (ch yu nm mt phng cha
nhn benzene) trng cm ng cng chiu vi trng H 0, n lm tng H 0. Ngi
ta ni khu vc c phn chn, k hiu du (-). Nh th 6 proton ca benzene
nm khu vc phn chn. Ni mt cch khc, dng in vng nhn benzene
khng gy tc dng chn i vi 6 proton m c tc dng phn chn i vi
chng. Do tn hiu cng hng ca cc proton b enzene phi chuyn v pha
trng yu. Nh phng php NMR c th xc nh c mt hp cht c phi l
thm hay khng.
Khng ch vng thm mi gy ra s chn xa bt ng hng. Cc lin kt
bi nh C C , C = C, C = O, C = N cc cp electron khng tham gia lin kt,
v c lin kt n cng u gy ra s chn bt ng hng. S chn bt ng
hng ca lin kt ba, lin kt i v lin kt n c ch ra nh hnh di:

(-) (+) (+)

(+)
CC (+)

(-)
(-) C=C (-) (-) C C (-)

(+) (+)

a)
b) c)

Hnh 5.10. S chn bt ng hng c a lin kt ba (a), lin kt i (b) v lin kt

n (c) ; (+) vng chn ; (-) vng phn chn
S chn bt ng hng ca nhm cacbonyl (C = O) v hnh thc ging nh
nhm C = C nhng cng th mnh hn, do proton ca nhm -CH = O b
phn chn mnh. Hn th, do s ht electron ca nhm C =O, s chn ti ch
proton ca nhm -CH = O cng b gim. Chnh v th, tn hiu ca proton nhm
andehit xut hin trng rt yu.
*)Ht nhn tng ng v chuyn dch ha hc: l cc ht nhn c cng
chuyn dch ha hc, cc ht nhn khc nhau v chuyn dch ha hc gi l
cc ht nhn khng tng ng v chuyn dch ha hc, v ph thuc vo v
tr khng gian ca cc proton trong phn t.
5.3. Cng vn ph cng hng t ht nhn
Nh chng ta bit , trong phn t c bao nhiu ht nhn khng tng
ng v chuyn dch ha hc th trn ph c by nhiu tn hiu, tc c by nhiu
vn ph. Cc vn ph c th cao thp rng hp khc nhau, tc c cng khc
nhau. Cn ni ngay rng cng vn ph trong 1H NMR t l thun vi s lng
proton gy ra vn ph , cn cng vn ph trong 13C th hon ton c lp
vi s lng 13C gy ra tn hiu. Ngoi ra cng vn ph cn ph thuc vo
my o.
Cng vn ph xc nh qua din tch ca vn ph g i l cng tch
phn. Khi mt vn ph tch thnh nhiu hp phn (do tng tc spin -spin ) th
phi tnh tng din tch ca cc vn hp phn . Trc y cc my ph c lp
b phn xc nh cng tch phn bng cch v ln ph cc ng bc thang.
cao ca mi bc thang t l vi cng ca mi vch ph. Bng cch so
snh cao ca cc bc thang ta c th tm thy t l v s lng gia cc nhm
proton gy ra tn hiu cng hng. hnh 5.11 - t l cao gia ba bc thang l
8:1:1, do ta c t l v s lng proton l H a:Hb:Hc = 8:1:1.

Hnh 5.11.ng bc thang ch cng tng i trn ph 1H NMR ca xyclopentanol

Vic xc nh cng tng i i khi gip chng ta la chn cu trc
ng trong nhng cu trc c th. V d axit feist cho hai tn hiu = 6,7 v 4,8
ppm (khng k tn hiu ca nhm COOH). Hai tn hiu ny c cng bng
nhau nh th ta phi chn cho n cu trc A ch khng phi cu trc B.
HC COOH C COOH
HC A) HC B)
2 3
HC COOH HC COOH

Mt c im quan trng v cn ph 13C NMR kh hon ton tng tc

spin - spin l nhng pic c cng nh thng tng ng vi cc nguyn t C
khng nh vi hiro, cn nhng pic c cng ln th ng vi cc nguyn t
Cacbon nh vi mt hoc nhiu nguyn t hiro. minh ha, ta hy xem xt
ph 13C NMR kh hon ton tng tc spin - spin ca 2 - clo - 1,4 - dimetoxyl
benzen (hnh 5.12).

Hnh 5.12. Ph 13C NMR kh hon ton tng tc spin - spin ca 2 - clo - 1,4 -
dimetoxyl benzen
5.4. S tch vn ph do tng tc s pin - spin
Vi mi ht nhn hoc mt nhm ht nhn ngi ta nhn c tn hiu c
trng ch c 1 nh nhng cng c khi gm 1 nhm 2,3,4,5 nh khc nhau.
V d ph cng hng t ht nhn ca C 2H5OH nhn cc tn hiu c trng
cho OH (12 nh), CH2(4 nh), CH 3(3 nh)

Hnh 5.13: Ph cng hng t nhn proton ca C 2H5OH

 Nguyn nhn ca s xut hin nhiu nh trn l do mi ht nhn c
I 1 (m= 1 ) sinh ra 2 t trng ring. Hai t trng ring n y tc dng
2 2
ln ht nhn bn cnh lm phn tch mc nng lng chnh ca n thnh 2 mc
nng lng khc nhau. Trng hp 2, 3 ht nhn cng tc ng t trng ring
ca mnh ln cng 1 ht nhn khc th nng lng cng hng ca ht nhn b
phn tch thnh nhiu mc nng lng khc nhau, mi mc nng lng ny do
mt nh trn ph cng hng t proton.
V d: xem xt ph 1 H NMR phn t 1,1,2- Tri clo etan.

Hnh 5.14: S tng tc spin -spin proton ca 1,1,2-tricloetan

Nhn xt:
HA tc dng ln H B 2 t trng ph, lm tch ra thnh 2 mc nng lng
ng thi H A tc dng ln H C 2 t trng ph, lm tch ra thnh 2 mc nng
lng.
V 2 mc nng lng ca HB v HC ging nhau nn chng chp li cho 2 tn
hiu cng hng.
HB cng tc ng ln H A 2 t trng ring ca mnh, lm tch ra 2 mc
nng lng, H C cng tc ng ln H A 2 t trng ring v lm tch ra thm 2 mc.
Nh vy H A s phn tch thnh 4 mc nng lng khc nhau, nhng v c 2 mc
nng lng bng nhau nn ch cn phn tch thnh 3 mc nng lng khc nhau
nn cho 3 tn hiu cng hng t proton khc nhau.
 *Vi trng hp n gin, s vch tch nh tnh theo s ht proton ca nhm
tng tc bn cnh. Nu nhm tng tc c n ht nhn th s vch t i a l n+1
V d: xem xt ph 1H NMR ca etanol trong CDCl 3

Hnh 5.15: Ph 1H NMR ca etanol trong CDCl 3

Cn phi ni ngay l cc ht nhn tng ng v cdhh th khng gy
tch vn ph ca nhau, v d H 2O, TMS ch cho mt vn ph n. Ch c c c
ht nhn khng tng ng v chuyn dch ha hc mi gy tch vn ph
ca nhau do tng tc spin - spin.
13
5.5. Ph C NMR
a) Ph 13
C NMR tng tc 13C - 1 H
Khi ghi ph tng tc 13 C - 1 H ta thu c cc nhm nh khc nhau. V
1
13
C v 1 H u c I nn quy tc a vch c p dng ging nh 1 H - 1 H ca
2
ph 1 H -NMR:
Singlet (1 vch) khng c H C
Duplet (2 vch) c 1 H CH
Triplet (3 vch) c 2 H CH2
Quartet (4 vch) c 3H CH3

- Tng tc C v H cch xa nhau hn 1 lin kt thng rt nh.

13 13
- Tng tc C v C cnh nhau cng rt nh.
b) Ph 13
C NMR xa tng tc 13C - 1 H
Ph 13 C tng tc 1 H cho nhiu nhm nh do s khc nhau v s proton
trong cc nhm CH, CH2, CH3 nhng cng ca nhiu nh qu nh ln vi c
nhiu ca my, do vic gii ph gp nhiu kh khn, v vy ngi ta ta a
ra cch lm n gin ha bn ph chn mt s thng tin cn thit, bng cch
xa i cc vch tng tc C-H, by gi ng vi mi nguyn t C ch c mt vch
ph.
Cng cc vch ph trong ph xa tng tc 13C - 1H ph thuc:
- S nguyn t hiro gn vi nguyn t cacbon
- S nguyn t cacbon tng ng
Thng th nhm CH 2 v CH3 cho cng vch ph nh nh au, nhng
nhm CH v C cho cng yu hn.
c) chuyn dch ha hc
V tr ca cc tn hiu cng hng rt quan trng cho vic xc nh cu to
cc hp cht. chuyn dch ha hc 13C nm trong mt vng rng hn so vi
ph 1H NMR, t 0 200 ppm. Hin nay cht chun thng dng l TMS, dung
mi ghi ph thng dng l cc cht d 6 - axeton, d 6 - benzen
chuyn dch ha hc 13C c xc nh bi:
- Mc lai ha ca nguyn t cacbon
- m in ca cc nhm th nguyn t cacbon
Cc nhm th nh hng mnh n s thay i v tr chuyn dch ha
hc, v d:
CH3I CH3Br CH3Cl CH3F
-33 9 24 75 ppm
Ngy nay ngi ta lp c bng thc nghim tnh chuyn dch
ha hc ca mt s hp cht:
5.6) Mt s v d tnh ton chuyn dch ha hc c a ph 13C - NMR

5.6)

5.7)

5.9)
5.8)

5.8)
Bng 5.6:
Bng 5.7:
Bng 5.8:
X1-CC-X2 , =
Bng 5.9:
5.7. Mt s v d v quy kt cc vn ph trong ph 1H NMR
V d 1: Ph 1H NMR ca hp cht cha It c M = 156

Ta thy xut hin h vn ph 4 nh ( = 3,3 ppm) v 3 nh ( = 1,8 ppm)

vi t l ng cong tch phn 2:3 xc nhn s c mt ca nhm CH 3 - CH2-
trong phn t.
V d 2: Ph 1H NMR ca hp cht c cng thc phn t C 3H6O2

= 8,3 ppm (1 nh), = 4,3 (4 nh), = 1,28 (3 nh), c t l ng cong

tch phn 1:2:3 chng t s c mt ca nhm -CH=O, CH3CH2-O- .
V d 3: Ph 1H NMR ca hp cht c cng thc C 8H8O

T l ng cong tch phn 2:3:3, xc nhn s c mt ca nhm CH 3 ( =2,5

ppm) v ca vng benzen (2H meta c = 8,2 ppm v 3H ortho v para c = 8,5
ppm).
V d 4 : Ph 1H NMR ca hp cht c cng thc C 8H9NO

T l ng cong tch phn 5:3, xc nhn s c mt ca nhm CH 3 ( = 2,1

ppm) v ca vng benzen (5H c = 7,17,5 ppm).
V d 5: Ph 1H NMR ca hp cht c cng thc C 8H14NOBr

T l ng cong tch phn 1:2:11, xc nhn s c mt ca NH ( = 4,60

ppm), CH 2 ( = 3,85 ppm) v ca vng no 6 cnh (11H c = 1 2 ppm).
V d 6: Ph 1H NMR ca hp cht c cng thc phn t C 5H4O2

T l ng cong tch phn 1:1. Trn ph cng ch ra = 7,8 ppm (2 nh) v

= 6,4 ppm (2 nh) chng t hp cht c cha 2 ni i dng -CH=CH- c
v tr khng gian tng t nhau.
 Chng V: Phng php ph khi lng
6.1. C s l thuyt v s cu to my ph khi
a) C s l thuyt
Khi cho phn t ca mt cht trng th i kh va chm vi mt dng
electron c nng lng nht nh th cc phn t s bt ra 1 hoc 2 electron tr
thnh cc ion c in tch +1( chim t l ln) hoc +2. Phn t cng c th tip
nhn electron tr thnh ion m.
ABC + e ABC+ +2e (ABC+ gi l ion phn t)
ABC + e ABC++ +3e
ABC + e ABC -
Hin tng ny c gi l hin tng ion ho phn t.
Khi va chm mnh hn, ion phn t c th tip tc b ph v thnh nhiu
mnh ion khc nhau. Hin tng ny c gi l hin tng phn ho. Vic phn
ho ny ph thuc vo nng lng va chm.
ABC+ C + AB+ ; AB+ A + B+
ABC+ A+ +BC ( AB+, B+, A+ gi l cc ion mnh)
Nng lng ca qu trnh phn ho khong 30 - 100eV, cao hn nng lng
ion ho phn t (8- 15eV)
Xc sut
Trn th ch ra xc sut c mt c mt
ca cc
ca cc ion ph thuc vo nng ion [CH3*C=O]+
lng va chm phn t a xeton.
Nng lng khong 15eV th s
[(CH3)2 *C=O]+
cc ion phn t t cc i nhng
s cc mnh ion tip tc tng n
nng lng khong 40eV th tng
chm v t cc i.
20 40 60 80 100 Nng lng(eV)

Nguyn tc tch ion theo khi lng : Hnh 6.1. Xc sut c mt ion mnh axeton
Cc ion c khi lng m, in tch e ngi ta gi t s m/e l s khi
ca cc ion.
 Khi cho cc ion qua mt in trng mnh (800 - 8000V) th tc chuyn
ng ca chng tng v t gi tr ln (xem hnh 6.2):
2eU
v (II.36)
m
Trong : v l tc ion.
e l in tch ion
m l khi lng ion
U l th in trng
Sau cc ion ny c dn qua mt t trng ng c cng H, chng
s chuyn ng theo hnh vng cung c bn knh r m khc nhau, bn knh ny ph
thuc vo s khi ca cc ion (m/e).
m.v
rm (II.37)
e.H
m 2U 1 m
Hay rm2 . 2 rm . 2 U. (II.38)
e H H e
Nh vy, mi ion c s khi khc nhau s c bn knh vng trn chuyn
ng khc nhau( Nu cng t trng & th tng tc khng i). Da vo
nguyn tc ny, ngi ta nhn bit c s c mt ca cc ion bng phng php
khc nhau.
b) S cu to my ph khi
Da trn nguyn tc chung, my ph khi gm 4 b phn chnh.
1- Bung ho kh mu: Cc mu rn hay lng c a vo bung mu, ti y p
sut 10-6mmHg, mu chuyn thnh dn g kh. Bung mu cn thit l 0,1 -1mmHg.
2- B phn to ion: Dng phn t kh c dn qua mt dng electron c hng
vung gc vi n to ra cc ion, sau i qua in trng tng tc.( Ghi
ch: dng electron c sinh ra t 2 tm in cc t s ong song).
3- B phn tch ion theo khi lng.
4- Nhn bit ion bng detect.
5- Ghi ph
 Hnh 6.2. S cu to my ph khi
1-Bung ho kh mu
2-B phn to ion
3-B phn tch ion theo khi lng
4-Detect
5-Ghi ph
c) Phn loi cc ion
1- Ion phn t
Ion phn t c hnh thnh do mt 1 electron.
L ion c s khi ln nht, chnh bng trng lng phn t ca cht mu.
K hiu ion phn t l M +
2- Ion ng v
Trong t nhin, cc nguyn t ho hc tn ti cc ng v c t l khc nhau.
V d: 13
C& 12
C (0,011:1); 15
N& 14
N; 17
O, 18
O & 16
O
Chnh v vy, bn cnh vch chnh vi ion M + cn c cc vch ph(M+1) +,
(M+2)+ vi cng nh hn.
3- Ion mnh
Ion mnh c hnh thnh do s ph v phn t khi va chm vi electron. Tu
theo nng lng va chm ln hay nh m phn t v thnh nhiu mnh khc
nhau. Thng thng nng lng va chm khong 70eV
Qu trnh ny l phn ho: u tin phn t mt 1e to thnh ion dng gc
ri chuyn dch theo cc trng hp:
a) To thnh 1 ion dng v 1 gc
b) To thnh 1 ion dng v 1 gc nhng v tr mch cacbon b gy b thay i
c) C s chuyn ch ca 1 gc H . to thnh 1 ion gc mi
4- Ion lc
Cc ion phi c thi gian sng(>10 -5s) nht nh th mi c th ghi li c. Mt
s ion(m*) xut hin bc trung gian gia ion c khi lng m 1& m2, c thi
gian sng khng ghi nhn c, nhng ngi ta c th nh du c s c mt
ca n.
Ion ny gi l ion metastable (m*)
(m*) m 22 / m1

6.2 C ch phn ha phn t

1- Tch ankyl

| | | | |

|

C| C| C|
C C
| |
C
|

| | | |

C| C| X
C C
| |
X (X = OH, Hal, SH, OR)

2- Tch olefin
Nhng ion ankyl mch di c th tch loi 1 phn t ole fin nh sau:

| | | | |

|

C| C| C|
CC
| |
C
|
3) Tch allyl
Nhng phn t olefin mch di do mt i 1e nn c s chuyn dch in t
trong phn t dn n vic tch loi 1 gc metyl:
| | | | | | |
C C C C C C C C
e


| | | | | |
| | | | |

C C C C

C C C
| | | | | | |

4) Tch ion tropolium (vng thm)

CH2 R CH2

+ R
+

5) C ch tch Retro-Diels-Alder
Cc hp cht vng cha ni i thng tch theo c ch sau cho cc
olefin:
+.
+ hoc +.
+

6) Chuyn v Mclafferty (S chuyn dch H)

* Vi nhm cacbonyl:

A
H
O
. + A
H
O
. +
X = O, CH 2, NH, S
Y = O, CH 2,
+ |
Y C Y C A = C , CH, CH2
X X
|
*Vng thm v anken:

H .
+ .
+
H2C CH2 CH2 CH3
+
H2C CH CH2 CH
C C

7) Chuyn v gc
+ + +
O O O
H . .
.
C
H

C
+ C CH

6.3 Khi ph ca mt s hp cht hu c

1- Hidrocacbon
- Ankan: S khi thng gp: 29,4 3,57.
- Anken: S khi thng gp: 27,41,55,
- Ankin: S khi thng gp: 39,53,67 . ion phn t M + yu hay vng mt. C
ch phn ho tch ankyl.
- Ankyl benzen: S khi thng gp:39,50,51,65,(76),77(78),91
V d: Ph khi ca n propyl benzen.
C ch phn ho.

+
. CH2
.+
CH2 + - C 2H4

.
- C 2H5
H H
H

m/e 120 m/e 92

m/e 91 + -C3H2
+ C +
C 3 H3
m/e 77 m/e 39
-HC CH -HC CH
+
C
+
m/e 51
m/e 65

2- Ancol, Phenol
- Ancol:
S khi thng gp: 31,45,59 M+ yu t xut hin.
Khuynh hng thng d tch H 2O cho ion M +=18.
- Phenyl ancol: khuynh hng tch cho 1 ion thm.
- Phenol: trong qu trnh ph v p hn t tch ra CO (M +=18) v CHO (M +=29) l
ch yu. C ch phn ha:

OH
.
+ O
H .
+ H H
.
+

H - CO -H
. +

m/e 94 m/e 65
m/e 66
3- Xeton: S khi thng gp: 58,72,86,
V d: n - butyl benzoat
C ch phn ho:

.
+
O
H
CH 3
.
+
OH

O O
CH3
+
CH2
m/e 178 (M +) m/e122 m/e 56

.
O+
H
CH 3
+
O
O

m/e105
H
O CH 3 O
CH 2
. O
+
O
+

4- Axit cacboxylic: Thng tch OH(m/e=17) & COOH(m/e=45).

V d: Ph khi ca axit m- metoxylbenzoic:
Xut hin s khi:152,135,107,122,94,77,45,

C ch phn ha:
+
O . O
+

H3 C O
H3 C O +
H3C O C
OH

m/e 107
m/e 135
H O .
+
O
.
+

O
OH OH

m/e 122
5- Amin:
S khi thng gp: 41,58,72, Cng vch ion phn t M + nh. i
vi mch di nhnh th cng M + ln hn.
Trong qu trnh phn ho, lin kt C - C bn cnh N thng xy ra
V d: Ph khi ca N,N - di- isopropyl methylamin thy xut hin cc s khi :
115,100,86,72,58,43,.

C ch phn ha:

H3 C CH3 CH3 CH3 CH3 CH3 H3C

H3C
N
+ . CH3 H3C
N
+
NH +
+ CH2
H3C
m/e 115 H m/e 58
m/e 100
6.7. Mt s v d v quy kt cc pc trong ph Khi lng
V d 1: Xc nh cng thc cu to ca mt hp cht c cng thc C 7H8O
Trc tin ta lp bng hiu s m/e rt t
ph ra (xem bng s khi ca mt s ion
mnh):
m/e 108 107 91 79 77
107 1
91 17 16
79 29 28 12
77 31 30 14 2
65 43 42 26 14 12

Trn ph xut hin cc s khi m/e = 91, 79, 77, 65, iu ny chng t vng
benzen gn vi nhm CH 2 trong phn t

+ CH+2

T M+ = 108 chuyn v m/e =91 ct i 17 tc nhm -OH do phn t c cu to

l:
OH

C ch phn mnh ngh:

H
+ .
OH

+O
. O
+
H

m/e 108

-H
.
m/e 106
-CH2OH

-C2H2
C+ + CH+2 +

O+ m/e 91
m/e 77 m/e 65
m/e 105
V d 2: Xc nh cng thc cu to ca hp cht c cng thc phn t C 6H15N
Trc tin ta lp bng hiu s m/e rt t
ph ra (xem bng s khi ca mt s ion
mnh):
m/e 101 86 58 44
86 15
58 43 28
44 57 42 14
29 72 57 29 15

- T m/e 101 v 86 ct 15 l nhm -CH3

- T m/e 101 v 58 ct 43 l nhm -C3H7
- Cng thc tng C 6H15N = 101, ct C 3H7 cn C3H8N = 58, tc nhm C 3H7-NH-,
do cng thc ca n c th l : C 3H7 - NH - C3H7. C 3 cng thc cu to c
th c u c s phn mnh ph hp vi ph khi l:
CH3 - CH2 - CH2 - NH - CH2 - CH2 - CH3 (1)
CH3 - CH2 - CH2 - NH - CH - (CH3)2 (1)
(CH3)2 - CH - NH - CH - (CH3)2 (1)
C ch phn mnh ngh:

H3 C CH3 CH3 CH3 CH3 H3C

.
+ +
N N NH +
+ CH2
H3C CH3 H3C H3C
m/e 101 H m/e 44
m/e 86
V d 3: Xc nh cng thc cu to ca hp cht c cng thc C 6H6N2O2

m/e 138 108 92 80 65

108 30
92 46 16
80 58 28 12
65 73 43 27 15
51 87 57 41 29 14

- T M+ =138 v m/e 108 ct 30 l nhm -N=O

- T M+ = 138 v m/e 92 ct 46 l nhm -NO2
- T cng thc: C 6H6N2O2 tr i NO 2 cn C6H6N, chng t c vng benzen
gn vi nhm th cha nit:

+
+ NH2 hay NH m/e 92

Do c th gi thit cng thc cu to ca n:

O
NH2
N+
O-

C ch phn mnh ngh:

NH 2 NH 2
HN H
NH 2
O
N+
.
+ +
O O
-
+ O +
-NO CH
m/e 108 m/e 108
m/e 138
-CO
NH
H H +
H +
C C NH2
C+
-HCN
m/e 80
m/e 92 m/e 65
Bng 6.1 Bng s khi ca mt s mnh ion
Bng 6.1 (tip theo)