1

CHNG 1. I CNG V QUANG PH

Ngy nay cc phng php vt l, c bit l cc phng php ph c s dng
rng ri nghin cu cc hp cht ha hc cng nh cc qu trnh phn ng ha hc.
Nhng phng php ny c bit c ngha i vi vic xc nh cc hp cht hu c. C
s ca phng php ph l qu trnh tng tc ca cc bc x in t i vi cc phn t vt
cht. Khi tng tc vi cc bc x in t, cc phn t c cu trc khc nhau s hp th v
pht x nng lng khc nhau. Kt qu ca s hp th v pht x nng lng ny chnh l
ph, t ph chng ta c th xc nh ngc li cu trc phn t.
Trong chng ny, chng ta kho st cc qu trnh trn.
1.1. M u
C 5 phng php ph:
- Phng php quang ph hp th phn t:
+ Phng php ph quay v dao ng: phng php quang ph hng ngoi
+ Phng php ph Raman
+ Phng php electron UV-VIS.
- Phng php ph cng hng t ht nhn NMR
- Phng php ph khi lng
Mi phng php ph c mt ng dng ring. Thng thng, chng ta kt hp cc
phng php vi nhau gii thch cu to ca mt hp cht hu c.
1.2. S tng tc gia vt cht v bc x in t
Cc bc x in t bao gm tia v tia v tr n cc sng v tuyn trong c bc
x vng t ngoi, kh kin v hng ngoi u c bn cht sng v ht.
Bn cht sng ca chng th hin ra hin tng nhiu x v giao thoa. Cc sng
ny lan truyn trong khng gian theo hnh sin c cc cc i v cc tiu. Khi coi l sng n
c c trng bi cc i lng:
- Bc sng (cm): khong cch gia hai u mt ca mt sng. Nhng bc x in
t khc nhau c di bc sng khc nhau. Bc sng c coi l i lng c trng cho
mi sng. Chiu di bc sng c o bng cc n v di: m, cm, nm, A
0



2









- Tc truyn sng c hay tc nh sng.
- Tn s v (hec): s ln bc sng truyn qua mt im trong khng gian trong mt
n v thi gian.
.v = c
- Chu k T (s): thi gian ngn nht truyn mt bc sng qua mt im trong khng
gian.
- Trong quang ph ngi ta cn dng i lng nghch o ca bc sng 1/ o
chiu di ca bc sng, k hiu ) (
1
1
= cm

Cc bc x in t cng mang nng lng, cc bc x c chiu di bc sng cng
nh th nng lng ca chng cng ln v tun theo nh lut:

c h
h E
.
. = =
Trong : h l hng s planck. h = 6,6262.10
-34
J.s
Nng lng E c o bng n v eV, kcal/mol, cal/mol.
Khi cc bc x in t tng tc vi cc phn t vt cht, c th xy ra theo hai kh
nng: trng thi nng lng ca phn t thay i hoc khng thay i. Khi c s thay i
nng lng th phn t c th hp th hoc bc x nng lng.
Nu gi trng thi nng lng ban u ca phn t l E
1
, sau khi tng tc l E
2
th
c th vit:
AE = E
2
E
1

: bc sng
3
AE = 0: nng lng phn t khng thay i khi tng tc vi bc x in t.
AE > 0: phn t hp th nng lng; AE < 0: phn t bc x nng lng.
Theo thuyt lng t th cc phn t v bc x in t trao i nng lng vi nhau
khng phi bt k v lin tc m c tnh cht gin on. Phn t ch hp th hoc bc x 0,
1, 2, 3n ln lng t h.v. Khi phn t hp th hoc bc x s lm thay i cng ca
bc x in t nhng khng lm thay i nng lng ca bc x in t, bi v cng
bc x in t xc nh bng mt cc ht photon c trong chm tia cn nng lng ca
bc x in t li ph thuc vo tn s v ca bc x. V vy, khi chiu mt chm bc x
in t vi mt tn s duy nht i qua mi trng vt cht th sau khi i qua nng lng ca
bc x khng h thay i m ch c cng ca bc x thay i.
Khi cc phn t hp th nng lng t bn ngoi c th dn n cc qu trnh thay
i trong phn t (quay, dao ng, kch thch electron phn t) hoc trong nguyn t
(cng hng spin electron, cng hng t ht nhn).







Cc trng thi kch thch phn t
Mi mt qu trnh nh vy u i hi mt nng lng AE > 0 nht nh c trng
cho n, ngha l i hi bc x in t c mt tn s ring gi l tn s quay v
q
, tn s dao
ng v
d
v tn s kch thch in t v

.
V th khi chiu mt chm bc x in t vi cc tn s khc nhau vo th cc phn
t ch hp th c cc bc x in t c tn s ng bng cc tn s trn (v
q
, v
d
v v

)
xy ra cc qu trnh bin i trong phn t nh trn. Do s hp th chn lc ny m khi
chiu chm bc x in t vi mt di tn s khc nhau i qua 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.
quay Dao ng
Kch thch electron
4
1.3. nh lut Lambert Beer
Khi chiu mt chng tia sng n sc i qua mt mi trng vt cht th cng
ca tia sng ban u I
0
s b gim i ch cn l I.
Nng lng nh sng: E = h.v = h.c/
Nng lng ca nh sng ph thuc vo v.
Cng nh sng I ph thuc vo bin dao ng a.





d: dy
Vi hai tia sng c cng nng lng nhng c cng nh sng khc nhau
T = I/I
0
.100%: truyn qua
A = (I
0
I)/I
0
.100%: hp th
ln ca truyn qua T hay hp th A ph thuc vo bn cht ca cht ha
tan, chiu dy d ca lp mng v nng C ca dung dch. Do , c th vit:
Lg(I
0
/I)

= c

.C.d = D

c

= D

/C.d; lgc

= lgD

/C.d
c c gi l h s hp th, C c tnh bng mol/l, d tnh bng cm v D l mt
quang. Phng trnh trn ch ng vi tia n sc.
1.4. Ph
- Khi cho bc x in t tng tc vi phn t vt cht, dng thit b my ph ghi
nhn s tng tc , ta nhn c mt dng th gi l ph.
- T nh lut Lambert-Beer, ngi ta thit lp v biu din s ph thuc:
+ Trn trc tung: A, D, c, lgc, T
+ Trn trc honh: tn s bc x v, s sng v, bc sng bc x kch thch
Thu c th c dng D

= f(), lgc = f(), T = f(v), A = f(v) th ny gi l
ph. Cc nh hp ph cc i gi l di (band) hay nh hp th (peak), chiu cao ca nh
peak gi l cng hp th.
I
0 I

d

5
Ring vi ph NMR v ph MS th i lng trn trc honh c m rng hn
thnh chuyn dch ha hc (ppm) hay s khi m/e.
1.5. ng cong hp th v phn gii
- S ph thuc ca D vo bc sng: D

= f()
Khi = const; d = const th D = f(C)
Dng phng trnh ny phn tch nh lng.








Vi cng mt cht nhng vi cc tia sng khc nhau s cho cc ng th khc
nhau.
- S ph thuc ca h s hp th vo chiu di ca bc sng kch thch.ng cong
biu din s ph thuc ny gi l ph. Cc nh hp th cc i gi l di hay nh hp th,
chiu cao ca nh hp th gi l cng .
c = f() hay lgc = f() khi C = const; d = const








ng cong c cc i v cc tiu V tr ca cc
max
v
max
ging nhau
Khng ph thuc vo nng C Mi gi tr ca C c mt th khc nhau
D
C [mg/l]

max
D

C [mol/l]
C
C
6
Hai ng biu din ny dng phn tch cu to ca cc hp cht.
Cc nh hp th c khi c tch ra khi nhau hon ton nhng c nhiu khi chng
chng ln nhau mt phn hay gn nh hon ton. S tch bit ny ph thuc vo kh nng
tch bit ca tng my m c gi l kh nng phn gii ca my. Ngi ta nh ngha
phn gii R ca my l kh nng tch bit hai nh hp th c chiu di bc sng v +
A. R = /A.
1.6. Vng ph Quang hc
Bc x in t bao gm mt vng chiu di sng rt rng, nhng kch thch cc
qu trnh quay, dao ng v kch thch electron ch c mt vng bc sng hp t 1mm n
100A hay 10
-1
n 10
-6
cm. Ph thuc vo vic s dng vt liu quang hc, ngi ta phn
chia cc vng nh sng nh sau:
- Vng sng 50 1200 A
0
. Dng vt liu quang hc l cch t v khng th s dng
vt liu trong sut. Khng c ngha i vi ha hc hu c.
- Vng sng 1200 1850 A
0
. Dng vt liu quang hc l CaF
2
. Cc tia sng thu nhn
c bng knh nh. ng dng nghin cu cc hp cht ha hc.
- Vng sng 1850 4000 A
0
(vng t ngoi trung bnh). Vt liu quang hc l thch
anh. Vng ny chnh vng quang ph ngoi, c ng dng rng ri nghin cu cc hp
cht. Ngun sng l en deuteri.
- Vng sng 4000 8000 A
0
(vng nhn thy). Vt liu quang hc l thy tinh, ngun
sng l n in thng (vonfram hay tungsten). Vng ny c s dng nghin cu cc
hp cht c mu.
- Vng sng 0,8 - 2m (vng hng ngoi gn). Vt liu quang hc c th l thy tinh
hay thch anh. Ngun sng n in thng.
- Vng 2 - 40m (vng hng ngoi c bn). Vt liu quang hc dng ng thi l LiF
(n 6m), CaF
2
(n 9m), NaCl (n 15 m), KBr (n 27 m), CsI (n 40 m). Ngun
sng dng n Nernst. C ngha thc t ln nghin cu cc hp cht ha hc.
- Vng sng 40 200 m (vng hng ngoi xa). Vt liu quang hc dng cch t.
1.7. S khi ca ph k quang hc
S khi ca ph k quang hc gm cc b phn chnh sau:
7




(1) Ngun sng: ty thuc vo mi loi ph k m c cc ngun sng ring. V d,
ph k hng ngoi dng ngun pht bc x hng ngoi, ph k t ngoi dng ngun pht
bc x t ngoi.
(2) Cuvet mu:
(3) B chn sng: c th dng knh lc hay b n sc (vi lng knh hay cch t)
tch bc x a sc thnh bc x n sc.
(4) Detect: b phn pht hin tn hiu, bin tn hiu quang thnh tn hiu in. C
nhiu loi detect khc nhau nh Vonteic, detect ng nhn quang, detect chuyn in tch,
detect cp nhit in, detect ha nhit.
(5) Khuych i tn hiu
(6) B phn c tn hiu: ng h in k, b hin s, b t ghi, my tnh
V mt thit k, ngi ta ch to hai kiu my: kiu mt chm tia v kiu hai chm
tia. Trc kia kiu mt chm tia ch s dng o tng im ca chiu di sng dng cho phn
tch nh lng cn kiu hai chm tia c th qut ng thi c mt vng chiu di sng lin
tc. Ngy nay, do vic s dng my tnh lu tr v c tn hiu cho nn cc my mt
chm tia c thit k cho c mt ph lin tc nh my hai chm tia.


(1)
(2) (3) (4) (5)
(6)
8
CHNG 2. PH HNG NGOI

2.1. Cc nguyn l c bn ca ph hng ngoi
Khi cc phn t hp th nng lng t bn ngoi c th dn n qu trnh quay, dao
ng xung quanh v tr cn bng ca n. Ty theo nng lng kch thch ln hay nh c th
xy ra qu trnh quay, dao ng hay c quay v dao ng ng thi. kch thch cc qu
trnh trn c th s dng tia sng vng hng ngoi (ph hng ngoi) hoc tia khuych tn
Raman (ph Raman).
Bc x hng ngoi lin quan n phn ph in t nm gia vng kh kin v vng
vi sng c bc sng nm trong vng: vng hng ngoi gn: 14290 4000 cm
-1
v hng
ngoi xa: 700 200 cm
-1
. Vng ph c ngha quan trng nht l vng gia 4000 v 400
cm
-1
.
2.1.1. S xut hin ca quang ph quay
i vi cc phn t gm hai nguyn t c khi lng khc nhau (nh CO, HCl) c
= 0 c th xp vo mu quay ca hai qu t c khi lng m
1
v m
2
. Gi thuyt v trong qu
trnh quay th khong cch gia hai nguyn t khng thay i.






Khi phn t gm hai nguyn t quay theo mt hng trong khng gian th momen
qun tnh I ca qu trnh c tnh theo biu thc:
I = mr
0
2

Vi r
0
= r
1
+ r
2

V
2 1
2 1
m m
m m
m
+
=
Theo c hc lng t th nng long quay E
q
ca cc phn t gm hai nguyn t
c tnh theo phng trnh:
m
1
m

r

r
1
r
2
0

9

j q
E J J
I
h
E = + = ) 1 (
8
2
2

Trong I v mmen qu trnh, h l hng s Planck, J l s lng t quay v J =
1,2,3
Chia hai v ca phng trnh cho hc c:
) 1 (
8
2
+ = = J J
Ic
h
hc
E
F
j
j

t
Ic
h
B
2
8
= th phng trnh trn c dng:
F
j
= BJ(J+1)
B c gi l s lng t quay v F
j
l s hng quay.
S ph thuc ca F
j
v AF
j
vo J
AF
j
= F
j
F
j
= v
q

Bc chuyn di nng lng trong qu trnh quay ca phn t gm hai nguyn t
tun theo quy tt AJ=1. Do :

) 1 ( 2
) 1 ( ) 1 ' ( '
'
+ =
+ + = =
J B
J BJ J BJ
hc
E
hc
E
q
j j
q

kch thch phn t quay, ngi ta thng dng ngun vi sng cho nn ph ny
c gi l ph vi sng hoc dng tia sng vng hng ngoi xa cho nn ngi ta cn gi
quang ph quay l quang ph hng ngoi xa.
2.1.2. S xut hin ca quang ph dao ng
i vi cc phn t gm hai nguyn t (CO, HCl), ngi ta xp vo mu hai hn bi
ni vi nhau bi mt chic l xo. Khong cch bnh thng gia hai hn bi l r
0
, nu gi
cht mt hn bi v ko hn bi kia ra mt on dr ri th t do th n s dao ng quanh v tr
cn bng vi bin dr khng i. Mu ny c gi l dao ng t iu ha.
Nng lng ca dao ng t iu ha c tnh theo phng trnh:

2
) (
2
1
dr k E
t
=
Do khi dr = 0 th E
t
= 0, ngha l khi dao ng t trng thi cn bng th nng
lng ca n bng 0. ng cong th nng ca n l mt ng parabol c cc tiu ti r
0
.
10
Theo c hc c in th tn s dao ng iu ha c tnh theo phng trnh:

M
k

2
1
=
Vi k l hng s lc v M l khi lng rt gn.
Theo c hc lng t, khi cc phn t dao ng chng ch c th chim tng mc
nng lng nht nh cha khng thay i lin tc v phng trnh nng lng ca phn t
thc c tnh theo cng thc:

E v h E
t
= |
.
|

\
|
+ =
2
1

Vi v = 0,1,2 c gi l s lng t dao ng
Khi v = 0 th E
v
= 0, nh vy khi phn t khng dao ng n vn cha mt nng
lng nht nh v gi l nng lng im khng.
AE = E
2
E
1
= hv[v + 1 + - (v + )]
AE = hv : khng ph thuc vo v.
V phn t thc khng dao ng iu ha (dao ng vi bin thay i) nn
phng trnh nng lng ca n c b chnh theo cng thc:
|
.
|

\
|
+ |
.
|

\
|
+ =
2
1
4 2
1
2 2
v
D
v h
v h E
v

D l nng lng phn li ca phn t.
Quy tt la chn vi phn t dao ng Av = 1, 2 Nh vy khi phn t dao ng
c th tip nhn cc bc chuyn nng lng sau:
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 2
v = 0 v = 4 gi l dao ng cao mc 3
.
v = 0 v = n gi l dao ng cao mc n -1

Tuy nhin, xc sut ca cc bc chuyn ny (cng vch ph) gim dn khi bc
dao ng tng.
11

Khi phn t phn li thnh ion th v tng nhng E khng tng.
2.1.3. Dao ng quay ca phn t
Khi kch thch nng lng thch hp thng xy ra qu trnh phn t va quay va
dao ng gi l dao ng quay ca phn t. Nng lng dao ng quay bng tng nng
lng quay v nng lng dao ng:
E
dq
= E
q
+ E
d
= (v + 1/2)hv + BhcJ(J + 1)
i vi phn t dao ng quay phi tun theo quy tc la chn AJ = 1 v Av = 1
i vi phn t thc phi c h s iu chnh.
Nhnh R AJ = +1
Av = +1
Ph hp vi quy lut cm
P AJ = -1
Av = +1
Ph hp vi quy lut cm
im Q AJ = 0
Av = +1
Khng xy ra s kch thch
Theo quy tt la chn trn, ph dao ng quay ca cc phn t gm hai nguyn t c
hai nhnh Pv R im Q = 0.
12

2.1.4. Dao ng chun ca phn t
Cc nguyn t trong phn t dao ng theo ba hng gi l dao ng chun ca phn
t. i vi phn t c cu to nm trn ng thng, s dao ng chun ca phn t c N
nguyn t ti a bng 3N 5 v 3N 6 i vi phn t khng thng.
Mi dao ng chun c mt nng lng nht nh, tuy nhin c trng hp 2, 3 dao
ng chun c mt mc nng lng . Cc dao ng chun c cng mt mc nng lng gi
l dao ng thoi bin.
Ngi ta phn bit dao ng chun thnh hai loi:
- Dao ng ha tr (k hiu l v) l nhng dao ng lm thay i chiu di lin kt ca
cc nguyn t trong phn t nhng khng lm thay i gc lin kt.
- Dao ng bin dng (k hiu o) l nhng dao ng lm thay i gc lin kt nhng
khng lm thay i chiu di lin kt ca cc nguyn t trong phn t.
Mi loi dao ng cn c phn chia thnh dao ng i xng v bt i xng.
V d:
- Phn t CO
2
thng c 3N 5 = 3.3 5 = 4 dao ng chun trong c 2 dao ng
ha tr (mt i xng v mt bt i xng) v 2 dao ng bin dng i xng.
13
- Phn t nc khng thng c 3N 6 = 3.3 6 = 3 dao ng chun trong c hai
dao ng ha tr v mt dao ng bin dng i xng.
iu kin kch thch dao ng:
Khng phi khi no c nh sng chiu vo phn t cng c ph hng ngoi. Khi nh
sng chiu vo phn t, phn t dao ng, trong qu trnh dao ng momen lng cc ca
phn t khc 0 v phn cc o ca phn t khng i mi xut hin ph. Nu mmen
lng cc bng 0 v phn cc khc 0 th ph hng ngoi khng hot ng.
2.2. S lin quan gia tn s hp th v cu to phn t
2.2.1. Cc nh hng lm dch chuyn tn s c trng
Tn s dao ng ca cc nguyn t ph thuc vo hng s lc ca lin kt v khi
lng ca chng. Do cc nhm chc khc nhau c tn s hp th khc nhau v nm trong
vng t 5000 200 cm
-1
.
nh hng ca dung mi, nng , nhit v trng thi tp hp n v tr ca cc
cc i hp th.
- Dung mi: c nh hng n s thay i v tr ca cc cc i hp th ty theo
phn cc ca chng
- Nng dung dch cng gy nh hng n s thay i v tr ca nh hp th, c
bit i vi cc cht c kh nng to cu lin kt hiro nh ancol, phenol, amin
- nh hng ca nhm th. Cc nhm th trong phn t cng gy nh hng n s
thay i v tr nh hp th ty theo nhm th gy hiu ng cm ng hay lin hp.
- Phc cht: Khi to phc, tn s hp th c trng ca nhm chc thay i theo kim
loi trung tm v s phi tr.
2.2.2. Tn s c trng ca cc nhm chc hu c
1. Ankan
Cc ankan cha nhm CH
2
v CH
3
trong phn t c cc dao ng c trng C-H ha
tr v bin dng.

Dao ng ha tr CH
3
CH
2

2850 2960 v(CH) bt i xng v(CH) i xng v(CH) bt i xng v(CH) i xng
2960 2870 2925 2850
14
Dao ng bin dng
720, 1000 1465 o(CH) bt i xng o(CH) i xng o(CH) o(CH) o(CH)
1460 1375 1465 720 1250
o bt i xng
1045
2. Anken
Dao ng ha tr v
C-H
3000 cm
-1
v
C=C
1600 1650 cm
-1

3. Ankin
Dao ng ha tr v
C-H
3300 cm
-1

v
CC
3150 cm
-1

4. Anlenic
Dao ng ha tr v
C=C=C
1960 -1940 cm
-1

5. Hirocacbon thm
Dao ng ha tr v
C-H
3050 cm
-1

v
C=C
1600, 1500, 1470 cm
-1

Dao ng bin dng o
C-H
700 900 cm
-1

Dao ng t hp (cng rt yu) 1900 1750 cm
-1

6. Ancol, phenol
Dao ng ha tr: v
OH t do
(dung dch long) nng < 0,01M: 3300 3500 cm
-1
(3600)
v
OH t do
(dung dch c) nng > 1M: 2500 3200 cm
-1

v
C-O
1100 1300 cm
-1

7. Andehyt/xeton
Dao ng ha tr v
C=O
1650 1800 cm
-1

8. Anhidrit
Dao ng ha tr v
C=O
1800 1870 cm
-1

1750 1790 cm
-1

9. Axit cacboxylic
Dao ng ha tr v
C=O
(dime) nng bnh thng 1680 1720 cm
-1

15
v
C=O
(monome) nng rt long 1740 1800 cm
-1

Nhm OH ca axit v
OH
2500 3500 cm
-1

Pic ca nhm OH ny c chn rng
10. Mui axit cacboxylic
Dao ng ha tr v
C=O
1600 1650 cm
-1

11. Clorua axit
Dao ng ha tr v
C=O
(thng) 1795 1810 cm
-1

Dao ng ha tr v
C=O
(thm) 1765 1785 cm
-1

12. Este
Dao ng ha tr v
C=O
1720 1750 cm
-1

v
C-O-C
1150 1250 cm
-1

13. Amin
Bc 1 v
NH2
hai nh 3500 3600 cm
-1

o
NH2
1650 cm
-1

v
C-N
vng thm 1150 1200 cm
-1

1030 1120 cm
-1

Bc 2 v
NH
1 nh 3500 cm
-1

o
NH
1650 cm
-1

v
C-N
1150 1200 cm
-1

1080 1150 cm
-1

Bc 3 v
C-N
1130 1230 cm
-1

1030 1120 cm
-1

14. Amit
v
C=O
amit I 1600 1690 cm
-1

o
N-H
amit II 1500 1600 cm
-1

v
N-H
3500 v 3600 cm
-1
(-NH
2
)
3500 cm
-1
(-NH-)
15. Nitro
Dao ng ha tr v
NO2
1530 cm
-1

16
v
NO2
1330 cm
-1

2.3. Mt s v d gii ph hng ngoi
- Ghi tt c cc vng ph (chn peak), (nh peak). Ch cc peak c trng: c
im (nh kp, mnh v rng, yu v hep, nhn v hp, chn rng v ging... )
- T cng thc phn t, d on c th cha dao ng ca nhng nhm cha no?
- Cc peak ca ph c th ng vi dao ng ca nhng nhm chc no?
- i chiu
Nu ch s dng ph IR, ng vi mt s cng thc phn t v mt ph c th d
on c nhiu cng thc cu to tng ng.


ph hng ngoi ca hecxen -1
17









ph hng ngoi ca toluen

ph hng ngoi ca toluen

ph hng ngoi ca pentin - 1

18





ph hng ngoi ca anilin
ph hng ngoi ca phenol
ph hng ngoi ca anilin
19


2.4 My o ph hng ngoi
Ph k hng ngoi hin nay gm cc loi: ph k hng ngoi mt chng tia dng knh
lc, ph k hng ngoi hai chng tia tn sc v ph k hng ngoi bin i Fourier (FTIR)
- Ph k hng ngoi mt chm tia dng knh lc l loi n gin dng cho phn tch
nh lng kh. Trong my c h thng quang hc v mt bm ht mu kh dng ngun
pin.
- Ph k hng ngoi hai chm tia tn sc l loi ph bin trc y, my ghi ph qut
c vng t 4000 cm
-1
n 200 cm
-1
c ni vi b t ghi hay my vi tnh.
S ph k hng ngoi hai chm tia tn sc t ngun sng S
1
pht ra hai chm tia
song song, mt i qua mu, mt i qua cuvet so snh, sau chp li qua khe vo S
3
n
lng knh (hoc cch t) ri qua khe ra S
4
i n detect.
+ Ngun sng cho my ph hng ngoi thng dng en Nernst (hn hp oxit kim
loi 85% ZrO
2
v 15% Y
2
O
3
), n Globa (silic cacbua SiC
2
), n Nicrom (dy t niken
crom). Nhit t nng khong 700 800
0
C.
ph hng ngoi ca isobutyl nitrin
20
+ Lng knh: gm 3 ci c ch to t cc vt liu KBr, NaCl v L v mi loi ch
cho mt vng nh sng hng ngoi i qua. Cch t ch to bng thy tinh, trn mi milimet
c vch t 200 n 300 vch cch u nhau.
+ Detect: thng hay dng l lai detect t bo nhn quang, cp nhit in hoc ta
nhit.
Detect t bo nhn quang gm nhiu l kim loi trn ph bt kim loi nhy sng
nh selen, silic. Khi c mt photon p vo b mt kim loi s pht ra hng trm electron,
cc electron ny li chuyn ng n l kim loi th hai v mi electron p vo s pht ra
hng trm electron na v c tip tc nh vy i n cc l kim loi sau. Cui cng c hng
triu electron c pht ra t mt photon. Cc electron ny i n anot, to ra mt dng in
m in th ca n t l vi cng nh sng p vo.
Detect cp nhit in c ch to t hai thanh kim loi khc nhau nh bmut v
antimoan, to ra mt in th nh khi t nng ch tip gip nhau bng bc x hng ngoi.
Ch cn c mt s thay i rt nh nhit ca bc x chiu vo lm bin thin cng
dng in sinh ra (nhit bc x thay i 10
-6

0
K, in th thay i 6 8 V/W). Detect
cp nhit in c tr khng thp nn thng c ni vi b tin khuych i c tr khng
cao.
Detect ha nhit c ch to t nhng ming n tinh th ca cc cht ha nhit.
Chng l cht cch in c tnh cht in v nhit rt c bit. Cc cht ny c kp vo
gia hai in cc ng vai tr mt t in m in dung ca n ph thuc mnh vo s thay
i nhit . Khi ni hai in cc vo mt mch in s xut hin mt dng in m in
th ca n thay i rt nhy vi s thay i nhit ca bc x hng ngoi chiu vo.
+ Cuvet: cuvet o ph hng ngoi thng c hai loi cuvet o mu lng v cuvet o
mu rn.
Cuvet o mu lng (cht tinh khit hay dung dch) c cu to gm hai tm ca s
bng NaCl, KBr hoc LiF, mt vng m gia c dy bng dy cuvet, vng m v
gi bn ngoi, mt tm ca s v gi c khoan hai l np mu. Trn cuvet c ghi
r dy lp mng dung dch bn trong, khi o phi chn cp cuvet c dy nh nhau
ng mu cht v dung mi so snh. kim tra chnh xc dy cuvet, ngi ta t mt
21
cuvet khng vo my ri o trong mt vng bc sng c tn hiu ph hnh sin ri tnh
theo cng thc:

) ( 2
2 1
v v
N
d

A
=
Vi d l chiu dy ln mng. AN l s nh cc i, v
1
v v
2
l s sng.
Cc mu kh c o bng mt cuvet c bit, v hp th ca cc kh thp nn
ng nh sng i qua mu phi di. Chiu di thc ca mi cuvet kh ch 10 cm nhng
ng nh sng i qua phi di hng met, do cn c mt h thng gng t trong cuvet
nh sng i qua li mu nhiu ln.
- Ph k hng ngoi bin i Fourier (FT-IR)
Ph k hng ngoi hin i l loi ph k bin i Fourier. Loi ph k mi ny khc
loi ph k tn sc c l thay b n sc (lng knh hoc cch t) bng mt giao thoa k
Michelson nh s ch ra hnh di.

`













Cu to ca giao thoa k Michelson gm gng phng di ng M
1
, mt gng c
nh M
2
v mt tm knh phn tch nh sng S. nh sng t ngun chiu vo tm knh S
ngun sng
M2
M1
mu o
detect
1
2
O
S
22
tch lm hai phn bng nhau, mt phn chiu vo gng M
1
v mt phn khc chiu vo
gng M
2
, sau phn x tr li qua knh S, mt na tr v ngun, cn mt na chiu qua
mu i n detect. Do gng M
1
di ng lm cho on ng ca tia sng i n gng
M
1
ri quay tr li c di ln hn on ng tia sng i n gng M
2
ri quay tr li
v c gi l s tr. Do s tr ny lm nh sng sau khi qua giao thoa k bin i t tn
s cao xung tn s thp. Sau nh sng qua mu b hp th mt phn ri i n detect,
nh k thut bin i Fourier nhn c mt ph hng ngoi bnh thng ghi trn ph k
hng ngoi tn sc nhng c phn gii v t s tn hiu/nhiu (S/N) cao hn, ngha l ph
nhn c c cht lng tt hn, c bit thi gian ghi ph nhanh, ch khong 30 giy.
2.5. Mt s ng dng
Phng php ph hng ngoi c th c ng dng trong phn tch nh lng mt
cht trong dung dch hay trong hn hp. C s ca phng php ny da trn phng trnh
nh lut Lambert Beer biu hin mi quan h gia s hp th nh sng v nng cht:

D d C
I
I
= = . . log
0

Theo phng trnh trn, mt boc sng xc nh, s hp th nh sng t l vi nng
C v chiu dy cuvet d v bn cht ca cht mu. Nh vy, khi phn tch mt cht, o
mt bc sng xc nh vi mt cuvet c chiu dy d bit th mt quang D

ch cn t
l vi nng C ca mu cht. V phng trnh trn ch chnh xc vi dung dch c nng
long nn phng php phn tch nh lng bng ph hng ngoi ch p dng o trong
dung dch, cn theo phng php p mu rn (p KBr) th ch phn tch bn nh lng.
Phng php phn tch nh lng nh ph hng ngoi cng c th thc hin theo
cch lp ng chun. Pha mt lot mu vi cc nng khc nhau ca cht cn xc nh
dng tinh khit ri o gi tr D

ca chng, sau v th biu din s ph thuc D

vo
nng C. Vn kh khn v mc sai s trong phng php ny l tnh t s I
0
/I. V
nguyn tc, gi tr I
0
v I c th xc nh trn ph theo cc tm ng nn ri o gi tr I
0
v
I. Kh khn y l xc nh ng nn sao cho sai s phng php l nh nht bi v trn
ng cong ph c s che ph nhau ca cc nh cho nn c th c mt s v tr khc nhau
khi v ng nn. V th ngoi phng php ng nn, ngi ta cn tin hnh theo mt s
phng php khc t chnh xc cao hn.
23
Sau khi thit lp c th ng chun, cn ch ng chun ny ch s dng
c trong phm vi gii hn nng ng vi on thng ca ng biu din, bi v trong
gii hn ny mi c s tuyn tnh gia mt quang v nng dung dch. Sau c th
xc nh nng ca dung dch mu cn tm bng cch o gi tr D
x
ri chiu ln th
tm gi tr C
x
.
Phng php ph hng ngoi cng c th p dng phn tch nh lng hn hp
nhng thc hin rt phc tp.
2.6. Bi tp


24
CHNG 3. PH T NGOI KH KIN
Ph t ngoi v kh kin, vit tt l UV-VIS (ultraviolet-Visible) l phng php
phn tch c s dng rng ri t lu.
Vng sng: t ngoi (UV) 200 400 nm
Kh kin (VIS) 400 800 nm
Ph t ngoi v kh kin ca cc cht hu c gn lin vi bc chuyn electron gia
mc nng lng electron trong phn t khi cc electron chuyn t cc obitan lin kt hoc
khng lin kt ln cc obitan phn lin kt c mc nng lng cao hn, i hi phi hp th
nng lng t bn ngoi.
Cc electron nm obitan lin kt o nhy ln obitan phn lin kt o
*

c mc nng
lng cao nht, ng vi bc sng 120 150 nm, nm vng t ngoi xa. Cc electron t v
cc electron p (cp electron t do) nhy ln obitan phn lin kt t
*
c mc nng lng ln
hn, ng vi bc sng nm trong vng t ngoi 200 400 nm hay vng kh kin 400
800 nm ty theo mch lin hp ca phn t.
Ph t ngoi v kh kin lin quan cht ch n cu to, ni i lin hp v vng
thm. c ng dng rng ri.
3.1. C s l thuyt
3.1.1. Bc chuyn di nng lng
iu kin bnh thng, cc electron trong phn t nm trng thi c bn, khi c
nh sng kch thch vi tn s v thch hp th cc electron 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,
trng thi c bn cc electron c sp y vo cc obitan lin kt o, t hay n c mc nng
lng thp, khi b kch thch s chuyn ln cc mc nng lng cao hn:
o o
*

t t
*

n t
*
, o
*

Hiu s mc nng lng gia hai obitan chnh l nng lng hp th t ngun sng
kch thch t bn ngoi.


25










Bc chuyn di nng lng (nm) Nng lng kch thch (E, kcal/mol)
o o
*
120 230
t t
*
160 184
n o
*
180 162
n t
*
280 82
Hiu s gia cc mc nng lng ny khc nhau. V:

hc
h E = = A
Do chiu di bc sng ca cc cc i hp th s ngc li:

* * * *



< < <
n n

Thng thng trong qu trnh kch thch electron 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:

e d q
E E E E + + =
Trong : E
e
nng lng kch thch electron.
E
d
nng lng dao ng ca cc nguyn t
E
q
nng lng quay
Bc nhy nng lng i vi s kch thch electron ln hn bc nhy nng lng
i vi s dao ng v ln hn bc nhy nng lng ng vi s quay phn t:
E
e
>> E
d
>> E
q

n
t
o
t
*
o
*

S bc chuyn nng lng ca cc electron
26
3.1.2. Nhm mang mu v s lin hp ca cc nhm mang mu
Cc cht c mu l do trong phn t ca cc cht cha nhiu nhm ni i hay ni ba
nh C=C, C=O, C=N, N=N, CC, NN, -NO
2
Do vy, chng c gi l nhm mang
mu. Nu trong phn t c nhiu nhm mang mu lin hp to thnh mch di th mu ca
cht s cng m. Cc cht mu m khi o ph t ngoi kh kin cho
max
nm vng c
bc sng di. Do , nhng hp cht hu c c mch lin hp di th cc i nm pha
sng di. Cc kiu lin hp sau:
- Lin hp t - t
Loi ny xut hin khi trong hp cht c cha cc ni i lin hp, cc cc i hp
th chuyn dch mnh v pha sng di v cng hp th tng khi s ni i lin hp
tng.













(t
1
t
2
)
2
(t
1
*
t
2
*
)
2
AE < A E
t
1
, AE
t
2

>
1
,
2

Cc i hp th tng ng vi bc chuyn di ca e t t
*
ca ni i bit lp t
quan trng v nm trong vng t ngoi chn khng l
max
< 180 nm nhng ca h ni i
H
1
H
2

H
2

+
1
+
2

+
1
+ +
2


+
1
- +
2


H
1
H
2

H
2

+
1
+
2

+
1
+ +
2


+
1
- +
2


t
1

t
1
*

t
2
*

t
2

t
1
+ t
2

t
1
- t
2

t
1
*

+ t
2
*
t
1
*

- t
2
*
AE
t
2

AE
t
1

AE

S kiu lin hp t - t
27
lin hp li rt quan trng lin quan cht ch vi h lin hp ca phn t v
max
nm trong
vng t ngoi kh kin (
max
> 200 nm).
Nguyn nhn ca s thay i ny l do s lin hp gia cc lin kt t lm thay i
mc nng lng ca cc obitan (mc nng lng ca obitan lin kt c electron chim tng
ln cn mc nng lng ca obitan phn lin kt h xung lm cho nng lng ca bc
chuyn di ele4ctrron gia hai obitan gim xung do
max
tng ln.
Di hp th ny k hiu l K. Di K nm v pha sng ngn nhng cng hp th
ln (c ~ 10
4
).
Ca etilen cho nh hp th cc i 175 nm ca butadien 217 nm cn ca
hecxatrien 274 nm.
i vi vng benzen cn xut hin di hp th ng vi bc chuyn di ca h thng
electron c bc sng 256 nm c gi l di B.
- Lin hp t - p
y l s lin hp ca ni i v cp electron t do cc d t trong cc lin kt i
C=Z (Z=O, N, S) v C-X (X=Cl, Br, I) tng ng vi bc chuyn electron n t
*
. S
lin hp ny dn n s chuyn dch cc i v pha sng di nhng cng hp th thp.










CH
2
= CH
2
CH
2
= CH CH =O -CH=O

max
= 175 nm
max
= 345 nm (n - t
3
*

)
max
= 305 nm (n - t
*

)
(t - t
*
)
max
= 218 nm (t - t
3
*

)
max
= 175 nm (t - t
*

)
t
t
*

t
*

t
t
1

t
4
*



n

S kiu lin hp t - p
t
3
*


28
Khi mch lin hp t - t tng ln th bc chuyn n t
*
cng rt ngn, do cc
i hp th chuyn dch v pha sng di. Di hp th ny c k hiu l di R. Di R c
cc i hp th nm v pha sng di hn di K nhng cng hp th lun nh hn (c ~
100).
max
nm trong vng 300-350nm.
- Lin hp t - o hay cn gi l siu lin hp
Nhm ankyl th lin kt t gy ra hiu ng siu lin hp. Hiu ng ny lm cc i
hp th chuyn dch v pha sng di mt t nhng khng ln nh hai hiu ng trn, c
max

khng tng hoc tng khng ng k.
Chuyn dch bc sng
max
v pha sng di: lin hp p > lin hp >
lin hp .
S tng cng hp th
max
: lin hp > lin hp p > lin hp .
3.1.3. Phn loi di hp th
Trong ph electron c cc bc nhy electron t qu o c mc nng lng thp
sang qu o c mc nng lng cao nh o o
*
, t t
*
, n t
*
, o
*
. V tr ca cc nh
hp th tng ng vi cc bc nhy ny c mt s tnh cht c trng ring do ngi ta
phn chng thnh tng loi gi l cc di hp th nh di R, di K, di B v di E.
- Di R: tng ng vi bc nhy electron n t
*
. N xut hin cc hp cht c
cha cc d t vi cp electron t do nh O, N, S, v lin kt t trong phn t. c trng
ca di R l hp th phn t thp, c
max
thng nh hn 100. Mt khc, n lun lun cn
li trong ph khi c s thay i cu to phn t lm xut hin cc di khc sng ngn. Khi
di R chuyn dch cht t v pha sng di v c cng cao hn.
- Di K: xut hin quang ph ca cc phn t c h thng lin hp t t
*
nh
butadien hay mesityl oxit. N cng xut hin trong cc phn t ca hp cht vng thm c
lin hp vi cc nhm th cha lin kt t nh styren, benzadehyt hay axetophenon. Di K
tng ng vi bc nhy electron t t
*
v c trng bi hp th cao, c
max
> 10.000.
- Di B: c trng cho quang ph ca phn t hp cht vng thm v d vng.
Benzen c di hp th rng cha nhiu nh cu trc tinh vi, vng t ngoi gn gia 230
v 270 nm (c ~ 230). Khi c nhm mang mu ni vi nhn thm, di B quan st c
vng sng di hn di K nhng di K c cng hp th cao hn
29
V d: stiren c di K
max
= 244 nm (c
max
= 12.000) v di B
max
= 282 nm (c
max

= 450).
- Di E: ging di B l c trng ca cu trc vng thm. Ngn gc ca n l do
bc chuyn electron h benzenoit ca ba lin kt etilen trong h thng lin hp vng kn.
Di E
1
v E
2
ca benzen tm thy gn 180 nm v 200nm. hp th phn t ca di E thay
i trong khong t 2.000 n 14.000.
3.1.4. Cc chuyn dch v hiu ng.
- Chuyn dch bathochrome (bathochrome shift): chuyn dch
max
v vng c bc
sng di.
- Chuyn dch hypsochrome (hypsochrome shift): chuyn dch
max
v vng c bc
sng ngn.
- Hiu ng hyperchrome (hyperchrome effect): tng cng hp th c
max
.
- Hiu ng hypochrome (hypochrome effect): gim cng hp th c
max
.
3.1.5. Cc yu t nh hng n cc i hp th
max
v cng hp th
max

Trong ph UV, i lng c trng l
max
(c
max
) v c xem xt cn c trn s lin
hp ca phn t.
1. Hiu ng nhm th
Khi thay th nguyn t H ca hp cht anken hay vng thm bng cc nhm th khc
nhau, ty theo nhm th c lin hp hay khng lin hp i vi h ni i ca phn t
m nh hng nhiu hay t n ph t ngoi ca phn t. i vi cc nhm th khng lin
hp (nh CH
3
, CH
2
OH, CH
2
COOH) th nh hng t cn cc nhm th lin hp (nh
C=CR
2
, COOH, OH, NO
2
) c nh hng mnh lm chuyn dch cc i hp th v pha
sng di v tng cng hp th.
2. Hiu ng lp th
Khi tnh ng phng ca phn t b mt i th s lin hp ca phn t b ph v, lm

max
gim i mt t nhng c
max
gim nhiu, v vy c th xem c
max
l cn c so snh tnh
ng phng ca mt dng phn t cho trc.
V d: Xt phn t biphenyl th orto: gi u l gc to nn gia hai mt phng cha
hai nhn phenyl, nng lng lin hp ca phn t c tnh theo phng trnh:
30
AE = E
max
cos
2
u; E
max
l nng lng lin hp khi u = 0.
u (s nhm th)
max
(nm) c
max

0 s u s 45
u > 45 (mt nhm CH
3
)
= 90 (hai nhm CH
3
)
248
236
226
19 000
10 000
800
Toluen 261 225
- V d: Cc ng phn cis v trans:
-
max
(trans) ln hn
max
(cis) mt t nhng c
max
(trans) ln hn c
max
(cis) mt nhiu.
- ng phn cis ca hp cht c mch lin hp di c kh nng xut hin thm mt
cc i hp th pha sng ngn hn.
V d: trans-|-caroten: 460 (148 000), cis-|-caroten: 340 (50 000), 460 (90 000).
3. nh hng ca dung mi
Ty theo bn cht phn cc ca dung mi v cht tan m ph t ngoi ca cht tan
thay i theo cc cch khc nhau. Khi tng phn cc ca dung mi th di K chuyn dch
v pha sng di cn di R (n t
*
) li chuyn dch v pha sng ngn.
3.1.6. Nguyn l Franck-Condon
Mi bc chuyn e u km theo bc chuyn dao ng v cc bc chuyn ny u
tun theo quy lut ka chn gi l nguyn l Franck Condon v bc chuyn t trng thi
e ny sang mt trng thi e khc xy ra rt nhanh (10-16s) trong khi dao ng ca ht
nhn xy ra chm hn (10-12s) nn khong cch ht nhn hu nh khng thay i trong
khong thi gian ny.
Theo nguyn l Franck Condon th trong s kch thch e rt nhanh, bc chuyn
gia cc trng thi dao ng no khng lm thay i khong cch ht nhn s c xc sut
ln nht. C hai trng hp xy ra:
- Khi b kch thch e, khong cch cn bng gia cc nguyn t khng i (r = r
0
),
ng cong th nng trng thi e c bn v b kch thch e khng lch nhau i vi khong
cch r. Bc chuyn dao ng v = 0 sang v = 0 c xc sut ln nht, trong cu trc dao
n ca ph t ngoi c cng ln nht cn cc nh khc c cng nh hn. ng
ph c cu trc khng i xng. c trng l ph ca naphtalen
31
- Khi b kch thch e, khong cch cn bng gia cc nguyn t ln ln (r > r
0
), ng
cong th nng trng thi e b kch thch b chuyn dch so vi trng thi c bn. Bc
chuyn dao ng v = 0 sang v = 0 khng phi c xc sut ln nht m ln trng thi dao
ng cao c xc sut ln hn m bo cho khong cch cc nguyn t khng i. ng
ph c cu trc i xng. c trng l ph ca benzen.
3.2. Cu to ca ph k t ngoi kh kin
Ph t ngoi v kh kin c thit k o c vng ph t 200 1000 nm. N gm hai
loi: loi 1 chm tia o im v loi hai chm tia qut c vng ph. C hai loi ny u gm
cc b phn sau:
1. Ngn sng: dng n Tungsten halogen (o vng 350-1000nm) v n teri hay
n hiro (o vng 200-350 nm).
2. B chn sng: dng knh lc hoc b n sc. B n sc dng lng knh ch to
bng thch anh hoc cch t (vch t 2000 3600 vch/mm).
3. Detect: ph bin dng t bo nhn quang, c nhay v bn cao. Mt s my
hin nay dng detect l dn diot gm 1024 diot cho c vng t ngoi v kh kin.
4. B phn c tn hiu: loi my o im thng c b phn c tn hiu l ng h
o in th hoc b phn hin s. My hai chm tia dng b phn t ghi hoc ghp ni vi
my vi tnh v my in.
S cu to ca ph k hai chm tia ca hng Perkin Elmer
3.3. ng dng ph t ngoi kh kin.
Phng php ph t ngoi v kh kin c ngha quan trng trong lnh vc phn tch
nh tnh, phn tch cu trc phn t v phn tch nh lng. Nguyn tt ca phng php
phn tch nh lng l da vo mi quan h gia mt quang v nng dung dch theo
nh lut Lambert Beer. u im ca phng php quang ph t ngoi v kh kin trong
phn tch nh lng l c nhy cao, c th pht hin c mt lng nh cht hu c
hoc ion v c trong dung dch, sai s tng i nh (ch 1 n 3%)
Ngoi ra, n cng cn c s dng xc nh hng s cn bng, hng s phn li v
nghin cu ng.
3.3.1. Phng php o mt bc sng
32
phn tch mt mu c th thc hin theo cch n gin l o mt mu chun v
m mu phn tch ri tnh ton theo cng thc di y. Gi nng ca cht chun l C
k
,
ca mu phn tch l C
x,
da theo nh lut Lambert Beer c th vit:
D
k
= c
k
C
k
d
k
hay c
k
= D
k
/C
k
d
k

D
x
= c
x
C
x
d
x
hay c
x
= D
x
/C
x
d
x

vi: D
k
, D
x
l mt quang ca dung dch mu chun v mu phn tch.
d
k
, d
x
l chiu dy lp mng ca dung dch mu chun v mu phn tch.
c
k
, c
x
l h s hp th mol.
C
k
, C
x
l nng ca dung dch mu chun v mu phn tch.
T hai phng trnh trn suy ra:
x k
k k x
x
d D
d C D
C =
Nu chn cuvet o mu chun v mu phn tch c chiu dy nh nhau tc l d
k
= d
x

th c th vit:
k
k x
x
D
C D
C =
C
k
l nng mu chun c pha chnh xc, D
k
v D
x
l gi tr o c trn my do
tnh c nng mu phn tch.
3.3.2. Phng php lp ng chun
1. Chn
max

2. Pha dy cht chun c nng tng (gim) dn.
3. o mt quang ca cc mu bc sng trn.
4. V th ph thuc mt quang D vo nng C, ng biu din ca th
ny c gi l ng chun.
5. Pha mu phn tch sao cho nng dung dch mu o nm trong gii hn tuyn
tnh ca ng chun. Sau khi o mu phn tch nhn gi tr D
x
ri i chiu trn th c
c gi tr C
x
.
3.4. Phn gii ph UV-VIS
3.4.1. Dng ph U-VIS
D(), D(c), D(lgc);
33







3.4.2. Phn gii ph UV-VIS
Ph t ngoi ca |-carotene trong dungmi n-hexan, etanol
Ph t ngoi ca metyl propinyl xeton
34
Da vo
max
, c th bit c loi lin kt
-
max
< 150nm: ch c loi lin kt ca hp cht no.
-
max
> 150 nm: c lin kt bi
-
max
quanh vng 200 260 nm c th c benzen v benzen th.
-
max
>280 nm: h lin hp

max
cng ln th h lin hp cng di.
35
CHNG 4. PH CNG HNG T HT NHN (NMR)
Ph cng hng t ht nhn (ph CHTHN) vit tt ca ting Anh l NMR (nuclear
Magnetic Resonance) l mt phng php vt l hin i nghin cu cu to ca cc hp
cht hu c, n c ngha quan trng xc nh cu to cc phn t phc tp nh cc hp
cht thin nhin. Phng php ph bin c s dng l CHTHN-
1
H v ph CHTHN-
13
C.
4.1. C s vt l hc
4.1.1. Ht nhn trong t trng
- Ht nhn ca mi ng v ca mt nguyn t c c trng bi s lng t spin I
v s lng t t m.
I: s lng t ca spin ht nhn (I = 0, , 1, 3/2, 5/2 )
m
I
: s lng t t ht nhn m
I
= (2I+1) c cc gi tr khc nhau l -I, -I + 1, cho n
+I.
- Thc nghim: mi ht nhn nguyn t c mt s lng t spin I ht nhn nht nh,
ph thuc vo s khi ca nguyn t A v s th t ca nguyn t l Z:
S khi A l chn chn
S th t Z Chn/l Chn l
S lng t t spin , 3/2, 5/2 0 1, 3, 5
Cc ht nhn ca nguyn t tch in dng, lun lun t quay quanh trc ca n, khi
quay nh vy, n sinh ra mt mmen qun tnh gi l momen spin ht nhn P v momen t
. Mt khc, khi ht nhn nguyn t quay quanh trc ca n th in tch ht nhn s chuyn
ng trn mt vng trn quanh trc quay, lm xut hin mt dng in. Mi mt dng in
bao gi cng km theo mt t trng nn khi ht nhn quay cng xut hin mt t trng c
mmen t v ht nhn tr thnh mt nam chm vnh cu. Mmen spin ht nhn P t l
thun vi momen t :
P . = (1)
: h s t thm c trng cho mi ht nhn nguyn t.
Gi tr tuyt i ca momen spin ht nhn P tnh theo I:
P = (h/2).I (2)
Gi tr tuyt i ca momen t tnh theo I:
= (h/2).I (3)
36
I: s lng t spin ht nhn.
I = 0 th = P = 0
I 0 th 0 v P 0: ht nhn c gi l ht nhn t. y l iu kin c cng
hng t.
Bng 1. Nhng ht nhn thng gp trong hp cht hu c
ng v % trong t nhin s proton s ntron I nhy tng i
H
1

99,98 1 0 2,793 1,000
D
2

1,56.10
-2
1 1 1 0,857 9,64.10
-3

C
12
98,89 6 6 0
C
13
1,108 6 7 0.702 1,59.10
-2

N
14
99,635 7 7 0 0.404 1,01.10
-3

N
15
0.365 7 8 5/2 -0,283 1,04.10
-3

O
16
99,96 8 8 3/2
O
17
3,7.10
-2
8 9 3/2 -1,893 2,91. 10
-2

Cl
35
75,4 17 18 3/2 0.821 4,71.10
-3

Cl
37
24,6 17 20 3/2 0.683 2,72.10
-3

Br
79

50,57 35 44 3/2 2,099 7,86.10
-2

Br
81

49,43 35 46 3/2 2,263 9,84.10
-2

F
19

100 19 0 0,833
P
31

100 31 0 6,6310
-2


Ph cng hng t ht nhn ph thuc vo % ng v v momen t . Khi cng ln
th nhy cng cao.
4.1.2. S tch mc nng lng ca ht nhn trong t trng ngoi
1. Kim nam chm nhn bt k nng lng no ca t trng ngoi
Mt kim nam chm trong t trng ca tri t th kim nam chm s hng theo t
trng ca tri t. Nu lm lch kim nam chm mt gc ri th kim nam chm t do th
n s chuyn ng tr li v tr cn bng ban u. V tr cn bng l v tr c mc nng lng
thp nht. Gc lch cng cao th nng lng E ca kim nam chm cng ln:
37

0 0
. B E = (4)
u = cos . B E
0
(4)
Cos = (-1,+1) nn E = (+B
0
, -B
0
) c gi tr lin tc.
E: nng lng ca kim nam chm; B
0
: cng ca t trng ngoi.
: gi tr tuyt i momen t ca nam chm.
: gc lch
2. Ht nhn t khc vi kim nam chm, ch nhn nng lng gin on (lng t ho)
Khi khng trong t trng, cc ht nhn c cng u mc nng lng bng
nhau. Khi t mt ht nhn t vo trong mt t trng ngoi c cng B
0
th cc momen
t ca ht nhn t s xoay theo hng c ng sc t ca t trng ngoi.
Ht nhn nguyn t t khi trong mt t trng ngoi khc vi mt kim nam chm
trong t trng ca tri t: ht nhn t khng phi tip nhn bt k mt v tr no ca t
trng bn ngoi m n ch mt s v tr nht nh trong khng gian tng ng vi mt s
trng thi nn lng xc nh ngha l nng lng ca ht nhn t c th hin qua gi tr
ca cos: cos = m/I (5)
I: s lng t ca spin ht nhn (I = 0, , 1, 3/2, 5/2)
m
I
: s lng t t ht nhn (m = -I n +I) c 2I + 1 gi tr
V d 1: Ht nhn
1
H,
13
C,
31
P; c I =
Khi I = th m
I
= - v v m
I
c 2.1/2 + 1 = 2 gi tr
T (5) suy ra cos = -1 v +1 nn = 0 v =
V d 2: Ht nhn
2
D,
14
N; I = 1
Khi I = 1 th m
I
= -1,0,+1 c 2.1+1 = 3 gi tr
T (5) suy ra cos = -1,0,1 nn = /4; = 0 v = 3/4
3. S tch mc nng lng ca ht nhn trong t trng ngoi
Cc ht nhn nguyn t
1
H,
13
C,
31
P c s lng t spin ht nhn I = v s lng
t t m
I
= - v , khi t chng vo trong t trng ca nam chm th cc spin ny s
quay hng ngc chiu nhau v chim hai mc nng lng khc nhau c hiu s l:

0 0
B
2
1
hay B
2
h
. h E
t
= v
t
= v = A
38
y:
I
2
h
I
m
. . B cos . . B E
0 0
|
.
|

\
|
t
=
= u =

Do :
0
B . m .
2
h
E
t
=
Khi m = :
0 1
B . .
2
h
2 / 1 E
|
.
|

\
|
t
=
m = -:
0 2
B . .
2
h
2 / 1 E |
.
|

\
|
t
=
Vy:
0 0
B . .
2
1
hay B . .
2
h
. h E
t
= v
t
= v = A
y, E l nng lng cng hng, l tn s cng hng, B
0
l cng ca t
trng nam chm, l h s t thm, mi ht nhn c gi tr khc nhau nh (
1
H) ~ 4(
13
C).
Hnh v sau ch ra s phn tch mc nng lng ca ht nhn t t trong t
trng ngoi, ht nhn c s lng t t m = c mc nng lng thp cn ht nhn t c
s lng t t m = - c mc nng lng cao, hiu s gia hai mc nng lng l E.









S phn b ny khng bng nhau, s ht nhn nng lng thp bao gi cng nhiu
hn s ht nhn nm mc nng lng cao mt t v tun theo s phn b Boltzman:
1 e
N
N
kT
E
1
2
( =
A

N
1
: s ht nhn chim mc nng lng thp
N
2
: s ht nhn chim mc nng lng cao
E
m = -1/2
m = 1/2
E = (h/2t)B
0

vng t trng
39
T: nhit tuyt i
4. iu kin kch thch ht nhn t ( tch mc nng lng trong t trng B
0
)
Mun xy ra hin tng cng hng phi chiu vo ht nhn mt t trng B
1
c tn
s cng hng l
1
sao cho B
1
vung gc vi B
0
.
Khi :
0 1 0 1
B . .
2
1
B . .
2
h
E h
t
= v
t
= A = v

1
l tn s cng hng t (tng ng vi nng lng cn kch thch ht nhn chuyn
t mc thp ln mc cao nm trong vng sng v tuyn 10
8
10
6
Hz
4.1.3. Hin tng cng hng t ht nhn
Khi cho mt t trng B
0
tc dng ln cc phn t c cha ht nhn th s dn ti s
tch mc nng lng v dn n s phn b cc ht nhn theo cn bng Boltzmann.
Trong t trng B
0
, cc ht nhn khng nm yn m trng thi cn bng ng. Nu
mun ph v trng thi cn bng ng ny cn phi cung cp nng lng t ngoi vo bng
cch cho mt t trng khc c cng B
1
tc dng vo cc phn t ny. iu s lm
thay i li s phn b cc ht nhn gia hai mc nng lng trn. Mt s ht nhn s hp
th nng lng ca t trng B
1
nhy t mc nng lng thp ln mc nng lng cao
v ngc li, mt s ht nhn mc nng lng cao s bc x nng lng chuyn xung
mc nng lng hp. Nng lng cn thit cung cp cho qu trnh thay i ng bng
E = nng lng cng hng t nhn. Qu trnh hp th nng lng E phn b li cn
bng ngj trong t trng B
1
gi l hin tng cng hng t nhn. Hin tng cng
hng t xy ra khi ht nhn hp th cc nng lng c tn s bng
0
c gi l tn s
cng hng t.
4.2. chuyn dch ho hc
4.2.1. Hng s chn v t trng hiu dng
Hng s chn xut hin do hai nguyn nhn:
- Hiu ng nghch t: cc in t bao quanh nguyn t sinh ra mt t trng ring,
ngc chiu vi t trng ngoi nn lm gim tc dng ca n ln ht nhn nguyn t. Lp
v in t cng dy c th t trng ring ngc chiu vi t trng ngoi cng ln tc
hng s chn cng ln.

40


S hiu ng nghch t
V vy, cc proton nm trong cc nhm c nguyn t hay nhm nguyn t gy hiu
ng I (Cl, Br, I, NO
2
) s c hng s chn nh, tri li khi cc nhm nguyn t gy hiu
ng +I (CH
3
, C
2
H
5
) s c hng s chn ln.
- Hiu ng thun t: bao quanh phn t l lp v in t, cc in t ny chuyn
ng sinh ra mt dng in vng, do xut din mt t trng ring c hng thay i
ngc hng hoc cng hng vi t trng ngoi. Tp hp tt c cc im trn cc ng
sc m ti tip tuyn vung gc vi t trng ngoi s to nn mt mt parabon. Pha
trong mt parabon, t trng tng hp nh hn B
0
v t trng ring ngc hng vi t
trng ngoi, cn pha ngoi parabon th t trng tng hp ln hn B
0
v t trng ring
cng hng vi t trng ngoi. Do hng s chn pha ngoi parabon nh cn pha trong
th c hng s chn ln ngha l chuyn dch hc cng cc proton nm pha ngoi
parabon s ln cn pha trong s nh.

S hiu ng thun t : a) benzen; b) nhm C=C; c) nhm C=O; d) nhm CC
Khi t mt ht nhn nguyn t vo mt t trng ngoi B
0
th cc e quay quanh ht
nhn cng sinh ra mt t trng ring B c cng ngc hng v t l vi t trng
ngoi:
B = -B
0

41
T trng thc tc dng ln ht nhn l:
B
e
= B
0
B = B
0
B
0

B
e
= B
0
(1-)
B
e
l t trng hiu dng
: l hng s chn c gi tr khc nhau i vi mi ht nhn nguyn t trong phn t.
Ph thuc vo s e, nu s e cng nhiu th cng ln.
Hng s chn t l thun vi in tch e, mt e bao quanh ht nhn v t l nghch
vi khi lng e. Hng s chn cng ln th t trng hiu dng B
e
cng nh.
4.2.2. chuyn dch ho hc
i vi cc ht nhn trong phn t cng phc tp trong nguyn t do nh hng ca
cc m my electron ca cc nguyn t bn cnh.
V d: xt
1
H nhm CH
3
ca phn t TMS (CH
3
)
4
Si v
1
H nhm CH
3
ca axeton:
Do nh hng ca nhm CO ht e lm cho m my electron
1
H ca axeton <
1
H
ca TMS nn:
1
H (TMS) >
1
H (aceton)
B
e
(TMS) < B
e
(aceton) ti v tr ht nhn
1
H trong TMS so vi trong
aceton.
Do hiu ng chn t khc nhau nn cc ht nhn
1
H v
13
C trong phn t c tn s
cng hng khc nhau. c trng cho cc ht nhn
1
H v
13
C trong phn t l gi tr
chuyn dch ho hc .
Vi cng mt t trng ngoi B
1
, c tn hiu cng hng ca
1
H

vi t trng, tn
s cng hng (aceton) > TMS hoc t trng s dng i vi TMS phi c cng ln
hn i vi aceton. C hai phng php to ra iu kin tho mn iu kin cng hng
(
1
=(1/2)..B
0
) ghi tn hiu cng hng.
1. Phng php qut trng: thay i B
0

t TMS v aceton vo t trng B
0
v s dng mt t trng b sung, tng dn
cng ca t trng b sung n mt lc no cng t trng hiu dng tc
ng ln xut hin tn hiu cng hng. V Be(TMS) < Be (aceton) nn ch cn b sung mt
gi tr t trng B
0
B
e
nh hn th aceton xut hin tn hiu cng hng trong khi
th t trng tc dng ln v tr ht nhn
1
H (TMS) cha mnh cha c tn hiu cng
42
hng. Tip tc tng t trng b sung n mt gi tr no t trng tc dng ln
1
H(TMS) t bng B
0
th xut hin tn hiu cng hng ca
1
H (TMS).







Ph
1
H-NMR ca hn hp axeton-TMS
Khong cch gia hai tn hiu ca TMS v aceton l:

0 aceton TMS 0 aceton 0 0 TMS 0
B ) ( ) B B ( ) B B ( B o o = o + o + = A
Khong cch ny va ph thuc vo hng s chn va ph thuc vo cng t
trng ngoi B
0
.

aceton TMS
0
B
B
o o =
A
= o
Ch ph thuc vo hng s chn, khng ph thuc vo t trng ca thit b.
2. Phng php qut tn
Gi nguyn t trng B
0
, thay i tn s ca t trng B
1
c s cng hng
aceton > TMS.
- Khi t hai ht nhn nguyn t
1
H ca cng nguyn t hydro ca TMS v ca
aceton vo mt t trng ngoi B
1
, khi c cng hng th:

( )
( )
aceton 0 aceton
TMS 0 TMS
1 B . .
2
1
1 B . .
2
1
o + |
.
|

\
|
t
= v
o +
|
.
|

\
|
t
= v

Hiu s: ) ( B . .
2
1
aceton TMS 0 aceton TMS
o o
t
= v v = v A
( ) o = o o v =
aceton TMS 1

Vi k thut o ny cng c th ghi nhn c l i lng khng ph thuc vo
thit b bn ngoi.
axeton
TMS (xut hin mun nht
1
H (axeton)
43
Nh vy, d thay i cng t trng ngoi B
1
hay thay i tn s sng radio u
c th biu din theo l i lng khng ph thuc vo thit b bn ngoi. Trong k thut
o, ngi ta khng th o c gi tr tuyt i ca
TMS
,
aceton
v nhng c th o c
khong cch gia hai tn hiu proton , thay i tu theo ln ca t trng B
1
nhng
khng thay i.
TMS l cht c hng s chn ln nht nn dng n lm cht chun o chuyn
dch ho hc.i vi ht nhn
1
H th:

0
TMS H
H TMS
v
v v
= o o = o
y,
TMS
l hng s chn ca cht chun TMS (tetrametylsilan),
H
l hng s
chn ca ht nhn mu o,
TMS

H
l tn s cng hng ca cht chun v ca ht nhn mu
o. Hng s chn xut hin do nh hng ca m my electron bao quanh ht nhn
nguyn t, do tu thuc vo v tr ca ht nhn
1
H v
13
C trong phn t khc nhau m mt
electron bao quanh n khc nhau dn n chng c gi tr hng s chn khc nhau v
do chuyn dch ho hc ca mi ht nhn khc nhau.
Tng qut: =
TMS

X


X
: hng s chn ca cht cn o.
khng c th nguyn m c tnh bng phn triu (ppm).
i vi ph CHTHN
1
H th c gi tr t 1 n 12 ppm cn ph
13
C th c gi tr t
0 n 220ppm.
Vy chuyn dch ho hc l i lgn c trng cho nhng ht nhn cng loi
ca mt n v b che chn tng ng nhau trong mt hp cht. N khng ph thuc vo
thit b bn ngoi (cng t trng hay tn s sng) khng c th nguyn v c tnh
bng ppm.
V d:
+ Phn t C
6
H
5
-CO-CH
3
, ph CHTHN
1
H c:
CDHH = 7,5-8,2ppm ca C
6
H
5

= 2,5ppm ca CH
3

+ Phn t CH
2
=CH-COO-CH
2
CH
3
, ph CHTHN
1
H c:
CDHH = 6,2 ppm ca =CH
2
v 5,8 ppm ca =CH
44
= 4,2 ppm ca CH
2
- v 1,2 ppm ca CH
3

Thang CDHH

Da vo chuyn dch ho hc c th xc nh c cu to ca phn t.
V d: phn t CH
3
CH
2
OH s cho 03 tn hiu c trng cho mi nhm:







4.3. Tng tc spin spin
Phn t etanol CH
3
CH
2
OH l ra trong ph CHTHN-
1
H ch c 3 tn hiu ng vi 03
nhm CH
3
, CH
2
v OH nhng trn ph thc nghim xut hin bi nh mi nhm: CH
3
l
03 nh, CH
2
l 04 nh v OH l 03 nh (vi etanol khan tuyt i) hoc 1 nh (etanol
thng) nh hnh v di:





3,7
2,5 1,2 0 , ppm
HO CH
2
CH
3

3,7 2,5 1,2 0 , ppm
HO CH
2
CH
3

45

Ph cng hng t ht nhn ca
1
H ca etanol
Nguyn nhn ca s xut hin bi nh ny l do s tng tc ca cc proton nm
cnh nhau. Mi proton ging nh mt nam chm nh, n sinh ra hai t trng ph ngc
chiu nhau tc dng ln proton bn cnh lm phn tch mc nng lng ca t trng
ngoi B
0
tc dng ln proton , kt qu sinh ra tn hiu bi, s phn tch mc nng lng
th no tu thuc vo s proton mi nhm. Hin tng ny c gi l tng tc spin
spin.
hiu r vn ny, c th kho st mt v d c th l s tng tc ca cc proton
trong phn t 1,1,2-tricloetan di y trong cc proton c k hiu l H
a
, H
b
, H
c
.


Trc tin, c th coi H
a
l mt nam chm nh, n sinh ra hai t trng ph ngc
chiu nhau. T trng ph ny tc dng ln vng quanh ht nhn H
b
v H
c
c th qua khng
gian hoc e lin kt, phn tc dng qua khng gian gi l tng tc trc tip nhng i vi
46
cht kh v lng n xy ra rt nhanh khng o c, phn tc dng qua e xy ra chm hn c
th pht hin c gi l tng tc khng trc tip. i vi cht rn c th o c tng
tc spin spin qua khng gian, kt qua cho mt tn hiu rng.
y, ht nhn H
a
tc dng ln ht nhn H
b
v H
c
2 t trng ph ngc chiu nhau,
lm phn tch mc nng lng ca t trng ngoi tc ng ln H
b
v H
c
thnh 2 mc do
cho hai tn hiu ph. V H
b
v H
c
c ci l tng ng nn 2 tn hiu ph ny l ca c
H
b
v H
c
.
Ngc li, H
b
v H
c
cng tc ng ln Ha bng hai t trng ph ngc chiu nhau,
t hp li ta s c cc hnh khc nhau nh hnh di:
H
b

B
0
H
c

Nhn s trn thy c ba trng hp khc nhau: th nht H
b
v H
c
tc ng ln H
a

ngc chiu nhau, trng hp th 3 c H
b
v H
c
tc ng ln H
a
hai t trng ph ngc
chiu nhau vi t trng ngoi B
o
. Kt qu l mc nng lng B
0
tc ng ln H
a
phn tch
lm ba mc v do cho ba tn hiu ph khc nhau nh hnh v trn ng vi nhm Cl
2
CH-
nhn c ba nh cn i vi nhm ClCH
2
- nhn c 2 nh.
bi ca tn hiu (s nh trong mi nhm) ph thuc vo s proton nhm bn cnh
m n tng tc.
bi M = N + 1 (N-s ca nhng ht nhn t tng ng bn cnh)
V d: bi ca cc nhm nh sau:
1) 1,1,2-Tricloetan: Cl
2
CH-CH
2
Cl
CHCl
2
: 2+1 = 3 nh 1+1 = 2 nh : CH
2
Cl
Nhm CH c 3 nh cn nhm CH
2
c 2 nh
2) Etanol: HO CH
2
CH
3

CH
3
: 3 + 1 = 4 nh 2 + 1 = 3 nh
Nhm CH
2
c 4 nh cn nhm CH
3
c 3 nh
3) 2 Clopropan Cl-CH(CH
3
)
2

CH: 6 + 1 = 7 nh 1 + 1 = 2 nh: CH
3

Nhm CH c 7 nh cn 2 nhm CH
3
c hai nh v 2 nhm CH
3
tng ng coi
nh c 6H nh nhau.
47
T l cng tn hiu ca mi nhm tun theo tam gic Pascal nh sau:
T l chiu cao cc vch trong mi nhm S nh K hiu S proton (N)
1 1 nh Singlet 0
1:1 2 nh duplet 1
1:2:1 3 nh Triplet 2
1:3:3:1 4 nh Qualet 3
1:4:6:4:1 5 nh Quynlet 4
1:5:10:10:5:1 6 nh Sexlet 5
1:6:15:20:15:6:1 7 nh septet 6

Nhn s trn thy cc nhm tn hiu c bi ln th cng tn hiu nh gia
v nh ngoi gp nhau nhiu ln v th i vi nhm 6, 7 nh tr ln th ch xut hin mt
s t hn. V d nhm 7 nh thng ch xut hin 5 nh.
Ngoi ra khong cch gia hai nh lin nhau mi nhm c o bng Hertz (Hz)
v c gi l hng s tng tc spin-spin J. y l mt thng s ph quan trng nh
chuyn dch ho hc.
4.4. ng cong tch phn tn hiu
Din tch gii hn bi ng cong ph t l vi s proton ca mi nhm nhng do
vic o din tch ny kh chnh xc nn ngi ta s dng ng cong tch phn xc nh
t l s proton ca mi nhm, v chiu cao ca bc thang t l vi s proton mi nhm.
Ngoi ra, chiu cao bc thang cn t l vi nng cht trong dung dch, do ngi ta c
th tnh c nng cht da vo ng chun v cht chun.
V d, phn t toluen C
6
H
5
cho hai nhm tn hiu ng vi phn phenyl (cha 5H) v
vi nhm metyl (cha 3H) th din tch ny s l:
S (C
6
H
5
) : S (CH
3
) = 5:3
S: din tch ca mi tn hiu
Tuy nhin vic tnh ton din tch ny thng kh khn do s xut hin a vch
mi nhm. khc phc tr ngi ny, ngi ta s dng k thut tch phn tn hiu, v cc
ng cong bc thang. Chiu cao ca cc bc thang trn mi nhm tn hiu cng hng
cng t l vi s proton ca mi nhm. ng cong ny c gi l ng cong tch phn.
48

Ph cng hng t ht nhn proton ca etylbenzen. Chiu cao bc thang ng cong tch
phn t l vi s proton moix nhm
4.5. Phng php phn tch ph cng hng t ht nhn
1
H
Nhim v ca phn tch ph cng hng t ht nhn l phi tm c cc thng s t
cc ph ghi ra. y, gii hn vic tm cc gi tr: chuyn dch ho hc v hng s
tng tc spin spin (J) ca cc proton v cc ht nhn khc c I = .
4.5.1. K hiu ca ph
Khi gia hai hay nhiu ht nhn trong phn t c tng tc spin spin vi nhau
ngi ta ni n h ht nhn. Ngi ta k hiu cc ht nhn bng cc ch ci A, B, C, ,
M,X, Y...
Cc ht nhn ca cng loi ht nhn v c chuyn dch ho hc nh nhau gi l
cc ht nhn tng ng v c k hiu bng mt loi ch ci, cn s lng cc ht nhn
ny c ghi bng ch s pha di bn phi v d: A
2
B, A
2
X S nh gi cc ph ph
thuc vo t l ca hiu s chuyn dch ho hc v hng s tng tc spin:
K
J J
12 12
2 1
=
v A
=
v v

Nu hiu s ca chuyn dch ho hc ca hai nhm ht nhn nh hn hng s
tng tc ca chng (K < 1) th ngi biu din nhng ht nhn ny bng cc ch ci lin
tip nhau. V d: AB, A
2
B, ABC.
49
Ngc li, nu hiu s ca chuyn dch ho hc ln hn hng s tng tc ca
chng th ngi ta biu din h ht nhn bng ch ci cch xa nhau; v d: AX, A
2
X,
AMX,
Trng hp K > 6 th xp vo ph bc 1. Cn li xp vo ph bc cao.
4.5.2. Ph bc 1

i vi ph bc 1, c th p dng quy tt s vch ti v t l chiu cao cc nh
trong mt nhm tun theo quy tt Pascan.
H ph bc 1 thng c dn A
m
X
n
v A
m
M
n
X
y
. Cc h ph AX c h tm thy s
nh ca mi nhm d dng v hng s tng tc J v tn s
A
hay
X
.
V d:




50
Trng hp chung A
n
M
m
X
y
cng thu c 3 nhm nh nhng s nh mi nhm
ph thuc vo s proton nhm bn cnh. V d, hp cht 1-nitropropan CH
3
-CH
2
-CH
2
-
NO
2
thuc v h ph A
3
M
2
X
2
cho ph cng hng t ht nhn hnh sau:

Nh s khc bit v chuyn dch ho hc v tng tc spin spin ca cc ht nhn
nn c th xc nh c cu to cc phn t.
Hnh 3. ch ra ph
1
H-NMR ca etylformiat HCOCH
2
CH
3
cho
CHO
= 8,1 ppm,

CH2
= 4,2 (4 nh) v
CH3
= 1,3 ppm (3 nh).
4.5.2. Ph bc cao AB, A
2
B v ABX
Tt c cc loi ph khng th phn tch theo ph bc 1 gi l ph bc cao. Hu ht
cc loi ph ny c (
A

B
) J
AB
. Ngi ta k hiu cc ht nhn bng cc ch ci lin tip
nhau, v d AB, ABC, A
2
B. Vic phn tch cc loi ph ny phc tp hn cc ph bc1,
trong nhiu trng hp khng th phn tch trc tip c. Di y trnh by mt vi
trng hp n gin ca loi ph ny.
1. Ph AB
Cc ph c xp vo ph bc cao c K < 6 n gin nht l h AB v ABX. tm
cc thng s v J trc tip trn ph nh h ph bc 1, ta xt v d ph AB gm hai cp
nhm nh, cc thng s c tnh theo cng thc:
) ( 5 , 0
3 2 AB
v + v = v ( )( )
3 2 4 1 AB
v v v v = o

2
AB
AB A
o
+ v = v
2
AB
AB A
o
v = v
51
( ) ( )
4 3 2 1 AB
J v v = v v =
V d: ph cng hng t ht nhn ca 3-brom-2-tert-butoxithiophen

2. Ph A
2
B


ph l thuyt ca A
2
B
Ph A
2
B l h gm 3 ht nhn tng tc vi nhau trong c hai ht nhn tng
ng. Ph gm hai phn, v l thuyt phn A v 8 nh v phn B c 6 inh (hnh v)
nhng ph thc th s nh t hn. V d, ph
1
H-NMR ca 1,3,4 tribrombut-1-in phn A
52
ch xut hin 4 nh v phn B 4 nh (hnh v). C th phn tch ph A
2
B nh trn hnh v,
tnh cc gi tr nh sau:

( )
( )
8 , 5 4 , 1 AB
7 5 A 3 B
3
1
J
2
1
;
v + v =
v + v = v v = v


Ph
1
H-NMR ca 1,3,4-tribrombutin-1
3. Ph ABX
Ph ABX thng gp trong p cng hng proton c bit cc hp cht thm v
anken cng nh cc hp cht cha ht nhn t khc (
19
F,
31
P) gm ba ht nhn khng tng
ng tng tc vi nhau phn tch ph thnh hai phn ring bit. phn tch ph cn
tch ring bit phn AB v phn X, v d ph
1
H-NMR ca stirenoxit di, phn AB c 8
nh v phn X c 4 nh.

53
V l thuyt, h ph ABX gm hai phn, phn AB c 8 nh cn phn X c 6 nh,
thc hin ta tm chia phn AB thnh AB v AB, t phn ny c th tm c J
AB
v cc
gi tr:

BX B
,,
B X A A
,,
A
BX B
,
B X A A
,
A
J
2
1
; J
2
1
J
2
1
; J
2
1
+ v = v + v = v
+ v = v + v = v

Tu theo s cng du hay tri du ca J
AX
v J
BX
m dng ph thay i nh sau:

Trong phn AB c hai nhm 4 nh, t y tm c
A
,
B
, J
AB
, J
AX
, v J
BX
, trong
phn X ch tm c
X
.
4.5. Phn tch ph cng hng t ht nhn
13
C
V tt c cc hp cht hu c u cha nguyn t cacbon m tron nhin nguyn t
cacbon -13 chim t l 1,1% nn ph cng hng t nhn
13
C (CHTN-
13
C) hin nay c
ngha quan trng, n cho nhiu thng tin hn ph CHTN-
1
H, v d hp cht hu c
khmg cha hiro th khng c tn hiu trong ph CHTN-
1
H nhng n cho tn hiu ca ph
54
CHTN-
13
C. V t l ca
13
C nh v hng s t l gyromagnetic thp nn tn hiu cng
hng t thng nh, ngi ta phi o trn ph k cng hng t bin i Fourier (FT). Khi
dng my ny c th ghi ph CHTN-
13
C theo mt s cch khc nhau, nhng quan trng nht
l phng php ph
13
C tng tc
1
H v xo tng tc
1
H. C hai phng php u cho cc
thng tin gi tr trong vic phn tch cu trc cc hp cht hu c.
4.5.1. Ph
13
C tong tc
1
H
Trn ph tng tc
13
C -
1
H nhn c cc nhm nh khc nhau c th nh n
hay bi nh. V
13
C v
1
H u c I= nn quy tc a vch c p dng ging nh tng
tc
1
H -
1
H Ca ph CHTN-
1
H :
siglet (1 vch) khng c C
duplet (2 vch) c 1 CH
triplet (3 vch) c 2 H CH
2

quartet (4 vch) c 3 H CH
3

Hng s tng tc J(
13
C-H) ph thuc vo c trng s ca obitan lai ho nguyn t
cacbon.c trng s cng ln th hng s tng tc cng ln:
Lai ho J
C-H
(Hz)
CH sp
3
125
CH sp
2
160
CH sp 250
Khi c nhm th m in gn vo nguyn t cacbon th
1
J
H C
thng tng:
CH
4
125 H
Z
, CH
3
Cl 151 H
Z
, CH
2
Cl
2
178 H
Z
, CHCl
3
209 H
Z

Tng tc C v H cch xa nhau hn 1lin kt thng rt nh, v d
2
J
H C
= 5 H
Z
,
thng khng thy.
Tng tc gia
13
C v
13
C cnh nhau t c ngha cho vic chng minh cu to.
4.5.2. Phng php ph
13
C xo tng tc
1
H
Ph
13
C tng tc
1
H cho nhiu nhm nh do s khc nhau v s proton trong cc
nhm CH, CH
2
v CH
3
, nhng cng ca cc nh qu nh ln vi c nhiu ca my,
do vic gii ph gp kh khn, v vy ngi ta a ra cch lm n gin ho bn ph
55
chn mt s hng tin cn thit, bng cch xo i cc vch tng tc C-H. By gi ng vi
mi nguyn t cacbon ch co 1 vch ph. V d:

Ph CHN-
13
C c tng tc

(a) v xo tng tc C-H (b)
Trong tp ch, loi ph CHTN-
13
C xo tng tc C-H c k hiu l
13
C { } H
1
.
Thc t ph CHTN-
13
C tng tc C H ngy nay t o. Thay cho phng php , ngi
ta dng cc phng php k thut hin i nh APT.(Attached Proton Test) c th phn bit
c C, CH, CH
2
v CH
3
.
Khi dng k thut ny th tn hiu ca nhm C v CH
2
nm pha trn, cn tn hiu
ca nhm CH v CH
3
nm pha di ng nm ngang nh hnh 4.18.
Ngoi ra cn s dng phng php DEPT ghi ph, theo phng php ny tn hiu
CH
3
v CH pha trn cn CH
2
pha di. V d ph CHTN-
13
C ghi theo DEPT ca 2-
butanol di:






Cng vch ph ton ph xo tng tc
13
C-
1
H t l vi:
1- S nguyn t hiro gn vi nguyn t cacbon.
2- S nguyn t cacbon tng ng.
Thng th nhm CH
3
v CH
2
cho cng vch ph nh nhau, nhng nhm CH
v C cho cng yu hn. V d:
CH
3
-CH
2
CH(OH)-CH
3

CH
CH
2

CH
3
CH
3
56







4.5.3. chuyn dch ho hc
V tr ca cc tn hiu cng hng
13
C rt quan trng cho vic xc nh cu to cc
hp cht. chuyn dch ho hc
13
C nm trong mt vng rng hn nhiu so vi ph
CHTN-
1
H, t 0 n 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, d
1
-clorofom, d
12
-xiclohexan, d
6
-
dimetylsunfoxit, d
4
-metanol, tetraclometan
chuyn dch ho hc
13
C c xc nh bi:
a) Mc lai ho ca nguyn t cacbon.
b) m in cua cc nhm th nguyn t cacbon.
Cc nhm th c nh hng mnh n s thay i v tr chuyn dch ho hc, v
d:
CH
3
l CH
3
Br CH
3
Cl CH
3
F
-33 9 24 75 ppm

R-C(CH3)
3
CH
3

3xCH
3

C 1
2
3
4
1
2
4
3
R-C
6
H
11
R-C
6
H
5
57
CHNG 5
PH KHI CA CC HP CHT HU C
Phng php ph khi lng c ngha rt quan trng i vi vic nghin cu xc
nh cu trc cc hp cht hu c. Da trn cc s khi thu c trn ph c th xy dng
cu trc phn t hoc chng minh s ng n ca cng thc cu to d kin.
5.1. Qu trnh ion ho phn t
5.1.1. S ion ho
Nguyn tt chung ca phng php ph khi lng l ph v phn t trung ho thnh
ion phn t v cc ion dng mnh c s khi z = m/e (m l khi lng cn e l in tch
ion). Sau phn tch cc ion ny theo s khi v ghi nhn thu c ph khi lng. Da
vo ph khi ny c th xc nh phn t khi v cu to phn t ca cht nghin cu.
Khi bn ph cc phn t hp cht hu c trung ho bng cc phn t mang nng
lng cao s tr thnh cc ion phn t mang in tch dng hoc ph v thnh mnh ion v
cc gc theo s sau:
ABCD + e ABCD
+
+ 2e
ABCD
++
+ 3e
ABCD
-

S hnh thnh cc ion mang in tch +1 chim 95%, cn li cc ion mang in tch
+2 hoc ion m (-). Nng lng bn ph cc phn t thnh ion phn t khong 10eV. Nhng
vi nng lng cao th ion phn t c th ph v thnh cc mnh ion dng (+), hoc ion
gc, cc gc hoc phn t trung ho nh hn:
ABCD
+
+ e ABC
.
+ D
+

AB
.
+ CD
+

A
+
+ BCD
A + BCD
+

.
S ph v ny ph thuc vo cu to cht, phng php bn ph v nng lng bn
ph. Qu trnh ny l qu trnh ion ho.
Cc ion dng hnh thnh u c khi lng m v in tch e, t s m/e c gi l
s khi z. Bng cch no , tch cc ion c s khi khc nhau ra khi nhau v xc nh
58
c xc sut c mt ca chng ri v th biu din mi lin quan gia cc xc sut c
mt (hay cng I) v s khi z th th ny c gi l ph khi lng.
5.1.2. Phn loi cc ion
1. Ion phn t
Ion phn t c hnh thnh do mt i 1 electron, cho nn khi lng ca n chnh l
khi lng ca phn t hay trng lng phn t, c k hiu l M
+
. Ion phn t c cc tnh
cht sau:
- M
+
l ion c khi lng ln nht chnh l trng lng phn t
- M
+
l ion vi th xut hin nh nht.
- M
+
l s chn nu phn t khng cha d t N hay cha mt s chn d t N v M
+

s l s l nu cha mt s l d t N.
- Tt c s ph v phn t u c th tnh t hiu s khi lng ca cc phn t ion
vi ion phn t.
- Cng ca M
+
t l vi p sut mu. N ph thuc vo dy hp cht, nng lng
ca electron v kh nng ph v phn t. Cng ca M
+
c gi tr t 0 n 100%.
2. Ion ng v
Ion phn t ca cc hp cht khng phi ch l vch ring l v cc nguyn t cha
trong hp cht thin nhin u tn ti ng v nh
13
C bn cnh
12
C,
15
N bn cnh
14
N,
17
O,
18
O bn cnh
16
O,
37
Cl bn cnh
35
Cl.
Cc ng v tn ti trong t nhin vi cc t l khc nhau cho nn bn cnh vch
chnh ng vi ion M
+
cn c cc vch (M+1)
+
v (M+2)
+
vi cng nh hn. Chiu
cao ca cc vch ph ny t l vi s c mt ca cc ng v trong phn t. Ngi ta da
vo cc c im ny tnh cng thc cng ca cc hp cht nh phng php khi ph.
Chng hn, nguyn t cacbon trong thin nhin tn ti
12
C 100%,
13
C l 1,1%. Nh
vy, nu mt hp cht ch cha mt nguyn t cacbon nh metan th ion M
+
c chiu cao
100% (
12
CH
4
) th ion (M+1)
+
s c t l 1,1% (
13
CH
4
). phn t etan c hai nguyn t
cacbon nn ion M
+
c chiu cao l 100% (
12
C
2
H
6
) th ion (M+1)
+
s c chiu cao 2.1,1% =
2,2% (
13
CH
3
12
CH
3
). Nh vy, nu phn t c n nguyn t cacbon th ion (M+1)
+
s c t l
n.1,1% so vi chiu cao ca ion phn t M
+
.
59

h . 0011 , 0
h
n
'
=
h l chiu cao vch ph M
+
v h l chiu cao vch ph (M+1)
+
.
Khi bit c chiu cao ca cc vch ph c th tnh c s nguyn t cacbon trong
phn t.
Khi lng v thng gp trung bnh ca cc ng v trong mt s nguyn t:
ng v Khi lng thng gp tng i
1
H 1,0078 100
2
H

2,0141 0,015
12
C

12,0000 100
13
C

13,0034 1,12
14
N

14,0031 100
15
N

15,0001 0,366
16
O

15,9949 100
17
O

16,9991 0,037
18
O

17,9992 0,240
19
F

18,9984 100
28
Si

27,9769 100
29
Si

28,9765 5,110
30
Si

29,9738 3,385
31
P

30,9738 100
32
S

31,9721 100
33
S

32,9715 0,789
34
S

33,9679 4,433
36
S

35,9677 0,018
35
Cl

34,9689 100
37
Cl

36,9659 32,399
79
Br

78,9183 100
81
Br

80,9163 97,940
60
ng v Khi lng thng gp tng i
127
I

126,9044 100
3. Ion mnh
c sinh ra khi phn t b phn mnh do va chm vi electron.
4. Ion metastabin
Mt s ion xut hin nh bc trung gian gia cc ion c khi lng ln m
1
v m
2
c
thi gian sng ngn khng ghi nhn c y cng vch ph nhng cng c th pht
hin c s c mt ca n gi l ion metastabin m
*
m m
*
= m
2
/m
1
. Nh m
*
ta c th
khng nh c m
2
l do m
1
sinh ra.
5.2. C ch phn mnh
S phn ho phn t cc hp cht hu c qua s va chm vi e thng xy ra theo
nhng quy lut nht nh, da vo nhng quy lut ngi ta c th gii thch c cu to
cc hp cht hu c.
5.2.1. Ankan.
Nhng ankan v nhng hp cht cha nhm ankyl b ph v di s hnh thnh ca
mt ion ankyl v 1 gc.

RH
2
C
H
2
C
H
2
C CH
3
RCH
2
CH
2
CH
2
+
+ CH
3
.

Nhng ankyl gn vi cc nhm chc X = OH, SH, OR th trc tin s tch nhm
chc trc.
[CH
3
CH
2
-X] CH
3
CH
2
+
+ X
.
5.2.2. Anken
RH
2
C C
H
CH
2
RH
2
C
H
C CH
2
H
2
C C
H
CH
2
+ R

5.2.3. C ch tch ion tropylium (vng)
Cc hp cht benzen c nhm th CH
2
X (X=H, ankyl, OH, SH, -COR) gn vi
vng benzen thng tch gc R
.
cho cc ion tropylium theo c ch sau:
C
6
H
5
-CH
2
-R
+.
C
7
H
7
-R C
7
H
7
+
+ R
.

R=H: m/e = 91
61

H
2
C X
- X
.
CH
2
+

5.2.4. Ancol
Bc 1

R
OH
R
CH
2
+ CH
2
OH

H
3
C
H
2
C
H
2
C OH
H
2
O +
H
3
C C
H
CH
2
.
CH
2
OH + CH
3
CH
2
+
H
2
C OH
+ CH
3
CH
2
.
CH
2
=CH
+
+ H
2
O +
.
CH
3

Bc 2

R
H
C OH
R
,


H
3
CH
2
CH
2
C
H
C OH
H
2
O +
CH
3
H
3
CH
2
CHC CHCH
3
H
3
CHC OH
+ CH
3
CH
2
CH
2
.
H
3
CH
2
CH
2
C C
H
OH
+
.
CH
3
H
3
CH
2
CH
2
C C
OH
+ H
.
CH
3

Bc 3
62

R C OH
R
,
R

H
3
CH
2
C C OH
H
2
O +
CH
3
H
3
CHC
CCH
3
H
3
CH
2
C C
OH
+
.
CH
3
H
3
C C
OH
CH
3
CH
3
CH
3
CH
3
+ CH
3
CH
2
.


OH
CO +

5.2.5. Andehyt - Xeton
63


CH
H
2
C
C
H
2
C
O
H
R
H
R C
H
CH
2
+ H
2
C C
H
OH
RCH
2
CH
2
CH
2
.
+
HC O
RH
2
CH
2
CH
2
CC O
+ H
.
CH
H
2
C
C
H
C
OH R
H
H
CH
H
2
C
C
H
C
OH
2
R
H
H
C
H
2
C CH
CH R
-H
2
O

CHO
-H
.
C O
- CO
- C
2
H
2
C
4
H
3
+

R
,
C R
O

64
H
3
C
H
2
C
H
2
C C CH
2
CH
2
CH
2
CH
3
O
H
3
CH
2
CH
2
CC O
O C CH
2
CH
2
CH
2
CH
3
H
3
C C
H
CH
2
+ H
2
C
C
OH
CH
2
CH
2
CH
3 H
2
C C CH
2
CH
2
CH
2
CH
3
OH

5.2.7. Axit
H
OH
O
R
1
R
2
CH
2
R
1
H
R
2
OH
OH
H
R
1
R
2
+
+
.
COOH
H CH
3
R
1
R
2
+ CO
2
H C
R
1
R
2
O
+ HO
.
H C
R
1
R
2
O
+ H
2
O

5.2.8. Este
65
R C
O
OR
R C O +
.
OR
R C
O
O
+ R
+
R
+
+
.
COOR
R
.
+
+
COOR


5.2.9. S khi ca mt s mnh ion thng gp trong ph MS
m/e Mnh ion m/e Mnh ion
14 CH
2
28 CO, NH
2

15 CH
3
29 C
2
H
5

16 O, CH
4
43 C
3
H
7

17 OH, NH
3
44 CO
2

18 H
2
O, NH
4
45 COOH
19 F 77 C
6
H
5

20 HF

5.3. Nguyn l cu to khi ph k
Khi ph k gm 4 phn chnh
- Ho kh mu: cc cht rn hay lng c a vo bung mu c p sut gim 10
-6
mmHg bin thnh dng kh. Lng mu cn 0,1 1 mg.
- Ion ho: dn dng phn t kh chy qua mt dng electron c hng vung gc vi
n ion ho mu ri i qua in trng U tng tc.
- Tch ion theo khi lng
- Nhn bit cc ion bng detect.




Ho kh mu
Ion ho
Phn tch
ion
Detect
X l s liu
Ho kh mu
66

5.3.1. Ho kh mu
Cc mu c np vo ph k c th dng kh, lng hay rn. Trc tin mu c
np vo mt bung kn di p sut thp t 10
-5
n 10
-7
mmHg v nhit t nng c th
ln n 200
0
C. Di iu kin ny th hu ht cc cht lng v rn u bin thnh th hi.
5.3.2. Ion ho mu
Mu sau khi ho hi c dn vo bung ion ho bin cc phn t trung ho
thnh cc ion. Qu trnh ion ho ny c th thc hin theo mt s phng php khc nhau
nh:
- Phng php va chm electron: mu cht dng hi c dn vo trong mt bung,
y c mt dng e mang nng lng chuyn ng vung gc vi mu v xy ra va chm
gia chng, bin cc phn t trung ho thnh cc ion phn t hoc cc ion mnh. Nng
lng ca dng e vo khong 10ev n 100ev. Sau dng ion mi c to ra, chy qua
mt in trng E lm tng tc chuyn ng, th ca in trng c gi l th tng
tc U. Phng php ny c dng ph bin.
- Phng php ion ho ho hc: cho dng phn t kh va chm vi mt dng ion dng
hoc ion m bin cc phn t trung ho thnh ion phn t hay ion manh. Trong qu trnh
ny, trc tin phi bin cc phn t kh metan thnh ion, sau cc ion ny mi va chm
vi cc phn t mu
- Phng php ion ho trng: cho mu dng hi i qua gia hai in cc cm ng c
mt in trng mnh, di tc dng ca lc tnh in, phn t trung ho s bin thnh cc
ion dng.
- Phng php ion ho proton: cho dng phn t mu dng hi v p vi dng photon
c nng lng khong 10ev s xy ra qu trnh ion ho.
- Phng php bn ph nguyn t nhanh: mt dng kh agon hay xenon c bn ra t
mt khu sng p thng vo mu ho tan trong dung mi nh glixerin. Trc tin cc phn
t dung mi b ion ho ri chnh n ion ho phn t mu thnh cc ion tip theo.
5.3.3. Tch cc ion theo s khi
Cc ion hnh thnh c s khi m/e c phn tch ra k hi nhau bng cc thit b khc
nhau nh:
67
- Thit b phn tch hi t n
- Thit b phn tch hi t kp
- Thit b phn tch ion t cc
5.3.4. Detect
Cc ion i ra t b phn tch c cng nh nn cn khuych i pht hin. Mt
trong nhng thit b ny l my nhn electron. N to ra cc e th cp khi c e ban u p
vo b mt tm kim loi. khuych i khong 106 khi s dng 16 dint.
5.3.5. Ghi nhn tn hiu
Cc tn hiu t b khuych i truyn ra c np vo b nh my tnh v x l kt
qu ri in ra ph. Cc ph c biu din di dng phn trm basic (%B), nh cao nht c
cng 100%, cc nh khc nh hn. Dng ph MS c hnh dng sau:












50
100
M
+

m/e