Quang pho hong ngoai

QUANG PH�

(C) HKD 2012 2

QUANG PH� H�NG NGO�I

� Near Infrared: particle and composition analysis

� Middle Infrared: primarily used in compound characterization

� Far Infrared: not used

Visible IRUV

Middle IRNear IR Far IR

800nm�12,500cm-1�

2.5�m �4,000cm-1�

25�m �400cm-1�

50 � m �200cm-1�

(C) HKD 2012 3

Thermal Imaging (Thermography)


(C) HKD 2012 4

Night Vision Goggles


(C) HKD 2012 5


(C) HKD 2012 6

C� S� LÝ THUY�T

(C) HKD 2012 7


Radiation Outcome

• h� 109 nm Radiowave Nuclear Spin Flips

• h� 106 nm Microwave Molecular Rotation

• h� 104 nm Infrared Bond Vibrations

• h� 500 nm Visible Electronic Excitation

• h� 200 nm Ultraviolet Electronic Excitation

• h� 10 nm X-ray Molecular Ionization

• h� 0.1 nm Gamma Ray Bond Cleavage

(C) HKD 2012 8


Ph�n ng ca phân t� khi nh�n n ng l��ng h�ng ngo�i

h�

Low Energy High Energy

(C) HKD 2012 9


Các ki�u dao ��ng

(C) HKD 2012 10


Các ki�u dao ��ng

Symmetrical Asymmetrical Scissoring

Twisting Rocking Wagging(C) HKD 2012 11

h� = k(m1 + m2)m1 m2

m2

m1

k

�obs O-H > N-H > C-H > C-O > C-C > C-F

�obs C� > C=C > C-C


Ph��ng trình c� b�n

(C) HKD 2012 12


(C) HKD 2012 13


(C) HKD 2012 14


(C) HKD 2012 15

ALKANES

C-H bond “saturated”

(sp3) 2850-2960 cm-1

+ 1350-1470 cm-1

-CH2- + 1430-1470

-CH3 + “ and 1375

-CH(CH3)2 + “ and 1370, 1385

-C(CH3)3 + “ and 1370(s), 1395 (m)


n-pentane

CH3CH2CH2CH2CH3

3000 cm-1

1470 &1375 cm-1

2850-2960 cm-1

sat’d C-H

CH3CH2CH2CH2CH2CH3

n-hexane

2-methylbutane (isopentane)

2,3-dimethylbutane

cyclohexane

no 1375 cm-1

no –CH3

22(C) HKD 2012

ALKENES

=C—H bond, “unsaturated” vinyl

(sp2) 3020-3080 cm-1

+ 675-1000

RCH=CH2 + 910-920 & 990-1000

R2C=CH2 + 880-900

cis-RCH=CHR + 675-730 (v)

trans-RCH=CHR + 965-975

C=C bond 1640-1680 cm-1 (v)


1-decene

910-920 & 990-1000 RCH=CH2

C=C 1640-1680

unsat’dC-H

3020-3080 cm-1

4-methyl-1-pentene

910-920 & 990-1000 RCH=CH2

2-methyl-1-butene

880-900R2C=CH2

2,3-dimethyl-1-butene

880-900R2C=CH2

27(C) HKD 2012


BENZENES

=C—H bond, “unsaturated” “aryl”

(sp2) 3000-3100 cm-1

+ 690-840

mono-substituted + 690-710, 730-770

ortho-disubstituted + 735-770

meta-disubstituted + 690-710, 750-810(m)

para-disubstituted + 810-840(m)

C=C bond 1500, 1600 cm-1

ethylbenzene

690-710, 730-770mono-

1500 & 1600

Benzene ring

3000-3100 cm-1

Unsat’d C-H

o-xylene

735-770ortho

p-xylene

810-840(m)para

m-xylene

meta

690-710, 750-810(m)

styrene

no sat’d C-H

910-920 & 990-1000

RCH=CH2mono

1640C=C

2-phenylpropene

mono880-900R2C=CH2

Sat’d C-H

p-methylstyrene

para

35(C) HKD 2012


ALCOHOLS và ETHERS

C—O: 1050-1275 (b) cm-1

1o ROH 1050

2o ROH 1100

3o ROH 1150

ethers 1060-1150

O—H: 3200-3640 (b)

1-butanol

CH3CH2CH2CH2-OH

C-O 1o

3200-3640 (b) O-H

2-butanol

C-O 2o

O-H

tert-butyl alcohol

C-O 3oO-H

methyl n-propyl ether

no O--H

C-O ether

40(C) HKD 2012


CARBONYLS

C=O (ketones, aldehydes, and carboxylic acids) absorb ~1710 cm-1

C��ng �� l�n.

Aldehydes: 2 dao ��ng liên k�t C-H 2700 và 2800 cm-1

C=O liên hp v�i C=C: ~1680 cm-1.

C=O ca aminde:1640-1680 cm-1

The C=O ca ester ~1730-1740 cm-1

41(C) HKD 2012


CARBONYLS

42(C) HKD 2012


CARBONYLS

43(C) HKD 2012


CARBONYLS

44(C) HKD 2012


CARBONYLS

45(C) HKD 2012


LIÊN K�T C-N

C - N ~1200 cm-1

C = N ~ 1660 cm-1 m�nh h�n dao ��ng ca C = C.

C N h�p thu m�nh > 2200 cm-1 (tín hi�u ca C C y�u h�n và <

2200 cm-1

46(C) HKD 2012


LIÊN K�T C-N

47(C) HKD 2012


DAO ��NG C�A O-H VÀ N-H

Xu�t hi�n � vùng 3300 cm-1.

M�i O-H r�ng v�i m�i bè tròn.

Amin b�c 2 (R2NH), m�i r�ng v�i broad m�t ��nh nh�n.

Amin b�c 1 (RNH2), m�i r�ng v�i hai ��nh nh�n.

Amin b�c 3: không có tín hi�u h�p thu cho N-H

48(C) HKD 2012



49(C) HKD 2012



�Ph� IR có các m�i h�p h�n ph� UV

�Ph� IR cho nhi�u thông tin h�n ph� UV

�Có th� thu ph� IR t� nhi�u ��i t�ng m�u khác nhau: r�n, l�ng, khí

�Ph� IR kém thích h�p cho ��nh l��ng h�n ph� UV

�Ph� IR ��c thu nh�n ch�m và khó h�n ph� UV

�M�u cho ph� UV d� dàng chu�n b� h�n

�Quang ph� k� UV r! h�n

PH� IR VÀ PH� UV

(C) HKD 2012 50

230 240 250 260 270 280 290

Abs

orba

nce

PH� IR VÀ PH� UV

(C) HKD 2012 51

QUANG PH� K� H�NG NGO�I

� Quang ph� k� h�ng ngo�i tán s�c

� Dùng cách t�

� Quang ph� k� h�ng ngo�i bi�n ��i Fourrier (FTIR)

� Dùng giao thoa k�

(C) HKD 2012 52

QUANG PH� K� H�NG NGO�ITÁN S"C

(C) HKD 2012 53

FT = Fourier Transfrom

QUANG PH� K� H�NG NGO�IBI�N ��I FOURRIER

(C) HKD 2012 54

path “a”

path

“b”

ab

moving mirror

fixed mirror

detector

50% beamsplitter

x

sourcesample

j- stop


(C) HKD 2012 55

� = 0

for �= m�, get constructive interference

� is “retardation”

�=�/2

for �= (m+1/2)�, get destructive interference


(C) HKD 2012 56

Mirror travel

Frequency, (cm-1)

x = 0

x = 0

4004000

Interferogram:

Single beamspectrum of air

FT

100%

H2O H2OCO2


(C) HKD 2012 57

F(�) = f(t)e dt��t

Converts from units of time to units of frequency


(C) HKD 2012 58


(C) HKD 2012 59

�“Neat” (phân tích m�u l�ng tinh khi�t)

� Pellet (ép viên cho phân tích m�u r!n)

�Thin Cell (phân tích dung d�ch)

�Long Cell (phân tích m�u khí)


Chu#n b� m$u

(C) HKD 2012 60


Phân tích m$u “Neat”

(C) HKD 2012 61


Ép viên

(C) HKD 2012 62


Ép viên

(C) HKD 2012 63

�S� d"ng b�t khan KBr, KI, CsI

�Tr�n m�u v�i KBr theo t# l� 1:10

�Nghi�n ��n kích th��c 2 m diameter

�Cho vào khuôn và ép tay ho$c máy thy l'c

�L�y m�u ra kh�i khuôn, ti�n hành �o


Ép viên

(C) HKD 2012 64


Dùng cell l�ng

(C) HKD 2012 65


Dùng cell l�ng

(C) HKD 2012 66

� Lo�i tháo r�i (demountable liquid cell)

� ��nh tính.

� Ráp và tháo ra cho m�i l�n �o.

� B� dày có th �i�u chnh ��c (thông qua spacer).

� Lo�i kín (sealed liquid cell)

� Ch t l�ng d� bay h�i.

� B� dày có th �i�u chnh ��c (thông qua spacer).

� Lo�i kích th��c c� ��nh (fixed liquid cell)

� ��nh l��ng.

� B� dày c� ��nh.


Dùng cell l�ng

(C) HKD 2012 67

��

��

��

��

� ��

�� !"��#$ $%&' ( )"�

*�+� �,""��#$ $%!) ( )"�

��-#& �'&"��#$ '% . / ."�

��0' �.."��#$ $%!' / )"�

+�0' �$$""��#$ $% ) 1 )&�

� KBr là v�t li�u ph� bi�n nh t.

� KRS-5, BaF2 or CaF2 có th ��c dùng � �o dung d�ch trong n��c mà n�ng�� tác ch t l�n h�n vài %.


Dùng cell khí

(C) HKD 2012 68


Dùng cell khí

(C) HKD 2012 69

Long Path Cell


ATR (Attenuated Total Reflection)

(C) HKD 2012 70

� Không c�n ti�n x� lý m�u.

� Phân tích b� m�t.

� M�u ph�i ti�p xúc v�i l�ng kính.

� Lo�i m�u: film, nh�a (plastic), cao su (rubber), ch t ph! (coating on

same materials), …..



(C) HKD 2012 71

IR Beam

Prism

SampleSample Press

n1: Refractive Index of prism

212

2 )n/n(sin2dp

�

�

�Penetration Depth (dp) : �: Incident Angle

n2: Refractive Index of sample

�: Wavelength

Sample

Prism

dpZoom



(C) HKD 2012 72

� Ch�t l�ng� M�u có b mt ph�ng� B�t� M i h�p thu l�n (��ng truyn l�n)

� Ch�t l�ng� M�u không có b mt ph�ng� B�t� M i h�p thu nh� (��ng

truyn ng�n

Infrared beam

Prism

Sample

Prism

Infrared beam

Sample



(C) HKD 2012 73

� Multi-reflection ATR1) ATR-8000A

�Solid sample (Film, Plastic, Rubber, Coating)

�The incident angle can be selected form 302, 452, or 602

2) ATR-8200HA

� Liquid and Solid sample.

� Single Reflection ATR�MIRacle A

�DuraSamplIR�

ATR-8000A

ATR-8200HA

MIRacle A DuraSamplIR�



(C) HKD 2012 74

� MIRacle A: l�ng kính có ��"ng kính 1,5mm.

� L�ng kính ��c ch� t�o t# ZnSe, Ge ho�c kim c��ng.

� L�ng kính ZnSe��o l��ng m�u nh�.

�C�"ng �� m$i tín hi�u cao h�n l�ng kính Ge.

� L�ng kính Ge�Dùng cho m�u có chi�t su t l�n (black rubber).

� Phân tích b� m�t.

�



(C) HKD 2012 75

!&","".&")""$"&"$'""$ &"$&""$,&"$3""$)&"'!""'."" """ "" ,"" )""$4��

"

'%&

&

.%&

$"

$'%&

$&

$.%&

'"

''%&

'&

�5

6789:;<�=��>?�@

Ge

ZnSe

Diamond/ZnSe

Diamond



(C) HKD 2012 76

Prism Banned Samples

ZnSe Acid (less then pH 5), strong alkaline (more than pH 9)

KRS-5*)

acetoneammonium salt solutionsulfuric acidammoniaEDTAA solution of a compound that reacts with thallium to form a Complex

Ge Hot concentrated sulfuric acid

Diamond -*) Consist of TlBr and TlI



(C) HKD 2012 77

ATR-8200HA



(C) HKD 2012 78

"%"

"%""&

"%"$

"%"$&

��-

$"""%"$&""%"'"""%" """%"!"""%"$4�� A��B��#�5�

"%"

"%"'&

"%"&

"%".&

��-

$"""%"$&""%"'"""%" """%"!"""%"$4��C��B��#�5�

Single Hair with Hair Spray

Untreated Hair

Single Hair on Diamond Prism

DuraSamplIR�



(C) HKD 2012 79

"%"

"%$

��-

$"""%"'"""%"!"""%"$4��

"%"&

"%$

"%$&

��-

$"""%"'"""%"!"""%"$4��

"%&

��-

$"""%"'"""%"!"""%"$4��

"%'&

"%&

��-

$"""%"'"""%"!"""%"$4��

Acrylic Rubber NBR

So sánh hai lo�i l�ng kính MIRacle A

ZnSe ZnSe

Ge Ge

3""$"""$'""$!""$,""$3""'"""'!""'3"" '"" ,""!"""$4��

).

).%&

)3

)3%&

))

))%&

$""

�5

-�D �� A�� D� ��E��



(C) HKD 2012 80

C=O1750cm-1 : ch�t béo.1700 - 1500cm-1: protein.1000cm-1 : lactose (n�i ether).

3""$"""$'""$!""$,""$3""'"""'!""'3"" '"" ,""!"""$4��

�5

��E

Spectra of water and milk



(C) HKD 2012 81

V�t li�u gói th�c ph�m nhiu l�pPh� h�ng ngo�i c�a mt sau (PE) và mt tr��c(PET)

3""$"""$'""$!""$,""$3""'"""'!""'3"" '"" ,""!"""$4��

�5

��E

PE

PET



(C) HKD 2012 82

3""$"""$'""$!""$,""$3""'"""'!""'3"" '"" ,""!"""$4��

�D�

FG5

polyethylene terephthalate (PET)

ATR corrected spectrum

ATR spectrum


Ph�n x� (Specular Reflectance method)

(C) HKD 2012 83

� �o ��c hai d�ng m�u:

� Nh�a bóng (glossy flat plastic).

� Phim m�ng ph! trên kim lo�i (thin film on metal plate).

Det

ecto

r

Inte

rfer

omet

er

Sample



(C) HKD 2012 84

Film

Metal plate

abInfrared beam

a << bb

0.1�20�mSample

Infrared beama

b

Glossy flat plasticThin film



(C) HKD 2012 85

'%"

!%"

,%"

�5

&""%".&"%"$"""%"$'&"%"$&""%"$.&"%"'"""%"'&""%" """%" &""%"!"""%"$4��HIJ7K<LMNO

3&%"

)"%"

)&%"

$""%"

$"&%"

�5

&""%".&"%"$"""%"$'&"%"$&""%"$.&"%"'"""%"'&""%" """%" &""%"!"""%"$4��+�$%=�-PQR��STUVW6XI;7>YZ005O@

Bi�n ��i Kramers-Kronig

polymethylmethacrylate


Ph�n x� khu�ch tán (Diffuse Reflectance )

(C) HKD 2012 86

� Dùng �o m�u b�t: b�t h�u c�, xúc tác, g�m s� (ceramic powder).



(C) HKD 2012 87

� Dùng �o m�u b�t: b�t h�u c�, xúc tác, g�m s� (ceramic powder).

S

D

S : Specular reflectionD : Diffuse reflection

Infrared beam



(C) HKD 2012 88

&"%"

.&%"

$""%"

�5

&""%"$"""%"$&""%"'"""%" """%"!"""%"$4��

&"%"

.&%"

$""%"

�5

&""%"$"""%"$&""%"'"""%" """%"!"""%"$4��

Bi�n ��i Kubelka-Munk



(C) HKD 2012 89



(C) HKD 2012 90

UV(254nm)

RI

A

B

C

Sebacic Acid Dialkyl Ester

Phthalic Acid Dialkyl Ester

(B)

(C)

Dual Channel GPC Chromatograms of Polyvinyl Chloride


H%p thu ph�n x� (Reflection Absorption Spectroscopy)

(C) HKD 2012 91

� Phim m�ng trên kim lo�i (thin film on metal).

� Có th �o ��c phim có b� dày <1&m..

� �ôi khi k�t h�p v�i thi�t b� phân c�c ánh sáng (polarizer).

Det

ecto

r

Inte

rfer

omet

er

Sample

Mask

Shield Plate

RAS-8000A



(C) HKD 2012 92

Metal plate

Thin film1�1000nm

70��85�

(1) Vertical polarized light (2) Parallel polarized light

Incident beam Reflected beam



(C) HKD 2012 93

Lead Stearate

� Ki�m tra ��nh tính thu�c (vùng “vân tay”,fingerprint)

� Ki�m tra sàng l�c và nhanh chóng ��nh danh C=O

� Phân tích ��nh tính m�u r!n (kem, viên nén)

� Phát hi�n crystal isoforms (polymorphs)

� Xác ��nh hàm l�ng n��c


'NG D*NG

(C) HKD 2012 94

�Phân tích n��c ti�u và các ch�t l�ng sinh h�c (urea,creatinine, protein)


'NG D*NG

(C) HKD 2012 95

� *o glucose b;ng k? thu�t không xâm l�n


'NG D*NG

(C) HKD 2012 96

Documents

Quang pho hong ngoai