INFRARED SPECTROSCOPY (IR) [ : 2500-50.

000 nm (Middle IR, : 4000-200 cm1 ] ELECTRON TRANSITION BETWEEN ROTATIONAL AND VIBRATIONAL ENERGY LEVEL

FUNCTIONAL GROUP OF ORGANIC COMPUND

THE ELECTROMAGNETIC SPECTRUM

THE REGION OF IR ABSORPTION

FUNCTIONAL GROUP REGION

FINGER PRINT REGION

4000-1400 cm -1

1400-600 cm -1

ABSORPTION REGION OF MOST OF FUNCTIONAL GROUP

EVERY MOLECULE HAS SPESIFIC PATTERN AT THIS REGION

DEGREE OF FREEDOM OF MOLECULE

3 N (N = SUM OF ATOM)

DEGREE OF FREEDOM OF TRANSLATION

DEGREE OF FREEDOM OF ROTATION

DEGREE OF FREEDOM OF VIBRATION

LINIER = 2 NON LINIER = 3

LINIER = 3N-5 NON LINIER = 3N-6

NB : VIBRATION CAUSING IR ABSORPTION CHANGE OF DIPOLE MOMENT

THE KIND OF VIBRATION STRECHING VIBRATION

THIS VIBRATION CAUSE OSILATION CHEMICAL BOND BETWEEN TWO ATOMS CONTINOUESLY, THE DISTANCE CHANGE, BUT ANGLE BOND NOT CHANGE

SYMMETRICAL AND ASYMMETRICAL STRECHING

THE BENDING VIBRATION

THIS VIBRATION CAUSE CHANGE OF ANGLE BOND

WAGGING VIBRATION ( ) ROCKING VIBRATION ( ) TWISTING VIBRATION ( ) SCISSORING VIBRATION (s)

THE MAIN REGION OF IR ABSORPTION

No. VIBRATION FREQUENCY (cm-1) 3750-3000 3300-3000 3000-2700 2400-2100 1900-1650 1675-1500 1475-1300 1200-1000 1000-650 < 1000 TYPE OF BONDS ABSORPTING IR

1. 2. 3. 4. 5. 6. 7. 8. 9. 10.

STRECHING : O-H, N-H STRECHING C-H: C C-H,C=C-H,Ar-H STRECHING C-H: CH3-, -CH2-, C-H,-CHO STRECHING : C C, C N STRECHING :C=O STRECHING : C=C, C=N BENDING C-H : ALKIL STRECHING : C-O-C BENDING C-H : C=C-H, Ar-H ANORGANIC GROUP: C-Cl, SO42-, PO42-, CO32-, NO3-

The IR spectra of (a) 2-pentanol and (b) 3-pentanol. The functional group regions are very similar because the two compounds have the same functional group, but the fingerprint regions are unique for each compound.

PROBLEM
Which one of the following compounds is most consistent with the infrared spectrum given in Figure 13.31? Explain your reasoning.

THE POSITON OF IR ABSORPTION BAND (VIBRATION FREQUENCY) HOOKE LAW

TYPE OF BONDS O-H N-H C-H C=C

f (x105 dncm-1) 7,8 6,5 4,7-5 9,5-9,9

TYPE OF BONDS C C C N C-O C=O

f (x105 dncm-1) 15-17 16-18 5-5,8 12-13

NB: 1 sma = 1,67.10-24 g, c = 3.1010 cm.s -1

FACTORS ENFLUENCING THE VIBRATION FREQUENCY 1. PHYSICAL CONDITION OF SAMPLE IR spectrum of solid are more complex than liquid/ gas 2. PRIMARY FACTOR From Hooke equation e.g. : Methyl and ethyl groups have different effect to k (f) value of O-H bond 3. SECONDARY FACTOR a. Vibrational coupling Groups with the same frequency can interact each other Change value of k (f) b. Bond Orde Bond orde vibration frequency e.g. : C C (2100 cm -1 ) > C=C (1650 cm -1 ) c. Hydrogen bond Absorption band of OH is broad d. Electronic effect (Conjugation, resonancy, induction effect) Decrease value of vibration frequency Bond angle factor NB: e. Absorption intensity Dipol moment change Bond polarity Intensity of O-H > N-H > C-H

PROFIL SPEKTRUM IR BENZENA TERSUBSTITUSI