SPECTROPHOTOMETRY

DR.YAHYA AL-DOKHIN
 Spectroscopy

 Spectroscopy is the study of the interaction between

matter and electromagnetic radiation (EMR).
It is an instrumental technique for analysis and
structural elucidation of compounds.
Many spectra types can be measured with little
or no sample loss.
 Spectroscopy

 Spectroscopic identification of organic

pharmaceuticals was done using the following
techniques (complementary): 
• Ultraviolet/Visible spectroscopy (UV/VIS)
• Infrared spectroscopy (IR)
• Nuclear Magnetic Resonance spectroscopy (NMR)
• Mass Spectrometry (MS).
U.V Spectro Identify conjugated systems    

I.R Spectro ".…,identify functional groups "OH,NH2,COOH,C=C  

Mass spectro identify molecular weight & molecular formula  

N.M.R identify arrangement of H&C atoms and their number  

: Mechanism      

radiation source compound absorb energy response  

 Response of U.V Spectro : Electronic transition from ground

state to excited state.
 Response of IR Spectro : vibrational transitions
  Energy of electromagnetic radiation (EMR)
 is propagated at the speed of light , has properties of
particles and waves.
 E a 1/ λ Energy is inversely proportional to wave length.
 E a ν Energy is directly proportional to frequency.
  Energy of electromagnetic radiation (EMR)

• Exposure of molecules to high energy

radiations such as gamma rays and X-rays can
• lead to their ionization.
• Exposure of organic molecules to
• Microwave leads to Rotational transitions
• Exposure of organic molecules to
radiofrequency leads to Nuclear spin .
•  
 ”Infrared spectroscopy “IR

• IR region : wave length “ 2,5-15 µ “ & wave

number (600-4000 cm-1)
• Like frequency, wave number is directly
proportional to energy.
• Bond vibration :
i. Stretching vibrations (change bond length
“require high E “.
ii. Bending vibrations (change bond angle “require
low E “)
 types of vibrations
stretching vibrations:
Two types of stretching vibrations are known:
 types of vibrations
Bending vibration
• Rocking
• scissoring
• wagging
• twisting
 Search for "sharp intense peak 1800-1650"

 If present and there

is :

Broad peak at 3500-2500 → OH → COOH


Sharp 2 peaks at 3300 → NH2 → primary Amide

Sharp one peak at 3300 → NH → secondary amide

Two peaks at 2700-2800 → O=C—H → Aldehyde

Sharp peak at 1100-1300 → O=C → ester

Only C=O peak → k e to n e
Wave number depend on Type of vibration "stretching
"or bending

 ↑ Mass of atoms ↓ vibrational frequency.

 ↑ Resonance "conjugation" ↓ wave number.
 ↑Hydrogen bond ↓ vibrational frequency.

 ↓Ring size ↑ vibrational frequency .

 ↑Bond strength ↑ wave number.

Sp > Sp2 > Sp3 in bond strength

 INSTRUMENTS

The IR spectrophotometers are of two types:

1. Single beam 2. Double beam
 Ultraviolet and Visible Spectroscopy

• UV/Vis spectroscopy provides information about compounds

with conjugated double bonds
• It can be also used for qualitative and quantitative of organic
pharmaceuticals.
• UV-VIS region of EMR : 200 - 800nm.
• When U.V or visible radiation passes through compound ..,
electrons in ground state absorb certain quantity of energy and
transmitted to excited state
 Transition types
σ-σ* transition → Δ E is high, thus the transition requires short
ex: In CH3—CH3 σ-σ* transition requires λ max = 135 nm
N.B. Any transition that requires λ < 200 nm is out of scope (need
vacuum UV)
π-π* transition: → Δ E is lower than σ-σ*, thus the transition
requires a longer λ for example, π- π* CH2 ═ CH2 (λ max = 175
nm) n-π* transition: → Δ E is lower than π-π*, thus the transition
requires a longer λ, for example, n -π* of (CH3)2C=O (λ max =
279 nm).
n-σ* transition: n-σ* of H-O-H requires EMR with λ max = 180
nm
 Factors affecting on the UV -Visible
absorbtion
1. conjugation:
↑conjugation ↑ absorption λ max
2. Alkyl substitution:
↑ absorption λ max
3. Arrangment of dienes
 APPLICATIONS OF ULTRAVIOLET SPECTROSCOPY

 In qualitative analysis. The study provides an evidence in the

elucidation of structures of organic compounds.

 In quantitative analysis. A large number of reagents react with nm

absorbing species to yield products that absorb strongly in uv and
visible regions. Therefore, these reagents are frequently used for the
determination of an absorbing species.

 Analysis of organic compounds. Large number of organic molecules

absorb radiation in ultraviolet and visible region. So molecules
having high molecular absorptivities can be determined directly.
 APPLICATIONS OF SPECTROSCOPY

1. It is used for rapid detection of functional groups

2. Presence of hydrogen bonds. Shift of IR bonds to lower wave numbers
indicates the presence of hydrogen bonds. This is absorbed in alcohols,
animes, carboxylic acids and amides.
3. Impurities in a compound can be detected from the nature of bands
which no longer remain sharp and well defined.
4. When the presence of a carbonyl group (> O = O) has been established
further study will reveal whether the carbonyl group is aldehyde, ketonic,
ester or samide etc. Aldehydes can be recognised by its characteristics C-
H stretching, esters from its C-O stretching and
amides for N-H stretching.
REFERENCES
INSTRUMENTAL ANALIYSIS OF PHARMACEUTICAL -
PRODUCTS , DR.YHAYA A.S.AL-DOKHIN . Sana'a .2020

MECHANISMS IN ADVANCED ORGANIC CHEMISTRY . R.P -

.NARAIN .COPYRIGHT .2008
 ‫عمل الطالب‪:‬‬

‫‪ ‬مبارك هائل االسدي‬ ‫‪ ‬أبراهيم عبدهللا عبدالجليل محمد‬

‫‪ ‬محمد احمد النشواني‬
‫‪ ‬محمد احمد محمود‬
‫‪ ‬محمد احمد الهجامي‬
‫‪ ‬محمد مروان نعمان علي‬
‫‪ ‬مصطفى ابراهيم القاضي‬
‫‪ ‬معاذ احمد ناجي الصراري‬
‫‪ ‬موسى امين حسن‬
‫‪ ‬أمجد عبد القوي هزاع‬
‫‪ ‬رهيب علي محمد قحطان‬
‫‪ ‬صالح محمد سعيد الزعزعي‬
‫‪ ‬عدنان علي مطهر العثربي‬
‫‪ ‬علي عمارعلي سعد حسين‬
‫‪ ‬مالك سيف علي عبده الزعزعي‬