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Analysis & Structure of Molecules
문 명 희화학과 분석화학전공
CHEMISTRY
물질의 특성 및 변화
물질의 합성
유기화학무기화학
에너지변화
물리화학
분석분석법개발
분석화학
Analytical Chemistry & Life
Drunken driverAthletesRiver contaminationExplosives by terroristsFoodEnvironmentsQC in ManufacturingClinical ExaminationsEtc.
Detection of Chemicals
Accuracy Precision
Development of Analytical Technologies
ClassicalTechnologies
InstrumentalAnalysisComputer
Robotics
•Titration acid-base, redox, complex•Precipitation-Weighing Group Analysis•Colorimetry litmus paper,
•Spectrophotometric methods X-ray, Atomic Spectroscopy UV-VIS, IR, microwave•Separation (chromatography) GC, HPLC, SFC•Electrochemical
instrumentalreproducibleUltra low detection(10 억분의 1 영역 )
manualTime takingLabor orientedpoor detection limit
Classical Analytical Chemistry
• Quantitative Analysis– gravimetric analysis ( 중량분석 )
Ni Ni-dimethylglyoxime salt ( 침전 )
– Volumetric analysis ( 부피분석 )
titration ( 적정 )
무게측정
지시약첨가 색변화관찰
What is Titration ?
농도를 아는 용액( 산 , 또는 염기 )
분석대상용액( 염기 또는 산 )
H-Acid + M-Base BH + MA
Final Goal : Amount ?
types
Acid-Base titrationRedox titrationPrecipitation
Spectrophotometric
Physical Methods in AC
• A Great Advance
19th century - Atomic Spectroscopy
Chemicalcompound Light Colored
light
Ex) Na ---- 589.0 nm (bright yellow)
ICP (Inductively Coupled Plasma)
What if light source is plasma ?
Arsample solution
load coil(~27MHz, 2kW)
plasma
atomic emission
Inductively Coupled Plasma “torch”
(11~17L/min)
Ar 의 이온화 – coil 의 spark
4000 ~8000 K
ICP/ optical emissionspectrum of 100 ppm Cerium solution
ICPMS spectrumof 10 ppm Cerium
Ce emission
140Ce+
plasma continuum
Analysis of Complicated Mixtures ?
Needs Simplification of Matrix Separation (or isolation)
Emergence of Chromatography
ChromatographyIn Greek Word, Color + To Write
1903 Tswett (Russian Botanist)
First Observed Separation of Plant Pigments as bands on chalk column (CaCO3) with ether
Chromatographic Separation
SampleA
SampleB
Glass wools
SamplesA & B
Solid materials
M.P
Modern Instruments of Chromatography
injector
detector
PC
pump column
Data record
InjectorSample loop
column
Separation Process in Chromatography
Sample Components are carried by a mobile phase through a bed of stationary phase
Mobile Phase : Gas
LiquidStationary Phase : Solid (silica, alumina, etc.)
Liquid
Classifications by Phase Type
Mobile Stationary
Liquid Solid LSCLiquid LLC
Gas Solid GSCLiquid GLC
Supercritical Fluid SFC
Retention of sample molecules !
Where ? -- Stationary Phase (S.P.) By how ? -- Various Mechansims
1. Adsorption2. Partition3. Ion-Exchange4. Size Exclusion5. Affinity
1. Adsorption
Stationary Phase - Solid : silica, alumina LSC, GSC
Separation is due to a series of Adsorption/Desorption Steps
Solid(particle)
M.P.
Adsorption
Common S.P. : Silica & alumina
Both Solutes and Solvent are attracted to the Polar Sites on the S.P.
For Separation, Solutes need to have different degrees of ATTRACTION to the phase
2. Partition (distribution)
Solute Partitioning between TWO PHASESS.P.: Lig. M.P.: Gas --- GLCS.P.: Lig. M.P.: Liq --- LLC
Separation is Based on RELATIVE SOLUBILITY
Phase A Phase B
How does liq. S.P. exist ?Liq. Immobilized to solid (C18-silica)
Partition
Basic Principle - similar to EXTRACTION
High Affinity (Solubility) for S.P. Retain Longer
Separation of Solutes is based on differences in this relative solubility
One phase - polarThe other phase - nonpolar
i.e. S.P. : Nonpolar (C18) M.P.: Water or Methanol * separation order- order of interaction
between C18-sample
Example
3. Ion Exchange
Stationary Phase has ionically charged surfaceinteraction between
Surface-ions: counterionsS.P. : Exchange Resins (Cation, Anion Types)
-Solid(particle)
M.P.
+
+
+
sample
Ion Chromatography (IC)
Chromatographic Process to separateIons and some polar molecules
Stationary Phase attract ionic species by the following principles.
Typical Mechansims 1. Ion Exchange - IEC 2. Ion Exclusion 3. Complexation Effect
Ion Exchange Chromatography
Stationary PhasesAnion Exchange Resins Cation Exchange Resin
resin+
resin+
+
(analyte) ++
Ion exchange
resin NH+ Cl-
R
R
resin NH+ Cl-
H
H
strong
weak
resin SO3-H+
resin COO-H+
resin SO3-H
Ion Exchange
What Affects the Separation Order ?
Ionic Charge : Larger the stronger attraction
Li+, Na+, K+ < Ca+2, Mg+2
F-, Cl-, Br-, H2PO4-, < SO4
2-
Atomic Number : Higher the larger Electron Cloud -- stronger van der Waals Force
Li+ < Na+ < K+ , Ca+2 < Mg+2
F- < Cl- < Br- < H2PO4-
Ion ExchangeExample
Separation of Common AnionsEluent: 1.8mM Na2CO3, 1.7mM NaHCO3
Ion ExchangeExample
Separation of Common CationsEluent: 20mM HCl or Methansulfonic acid
Ion ExchangeExample
Separation of Organic AcidsEluent: 1.6mM Heptafluorobutyric acid
4. Size Exclusion
Stationary Phase : Porous GelSolute passes pores or is excluded Gel Permeation Chromatography
or Gel Filtration Chromatography
M.P.
polymer Porousparticle
Schematics of Porous Particlesbeing used in SEC
Size Exclusion
Various Columns needed to separate SAMPLES of SPECIFIC SIZE RANGES
Large Species Elute Firstsince they can pass through as many poresso they spend little time in S.P.
Useful for Determining Size & Size Distribution for
Polymers, Proteins, ...
Example Application by SEC
Gas Chromatography (GC)
First Commercial Instrumental Chromatographic System
Separation in GC
Sample should be converted to Vapor StateMobile Phase : Inert Gas (H2, He, N2, Ar)
GCTypes of Stationary Phases
Solid (GSC) : silica gel, alumina, charcoal, etcLiquid(GLC): nonvolatile liq. Coated on
firebrick (Chromosorb..), diatomaceous earththickness : ~ 0.25 m
i.e.: Poly(dimethyl siloxane)(Dipheny)0.05(dimethyl)0.95polysiloxane
Separation is achieved by order of Sample’s Polarity.Nonpolar Solute - attracted to Nonpolar S.P.
GCTypes of Columns
GCTypes of Columns
Conventional1/8-1/4 inch OD, SS or glass tube6-20 feet in length
Capillary0.1 - 0.5 mm ID10-100 meters in length
WCOTOTC
GC Operation
Isothermal : Constant TemperatureTemperature Programming :
Temp. varies during the analysis
By Increasing T,Increase the activity(diffusion, ad/desorption,etc.)
Increase speed recovery
For Temperature Programming, Solubility Variations, Volatility of Solutes should be considered
Example Applications
Example Applications
Example Applications
Chemical Structure ? By How
Molecule• Electromagnetic
- Radiation
• Electron Beam
• Neutron
MeasurePhysical & Chemical
changes
Most Typical Probe !
Electromagnetic Radiation
What is electromagnetic Radiation ?
Light, microwaves, x-rays, and TV and radio transmissions are all kinds of electromagnetic radiation.
They are all the same kind of wavy disturbance that repeats itself over a distance called the wavelength.
The different names refer to different wavelengths.
chhE
Planck const.
frequency Light speed
wavelength
What can happen when light shines on a material ?
heat
Visible light
Inner shellElectron transitionX-ray Diffraction
Outer shellElectron transition
UV-VIS SpectroscopyAtomic AbsorptionAtomic Emission Molecular vibration
IR SpectroscopyRaman Spectroscopy
Rotational MotionNMR, MRI, ESR
Atomiclevel
Molecularlevel
X-ray Diffraction or
X-ray Crystallography X-rays are diffracted by crystals scattered by the electron cloud of an atom of comparable size.
Diffraction Pattern Molecular structure
Crystallattice
X-Ray Diffraction (X-Ray Crystallography)
• The most straightforward way of examining the structure of a compound
Bragg’s Law
Conditions for constructive interference of the beam at angle θ
AP + PC = n
AP = PC = d sin θ
n = 2d sin θ
sin θ = d
n
2
1. Crystals are rotated through all angles to obtain diffraction pattern 2. The conversion of diffraction pattern to structure
If we know, and θ,We can get d (inter-atomic distance)
Bright X-ray:Synchrotron radiation
High-resolution X-ray crystallography
X-ray Diffraction or X-ray Crystallography
Light Spectroscopy II
UV-VIS Absorption Spectroscopy
• Interaction of UV-VIS light with electronic energy levels in molecules
• Good means of identification for transition metal coordination compound or some organic compounds (double bond 포함 시료의 경우 )
• Good for quantitation ( 정량분석 , HPLC 의 검출기 )
• Spectral band: provides a great deal of information about the electronic structures of molecules
v=1
v=2
v=3
h1
ho
ho-
h 1
RamanScattering
Fluorescence IRAbsorption
NIRAbsorption
virtual
state
excitedelectronic
state
Groundstate
Energy
rotational levels
UV-Visabsorption
S2
S1
overtones
Light Spectroscopy III
IR Spectroscopy
• Information on chemical groups in molecules
• Stretching and shaking of molecules: IR region (4000 cm-1 – 200 cm-1)
• Provides ‘fingerprint’ of the various chemical groups in the molecule ( 예 : carbonyl group: 1700 – 1800 cm-1)
• FT-IR (fast, better resolution and S/N) see box 2
CO stretching band
Vibrational Modes of Molecules
chhE
Light speed
wavelength
Vibrations in polyatomic molecules:
linear molecule: 3N-5 (N = number of atoms)
nonlinear molecule: 3N-6
for water: 3N-6 = 3
symmetric stretch 3652 cm-1
asymmetric stretch 3756 cm-1
bend1595 cm-1
30
22 12
16
67
1
3000 2500 2000 1500 1000
OSU FTIR(between NaCl plates)
Galactic Library1994 [Chloroform w/ 0.75% Ethanol; liquid]
3021
2401
1522
1425
1216
1045 92
9
772
3000 2500 2000 1500 1000
CHCl3
cm-1
abso
rban
ce
H
Cl
CCl
Cl
CHCl3 normal modes
3019 cm-1
(C-H stretch)364 cm-1
667 cm-1
(sym. stretch)
760 cm-1 260 cm-1
1215 cm-1
(C-H bend)
mode labels are from Hyperchem, e vibrations are doubly degenerate
4 3 9
7,8 1,2 5,6
Mirror travel
Frequency, (cm-1)
x = 0
x = 0
4004000
Interferogram:
Single beam spectrum of air:
FT
100%
H2O H2OCO2
Fourier Transform IR (FT-IR)
He-Ne lasertop of
beamsplitter
Perkin Elmer Galaxy 2000 FTIR
Nuclear Magnetic Resonance (NMR)
magnet
시료주입
Nuclear Magnetic Resonance • Depends on magnetic properties of certain nuclei (H, C, F, ..)• Certain nuclei rotates about an axis and thus have a property of spin• A spinning charged nucleus creates a magnetic field, thus magnetic moment.
Energy ~ radio wave 영역
Spin - spin coupling
Nuclear Magnetic Resonance I
Radio frequency 영역의 빛 흡수 (megahertz): depends on magnetic field and nucleus being studied
(chemical structure 에 의존 )
초기 NMR: radiowave 파 : 고정된 frequency 사용- magnetic field: 시간에 따라 변화시킴 Signal vs magnetic field
최근 NMR (Pulse FT NMR)- 강한 radiofrequency ( 다양한 frequency 함유 ) 의 pulse 를 가함- Free induction decay(FID) decayed- Time domain 의 신호를 Fourier Transformation 으로 frequency 의 영역으로 변화시킴
Magnetic Resonance Imaging (MRI)
Imaging tool for clear and detailed pictures of internal organs and tissuesusing magnet and radio frequency
MRI is particularly good for some types of brain tumour, for primary bone tumours and soft tissue sarcomas and f
or tumours affecting the spinal cord.