Yam Kah Meng A0086549  Dissolving inorganic materials by fusion 13.

Masking and Extraction of Metal Ions

CM2142 Analytical Chemistry Cheat Sheet  Decomposition of organic materials by dry or wet ashing  Masking is the prevention of the unwanted species from interfering
 Extractions in the analysis of another by using a masking agent.
1. Precision vs. Accuracy  The masking agent should be selective to the unwanted species.
 Precision is the measure of closeness of results to others obtained in 7. Figures of Merit for Analytical Methods  The metal – masking agent complex should be more stable than the
the exact same way and is affected by random errors.  Sensitivity is the magnitude of the slope of a calibration curve. metal – chelating agent complex.
 Accuracy is the measure of closeness of a measure value to the true  Specificity is responsiveness of an instrument or a method to the  The metal – masking agent complex should be more water – soluble
value and is affected by systematic errors. target analyte. than the metal – chelating agent complex.
 Detection limit is the lowest analyte concentration that can be
2. Repeatability vs. Reproducibility measured within a certain confidence level. 14. Ion Exchange Resins
 Repeatability: ability to obtain results with within-run precision  Dynamic range is the concentration range that can be determined  Cation exchange uses resins with acid groups (strong: sulfonic acid;
under same conditions. using the calibration curve. weak: carboxylic acid)
 Reproducibility: ability to obtain results with between-run precision  Anion exchange uses resins with base groups (strong: quarternary
under different conditions. 8. Calibration Methods amine; weak: secondary or tertiary amine)
Calibration
Usage Method 15. Equilibrium involving In Exchange
3. Significance Tests Methods
Significance Tests Usage Used when sample and  Cationic exchange: n H+ (resin) + Mn+ (aq) ⇌ H+ (aq) + Mn+ (resin)
External Calibrated using solutions
z - test Compares large sample to standard standard solutions have  Anionic exchange: An- (resin) + n OH- (aq) ⇌ An- (aq) + OH- (resin)
Calibration with different [Standard]
t - test Compares small sample to standard similar compositions  KD increases with increasing ionic charge and decreasing hydrated
Pooled t test Compares two data sets by their means Calibrated using solutions ion radius.
Standard Used when matrix effect
Compares two data sets by the mean of their with different [Standard]
Paired t test Addition is dominant
differences added to same [Sample] 16. Solid Phase Extraction
Fisher F test Compares variances of two data sets Used to mitigate Calibrated using solutions  The analyte is retained in the sorbent cartridge and the unwanted
Dixon Q test Compares outlier to the rest of the data Internal random error and with different [Standard] materials are washed through.
ANOVA Compares more than two data sets by their means Standard inconsistent readings of spiked with the same  The analyte is eluted out and the unwanted materials are retained in
the instrument [Internal Standard] the sorbent cartridge.
4. Type I Error vs. Type II Error  External calibration: [Unknown] found by interpolation.  The sorbent cartridge is first conditioned with a range of solvents.
 Type I error is when H0 is rejected even though it is true and has a  Standard addition: [Unknown] found by calculating x-intercept.  Elution is started with weak solvent and substances with weak
higher chance of occurring with lower CL and higher α.  Internal standard: [Unknown] found by calculating from the plot of interactions with the sorbent will be eluted out.
 Type II error is when H0 is retained even though it is false andhas a ratio of analyte response to the internal standard response versus  Solvent strength is then increased.
higher chance of occurring with higher CL and lower α. analyte concentration.
17. Solid Phase Micro Extraction
5. Classification of Analysis 9. Methods of Validation  The absorbent thin film is exposed to the liquid sample containing
 Equivalency testing compares results from the same sample but the analyte either by direct contact or headspace.
Based on sample size different existing methods.  Extraction is complete when the analyte concentration has reached
 Ultramicro: <0.0001 g  Collaborative testing compares results from the same sample but distribution equilibrium between the sample matrix and the film.
 Micro: bet. 0.0001 g and 0.01 g different laboratory.  The analyte is then thermally desorbed directly in the injection port
 Semimicro: bet. 0.01 g and 0.1 g of a GC.
 Macro: >0.1 g 10. Equilibria Involving Extraction of Weak Monoprotic Acids HA
 Dissociation of HA in aq phase: HA (aq) ⇌ H+ (aq) + A- (aq) 18. The Van Deemter Equation
Based on analyte level  Partition of HA bet. aq and org phase: HA (aq) ⇌ HA (org) d d
Cu C u d
 Ultratrace: <1 ppb u
 Trace: bet. 1 ppb and 1 ppm 11. Equilibria Involving Extraction of Metal Ions Mn+ Using Chelating Agents At low flow rate A is negligible. At high flow rate Csu is negligible.
HL
 Minor: bet. 1 ppm and 0.1 %
 Partition of HL bet. org and aq phase: HL (org) ⇌ HL (aq) 19. Instrument Parameters in GC and HPLC
 Major: bet 0.1 % to 100 %
 Dissociation of HL in aq phase: HL (aq) ⇌ H+ (aq) + L- (aq) Parameters GC HPLC
6. Laboratory Sample Preparation  Chelation of Mn+ in aq phase: Mn+ (aq) + n L- ⇌ MLn (aq) Packed or capillary
Column Type Packed
 Partition of MLn bet. aq and org phase: MLn (aq) ⇌ ML (org) (open tubular)
Includes Stationary Phase
 Choosing a sample amount 12. pH1/2 and Extraction of Metal Ions 3 – 6 mm; 0.1 – 0.53
 pH1/2 is the pH at which half the metal is extracted into organic Inner Diameter 1 – 5 mm
 Drying to remove moisture mm
 Grinding phase, i.e. D =1 Thickness of
 pH1/2 of two metal ions should differ by 3 pH units or more to 1.5 – μ
 Dissolving inorganic materials with acids Stationary Phase
achieve quantitative separation.
 Length 1 – 10 m; 10 – 100 m 5 – 30 cm Halides,  Bidentate C18 make silica stable at high pH.
Isothermal or Isothermal or conjugated  Isobutyl groups make silica stable at low pH.
Temperature
programmed programmed Electron carbonyls, Frequency of
5 fg/s
Mobile Phase H2 He or N2 Isocratic or gradient Capture nitriles, nitro voltage pulses 31. Elution in HPLC
Higher optimum flow Lower optimum flow and organo-  The greater the eluent strength, the more easily it displaces the
Linear Flow Rate metallics.
rate rate olute, ↓e tR and ↓e Rs.
Mass Mass/charge
Any 0.25-100 pg
20. Effect of each Instrument Parameter Spectrometer ratio 32. Normal vs. Reverse Phase Chromatography
 Column Type: Packed column has A; capillary column no A. H is  Normal phase is when stationary phase is polar and the mobile
generally higher for packed column. 25. Flame Ionisation Detector phase is non-polar. Elution strength increases when the eluent is
 Inner Diameter: Increasing d ↓es Ds, ↑e Cs, ↑e , ↓e N, ↓e Rs,  Analytes are pyrolysed and form cations and electrons. more polar.
↑e tR.  Collector electrode will capture the charge carriers and the resulting  Reverse phase is when the stationary phase is non-polar and the
 Thickness of Stationary Phase: Increasing dp / ds ↓e s, ↑e Cs, ↑e current is measured. mobile phase is polar. Elution strength increases when the eluent is
, ↓e N, ↓e Rs, ↑e tR.  The response is proportional to the no. of carbon atoms. more non-polar.
 Length: Increa ing L ↑e N, ↑e Rs, ↑e tR.
 Te erature: Increa ing T ↓es Rs, ↓e tR. 26. Thermal Conductivity Detector
 Carrier gas has a much higher thermal conductivity than the analytes.
21. Types of Capillary (Open Tubular) Columns in GC  Thermal conductivity is lowered with the presence of organic
 FSOT (Fused Silica): No coating compounds, temperature will increase and electrical resistance of
 WCOT (Wall Coated): Coated with stationary liquid phase the heated element increases.
 SCOT (Support Coated): Coated with stationary liquid phase on solid
support 27. Electron Capture Detector
 PLOT (Porous Layer): Coated with stationary solid phase  β-Emitter (usually Ni-63) emits electrons.
 Carrier gases ionise and form cations and more electrons.
21. Elution in GC  Analytes ionize and from anions and less electrons.
 A polar liquid stationary phase elutes analytes with increasing  The response is the frequency f the voltage pulses varied to maintain
polarity. constant current.
 A non-polar liquid stationary phase elutes analytes with increasing
volatility. 28. Types of HPLC
↑ing Polarity of nalyte →
22. Common Liquid Stationary Phases for GC Water Insoluble Water Soluble
In order of increasing polarity and decreasing max temperature:
Non Polar Non-ionic Polar Ionic
 PDMS (PolyDiMethylSiloxane)
 5 % Ph-PDMS (Phenyl-PolyDiMethylSiloxane)
↓ing Molecular Weight →

 50 % TFP-PDMS (TriFluoroPropyl-PolyDiMethylSiloxane) Reversed Normal

 50 % CP-PDMS (CyanoPropyl- PolyDiMethylSiloxane) Adsorption Phase Phase Ion Exchange
 PEG (PolyEthylene Glycol) Partition Partition

23. Separating Enantiomers Using GC

 Makes use of the different affinities of the enantiomers to a chiral
stationary phase. Size Exclusion (Gel Permeation Size Exclusion (Gel Filtration
 Common stationary phase: cyclodextrins bonded to PDMS. with Hydrophobic Packing) with Hydrophilic Packing)
 α-, β- and -Cyclodextrins are made up of 6, 7 and 8 D-glucose
molecules respectively.
29. Types of Packing in HPLC
24. Common Detectors in GC
 Porous Packing
Applicable
Detectors Signal LOD  Perfusion Packing
Samples
 Non-porous Packing
Flame
Hydrocarbons Current 0.2 pg/s  Monolithic Column
Ionisation
Thermal Thermal
Any 500 mg/mL 30. Bonded Stationary Phase
Conductivity conductivity
 Silanol groups can be capped with TMS groups to eliminate polar
sites.