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What are the main stages of a measurement system?
Sampling, separation, transduction and analysis
Why are chemical separations carried out?
Isolate analyte from other components to avoid possible interferences
To preconcrete the analyte to raise its concentration above the detection limit, or make it easier to measure.
To enable the use of a universal or non-selective detector (for e.g. flame ionisation detector in gas chromatography that responds to the presence of C in a molecule)
What is partitioning?
The distribution of an analyte between two phases
What causes partitioning to occur?
Differences in solubility and chemical potential between phases
What happens when chemical potential equilibrates between phases?
Partitioning stops because equilibrium is reached
What is the partition coefficient (K)?
The ratio of analyte concentration/activity between 2 phases at equilibrium
What assumption allows activity to be approximated by concentration?
Low analyte concentration
What is the distribution ratio (D)?
The ratio describing partitioning of all forms of a compound (e.g charged and uncharged)
Nernst’s Law
Concentration ratio between phases is constant at equilibrium
What is solvent extraction?
Separation based on partitioning between 2 immiscible liquids
What measurements may be used to determine analyte concentration?
UV/Vis spec or atomic absorption spec
What is counter current separation?
A process where fresh phases are introduced at each equillibrium step
What is the Craig appararus?
A discrete - vessel implementation of counter current separation
What is a theoretical plate?
An individual vessel
Used as there is a hypothetical zone, volume or distance over which an equilibrium partitioning occurs
What rule of thumb describes solubility?
Like dissolves like
What are dispersion (Van der Waals forces)?
Interactions between transient dipoles caused by electron oscillations
What are dipole dipole interactions?
Interaction between permanent dipoles
What is an ion-dipole interaction?
Attraction between ion and polar molecules
Why is water highly effective at stabilising charges?
Has high dielectric constant and hydrogen bonding
What does the dielectric constant describe?
Solvent’s ability to reduce electrostatic attraction between charges
What is the approximate dielectric constant of water?
80
Why is water’s dielectric constant unusually high?
Hydrogen bonding aligns dipoles into large effective dipole
What the mobile phase?
The moving phase carrying solutes through the system
What is the stationary phase?
The phase that remains fixed inside the column
What are the 4 main components of a chromatographic system?
Mobile phase
Injector
Column
Detector
Why do different solutes separate in chromatography?
They interact differently with the stationary and mobile phases based on their polarity and their affinity to each phase.
What determines solute velocity trhough a chromatographic column?
The time spent in the stationary phase
What is a chromatogram
The detector output showing the separated components over time.