Exam #2 Flashcards
Mass Analyzers can use static/dynamic ________ or _______ fields to separate gas phase ions based on their ___________.
Electric ; magnetic ; m/z values
Can mass analyzers be used alone or with other mass analyzers?
Both
Ions are accelerated out of the source to the mass analyzer by ______________.
electrostatic focusing
Why is it good that ions from the ion source usually have a negligible KE value?
Good because some mass analyzers measure the velocity and use it in their calculations. You don’t want to add to that.
KE is
kinetic energy of fully accelerated ion.
V is
Potential difference you’re accelerating ions with. You know what this value is and you can control it.
With mass analyzers, ions move _______ to the _______.
from the ion source ; mass analyzer
In mass analyzers, how are the ions moved through the vacuum chamber?
Via electrostatic focusing
What are the two definitions of resolution?
1) The separation of two ions of nearly identical m/z (chromatography)
2) Sharpness of a mass spectral peak (of just one single peak)
When talking about one peak’s sharpness (resolution), what is it talking about?
Full Width Half Maximum Method
What is the Full Width Half Maximum Method?
Resolution = m/Δm ; the m/z at the top of the peak divided by the width of the peak at half peak
What are wider peaks called?
Gaussian
What are sharper peaks called?
Lorentzian peaks
As a good rule of thumb, what m/z value is considered high resolution?
100,000 or more
High resolution mass spectrometers
- Double Focusing Sectors
- Orbitraps
- FT-ICR (100,000,000 resolution)
- Some TOFs (40,000 resolution right now but they are improving)
Why do we need high resolution?
1) Detection of isobaric ions
2) Exact Mass Measurements
3) Determination of an ion’s charge from m/z using C13 (or C12) isotope pattern
4) Increase selectivity and/or sensitivity (incr. resolution decreases the chemical noise; lower number of ions detected but again, the noise is lowered). Increases S/N
Small width of peak means
High Resolution
What is the highest form of resolution?
FT-ICR
What is meant by “Double Focusing”
electric sector followed by a magnetic sector (EB or BE)
What is the mass accuracy with high resolution?
+/- 0.0003 m/z
What calibration compound is used to calibrate the x-axis?
FC-43 (Perfluorotributylamine, aka PFTBA); Used for low volatile analysis (EI or CI)
-Calibrates the x-axis
What calibration compound is used to calibrate the y-axis?
Decafluorotriphenylphosphine (DFTPP)
-For calibrating ion intensity (y-axis)
Why are there so many hydrogens on the calibrants?
- Presence of Fluorines significantly decreases boiling point (30-40ºC). More volatility b/c there is less hydrogen bonding
- Because of its larger mass, it creates a larger range of analysis for your sample to peak
Time of Flight (TOF)
- Simplest mass analyzer (in terms of hardware and understanding it)
- Measures time (t) required for ions to travel down a flight tube (L)
- Not as sturdy (electronics get outdated over time)
- Pulse Mass analyzer
How do ions move out of the source / how are ions directed to the mass analyzer?
Ions are accelerated out of the source to the mass analyzer by electrostatic focusing.
Write out the kinetic energy equation for an ion fully accelerated from the ion source.
KE = (mv^2)/2 = zV
*Note: “z” is the charge on ions and “V” is the voltage in electrostatic focusing
What is the mass spect. definition of resolution?
Resolution is the sharpness of the spectral peaks.
What is the chromatography definition of resolution?
The separation of two ions of nearly identical m/z
Where are Lorentzian peaks typically found (what computational conversion)?
Fourier-Transform
With mass analyzers, in addition to having high resolution, what parameter also needs to be well-defined?
m/z range
Kicking out all chemical noise increases ______ and ______.
Resolution and specificity
What chemical is used to calibrate the x-axis for mass analysis? What is it calibrating?
Perfluorotributylamine (FC-43) ; m/z range
What chemical is used to calibrate the y-axis for mass analysis? What is it calibrating?
Decafluorotriphenylphosphine (DFTPP) ; ion intensity
What is the mass range for the x-axis in mass analysis?
50 to 502 m/z
Why does TOF require a high accelerating voltage?
-This is to minimize the KE spread that may occur from the ionization event. When ioniziation event occurs, KE is added to the ions. So you want to add such a large accelerating voltage (V) so that the KE added by the ionization event is negligible.
Why does fragmentation within the flight tube, along L, not effect the time of flight?
After the accelerating voltage is applied, it does not matter of there is fragmentation or not because the ions will still travel at the constant velocity. Velocity of the ions won’t change.
Name two ways to increase resolution by decreasing time spread.
1) Delayed Extraction - where you allow the ionization pulse to complete (200-350 seconds) before applying the pulse to extract the ions from the ion source.
2) Reflectron (or Reflector) - Ions are exposed to an electromagnetic field in the middle of the flight path. This fixes the time spread, not the velocity spread.
What is the purpose of reflectrons?
- Reflectrons are used to fix the time spread.
- Ions that are moving at a greater velocity have to travel a longer flight path, which means it takes longer to reach the detector. This is so that it and another ion with the same m/z (but may be moving at a slower velocity) will reach the detector at the same time.
What is TOF often coupled with (ionization technique(s))?
Any continuous source of ions. Also works really well with pulsed ionization methods.
- MALDI, LD, & 252CfPD (Good because of their pulsed ionization method)
- TOF/SIMS (more common with newer TOF machines)
- ESI and APCI (ions are made continuously but can be “trapped” and pulsed into the extraction region as needed.
- EI, CI, FAB, GC, LC-MS
Reflectrons increase resolution by (2 methods)
1) Decrease the time spread for ions of the same m/z
2) Increase the flight path, (L)
What detector is used for TOF?
Multichannel Plate (MCP)
Describe the detector.
-A circular device that is about 2-3 mm wide in diameter. -Composed of multiple glass capillary tubes that each are 0.5-1.0 mm long and have a 5 micrometer diameter. The capillaries are coated with an electron emissive material such as PbO.
Why is the detector a good choice for TOF?
- It is fast
- Can go up or down as the ions hit the detector
- Good multiplication of signal.
What is signal averaging?
Also known as ensemble averaging
- Not related to Fourier Transform
- Recorded mass spectrum is usually an average of spectra from 100 or more individual ionization events (i.e. laser shots)
Signal/Noise ratio is equal to
The square root of the number of scans (n)
Overall features of TOF
- Entire mass spectrum is obtained in 500 microseconds
- Pulsed ; can be combined with MALDI, LD and PD
- Can be used with continuous ion sources as well
- Moderate to high resolution (better than quadrupoles, less better than double-focusing, much less better than FT-ICR)
- Has the widest dynamic and linear range of any technique
- The fastest mass analyzer
- Can be used on large molecules (both volatile and nonvolatile)
- Has very high efficiency of ion transmission, meaning it can detect extremely small amounts of ions
- Very low limits of detection
- Uses signal averaging
What feature is needed for a TOF digitizer?
Needs a fast analog to digital converter
With a magnetic sector, what two forces must be equal to each other in order for the turn/curve to take place?
Magnetic force and the centrifugal force
What is the equation for magnetic force?
Bzv
What is the equation for centrifugal force?
mv^2/r
How do magnetic sectors discriminate m/z?
Using momentum to charge ratio
Derive the BS equation for m/z.
mv/z=Br
m/z=B2z2/2V
What is the special focusing feature of BS?
Directional Focusing-
ions with the same m/z and velocity but take different paths through B will come into focus at the exit slit.
Name two parameters which affect ions reaching the exit slit.
1) Scanning V while B is held constant (needs continuous ion source)
2) Scanning B while V is held constant
- Most common
- Scanning analyzer
- Yields a non-linear mass scan