MASS SPECTROSCOPY (CHAP 3)
• Mass Spectroscopy: A technique to measure the mass and molecular weight of a molecule.
- Can provide details about the molecule's structure.
How Mass Spectrometry Works
1. Ion Formation:
- Electrons hit the molecule.
- This causes the molecule to break into ions.
2. Acceleration:
- Ions are pushed through a narrow slit.
- They enter an analyzer tube.
3. Kinetic Energy Calculation:
- Each ion moves with a certain speed.
- We measure this speed based on the ion's mass and charge.
4. Velocity of Ions:
- Heavier ions move slower than lighter ones.
- This happens because all ions have the same kinetic energy.
5. Fragmentation Patterns:
- We look at how the molecule broke apart.
- This pattern helps us identify the original molecule.
6. Positive Charges:
- Some fragments have a positive charge.
- These charged fragments are more stable.
- They are easier to identify.
Mass Spectrometry of Small Molecules
1. Vaporization:
- Sample molecules are turned into gas.
2. Electron Bombardment:
- Electrons are shot at the gas molecules.
3. Cation Radical Formation:
- This creates positively charged, unstable molecules (cation radicals).
4. Fragmentation:
- Bonds in the molecules start to break, forming smaller pieces.
5. Charge-to-Mass Measurement:
- The analyzer measures how much charge each piece has compared to its mass.
This process helps scientists understand the structure and composition of small molecules.
how mass spectrometry works.
here's a simpler and shorter explanation:
1. Ions are created by bombarding the sample with
electrons. 1. Ions are created and accelerated into an analyzer
tube.
2. These ions are then accelerated through a small
opening (slit) into the analyzer tube. 2. All ions get the same energy from this acceleration.
3. As the ions exit the slit, they have kinetic energy 3. Heavier ions move slower, lighter ions move faster.
(KE). This energy depends on:
- The ion's mass (m) 4. This difference in speed helps separate ions based
- Its charge (z) on their mass.
- The accelerating voltage (V)
5. The device can then measure these separated ions
4. The relationship between these factors is given by to determine their mass-to-charge ratio.
the equation: KE = zeV = ½ mv²
This process allows the mass spectrometer to identify
5. All ions with the same charge (z) are assumed to different molecules in a sample.
have the same kinetic energy after acceleration.
6. However, ions with different masses will travel at
different speeds:
- Heavier ions will move more slowly
- Lighter ions will move more quickly
7. This difference in velocity allows the mass
spectrometer to separate and detect ions based on their
mass-to-charge ratio.
In essence, this process is like a race where all
participants (ions) start with the same energy, but
heavier participants move more slowly, allowing the
device to distinguish between them based on when
they reach the detector.
concept of a mass spectrum
1. A mass spectrum is a graph:
- The x-axis shows the mass-to-charge ratio (m/z) of ions
- The y-axis shows how many of each ion were detected (signal intensity)
2. The tallest peak on this graph is called the base peak:
- It's given a value of 100%
- All other peaks are measured as a percentage of this peak
3. There's a special peak called the parent peak or molecular ion:
- This represents the original molecule that hasn't broken apart
- It shows up as M+ on the graph
- It helps determine the molecular weight of the compound
In essence, a mass spectrum is like a bar chart that shows different pieces of a molecule. The height of each bar
tells you how much of that piece is present, and the position of the bar tells you how heavy that piece is. The
tallest bar is used as a reference point, and there's one special bar that represents the whole, unbroken molecule.
Peak that corresponds to the unfragmented radical cation is parent peak or molecular ion ( M + )
i still dont understand this one, explain to me easily
1. In mass spectrometry, the sample molecule is turned into an ion by removing an electron. This creates what's
called a "radical cation."
2. Sometimes, this ion doesn't break apart (or "fragment") during the process. It stays whole.
3. When this whole, unfragmented ion shows up on the mass spectrum, we call it the "parent peak" or "molecular
ion."
4. It's labeled as M+ on the spectrum.
5. This peak is important because it tells us the molecular weight of the original molecule.
Think of it like this: Imagine you have a Lego structure. The parent peak or molecular ion is like the whole Lego
structure before you take any pieces off. It represents the complete, original molecule before any breaking apart
happens in the mass spectrometer.
Interpreting Mass Spectra
1. Molecular weight:
- We can find the molecular weight of a compound from the mass of the molecular ion (parent peak).
2. High-resolution instruments:
- Some advanced machines can measure mass very precisely.
- They can measure up to 0.0001 atomic mass units (amu).
- This precision helps identify specific atoms in a molecule.
3. Example of why precision matters:
- A molecular weight of 72 could be two different molecules:
a) C5H12 (pentane)
b) C4H8O (butanal)
- But with high precision, we can tell the difference:
a) C5H12 has an exact mass of 72.0939 amu
b) C4H8O has an exact mass of 72.0575 amu
4. Why the difference:
- This difference comes from the tiny mass differences between atoms:
- Oxygen (O) = 15.99491 amu
- Carbon (C) = 12.0000 amu
- Hydrogen (H) = 1.00783 amu
In simple terms, it's like having a super-accurate scale that can tell the difference between two people who weigh
almost exactly the same. This helps chemists identify molecules precisely, even when they have the same
approximate weight.
Other Mass Spectral Features
1. Missing parent ion:
- Sometimes, the original molecule breaks apart completely during the process.
- This means we can't see the parent ion (whole molecule) in the spectrum.
- When this happens, scientists use gentler methods like "chemical ionization" to avoid breaking the molecule.
2. Heavier peaks:
- Sometimes you might see peaks that are heavier than the parent ion.
- These come from naturally occurring heavier versions of atoms (isotopes) in the molecule.
3. Example of a heavier peak:
- You might see a peak at M+1 (one mass unit heavier than the parent ion).
- This often comes from carbon-13 (13C), a heavier version of normal carbon.
- Carbon-13 occurs naturally in small amounts in all carbon-containing molecules.
Think of it like this:
- If the parent ion is missing, it's like trying to identify a cake after it's been cut into pieces. Scientists use gentler
methods to keep the "cake" whole.
- The heavier peaks are like finding a few heavier ingredients mixed into your recipe. They're natural variations
that give extra information about the molecule.
what is an isotope?
An isotope is a version of an element that has the same number of protons but a different number of neutrons in
its nucleus.
To understand this better, think of it like this:
1. Atoms are like buildings:
- Protons and neutrons are in the "foundation" (nucleus)
- Electrons are like "floors" above the foundation
2. Isotopes are like buildings with the same number of floors (electrons) and the same type of foundation material
(protons), but with a slightly different foundation size (different number of neutrons).
3. For example, carbon has three main isotopes:
- Carbon-12: 6 protons, 6 neutrons (most common)
- Carbon-13: 6 protons, 7 neutrons
- Carbon-14: 6 protons, 8 neutrons
4. All of these are still carbon because they have 6 protons, but they have slightly different masses due to the extra
neutrons.
5. Most elements in nature are mixtures of different isotopes.
In the context of mass spectrometry, isotopes can cause additional peaks in the spectrum, giving scientists more
information about the molecule they're studying.
Interpreting Mass - Spectral Fragmentation Patterns
1. Molecule breaking apart: 1. When molecules break in a mass spectrometer, they
- When a molecule is put into a mass spectrometer, split into smaller pieces.
it breaks into smaller pieces (fragments).
2. Each type of molecule breaks in its own unique
2. Unique breaking pattern: way.
- Each type of molecule tends to break in its own
unique way. 3. This unique breaking pattern is like a fingerprint for
- This creates a specific pattern of fragments. the molecule.
3. Fingerprint analogy: 4. Scientists compare this "fingerprint" to known
- This pattern of fragments is like a fingerprint for patterns to identify the molecule.
the molecule.
- Just like how each person has a unique fingerprint, 5. The broken pieces that can best hold a positive
each type of molecule has a unique fragmentation charge tend to show up more in the results.
pattern.
Think of it like solving a puzzle - the way the pieces
4. Identification: break and fit together helps scientists figure out what
- Scientists can compare this "fingerprint" to the whole picture (molecule) was.
patterns of known molecules.
- This helps them identify what the unknown
molecule is.
5. Positive charge preference:
- When the molecule breaks, the positive charge
tends to stay on certain fragments.
- It goes to the pieces that can hold the charge most
stably.
Think of it like this: Imagine you have a LEGO
structure. If you drop it, it will break in a specific way
based on how it was built. By looking at the broken
pieces and how they fell apart, you could figure out
what the original structure was. That's similar to how
scientists use fragmentation patterns to identify
molecules.
Mass Spectral Fragmentation of Hexane
1. Hexane is a molecule with a mass of 86 (this is the "molecular ion").
2. When hexane is put into a mass spectrometer, it breaks apart into smaller pieces.
3. These smaller pieces have different masses:
- One piece has a mass of 71
- Another has a mass of 57
- Another has a mass of 43
- And another has a mass of 29
4. These masses (71, 57, 43, 29) show up as peaks on the mass spectrum graph.
5. The "m/z" you see just means "mass-to-charge ratio", which in this case is essentially just the mass of each
piece.
Think of it like breaking a cookie into smaller pieces.
The whole cookie (hexane) weighs 86 units. When you break it,
you get crumbs of different sizes - some weighing 71 units, some 57,
some 43, and some 29. These different-sized crumbs create the pattern
that helps identify the original cookie (hexane).
Mass Spectrometry of Some Common Functional Groups Alcohols:
1. This is talking about how alcohol molecules break apart in a mass spectrometer.
2. Alcohols are molecules that have an -OH (oxygen-hydrogen) group attached to a carbon atom.
3. When alcohols break apart, they do so in two main ways:
a. α-cleavage:
- This means the bond next to the C-OH group breaks.
- Think of it like cutting a string right next to where a bead (the OH group) is attached.
b. Loss of H-OH:
- This means the entire OH group, plus an extra hydrogen, breaks off.
- When this happens, the two carbons that were on either side of the OH form a double bond (C=C).
- It's like removing a link in a chain, and the two parts on either side clasp together more tightly.
4. These breaking patterns are characteristic of alcohols, which helps scientists identify them in a sample.
In simple terms, it's describing the predictable ways that alcohol molecules fall apart when analyzed, which helps
in identifying them.
Mass Spectrometry in Biological Chemistry:
1. Time-of-Flight (TOF) Instruments: Time-of-Flight (TOF) instruments are used to study
- These are special tools used in mass spectrometry biological molecules. They work like this:
for biological samples.
- They measure how long it takes for molecules to 1. First, they turn the biological sample into tiny,
"fly" through a tube. charged particles. This is done using either a spray
method (ESI) or a laser method (MALDI).
2. Two main ways to prepare biological samples:
a. Electrospray Ionization (ESI): 2. Then, these particles are sent flying through a long
- Imagine spraying a fine mist of your sample. tube.
- This turns large biological molecules into
smaller, charged particles. 3. By measuring how long it takes each particle to
reach the end of the tube, scientists can figure out what
b. Matrix-Assisted Laser Desorption Ionization the original biological molecules were.
(MALDI):
- The sample is mixed with a special material It's like a race where different sized molecules run
(matrix). down a track, and we time them to figure out what
- A laser is used to turn this mixture into charged they are.
particles.
3. Time-of-Flight Mass Analyzer:
- After the sample is prepared (using ESI or
MALDI), it's sent through a long tube.
- Smaller particles travel faster, larger ones slower.
- By measuring how long it takes particles to reach
the end, we can figure out their size and mass.
In simple terms, these are methods to gently turn big
biological molecules into smaller, charged pieces, and
then measure these pieces by seeing how fast they fly
through a tube. This helps scientists identify and study
complex biological molecules like proteins.
Relative Atomic Mass (RAM)
1. RAM is a way to measure the average mass of an Relative Atomic Mass (RAM)
atom of a particular element. 1. Definition:
o Average mass of an atom of an
2. It's called "relative" because it's compared to a element.
standard: 1/12 of the mass of a carbon-12 atom. 2. Comparison Standard:
o Measured relative to 1/12 of a
3. Many elements have different versions called carbon-12 atom.
isotopes, which have slightly different masses. 3. Isotopes:
o Elements have different versions
4. RAM takes into account all these isotopes and how with slightly different masses.
common each one is in nature. 4. Natural Abundance:
o Considers how common each
5. It's a "weighted average" because it considers not isotope is in nature.
just the mass of each isotope, but also how much of 5. Weighted Average:
each isotope is typically found. o Calculates average mass based on
isotope masses and their
Think of it like this: If you're calculating the average abundance.
age of people in a room, but there are more young
people than old people, the average will be closer to
the younger age. That's similar to how RAM works
with isotopes.
So, RAM gives us a single number that represents the
typical mass of an atom of an element, considering all
its naturally occurring forms.
This example is explaining how to calculate the Relative Atomic Mass (RAM) of boron using a simple
scenario. Let me break it down:
1. Imagine you have 123 boron atoms:
- 23 of them are lighter (mass 10)
- 100 of them are heavier (mass 11)
2. To find the total mass:
- Lighter atoms: 23 × 10 = 230
- Heavier atoms: 100 × 11 = 1100
- Total: 230 + 1100 = 1330
3. To get the average (RAM), divide the total by the number of atoms:
1330 ÷ 123 = 10.8
4. This 10.8 is the RAM of boron.
5. Why not 10.5?
- A simple average of 10 and 11 would be 10.5
- But there are many more heavier atoms (100) than lighter ones (23)
- So the average is "pulled" closer to 11, giving us 10.8
This "weighted" average (10.8) better represents the actual mix of boron atoms in nature, where the heavier type
is more common.
