Analysis and Spectra

Question 1

Two common analytic techniques in organic chemistry are infrared (IR) spectroscopy and ultraviolet (UV) spectroscopy. What do these procedures have in common?

Answer 1

Both techniques involve absorption of electromagnetic radiation by the molecule that is being analyzed.

Radiation with a specific frequency will be absorbed by the electrons in a molecule, exciting them to higher energy states.

Question 2

What happens if a molecule is simultaneously exposed to several frequencies of light?

Answer 2

The molecule will only absorb radiation from the particular frequencies at which it has matching energy states. This concept is known as resonance.

Radiation with other frequencies will pass through or reflect. Spectroscopy, or the process of measuring the absorbed radiation, can yield information about the composition of the molecule.

Question 3

What can infrared (IR) spectroscopy identify about an organic molecule?

Answer 3

It can identify the functional groups present on the molecule.

Different covalent bonds vibrate at different, characteristic frequencies when light is absorbed by the molecule. These frequencies correspond to certain common groups.

Question 4

In infrared (IR) spectroscopy, how can molecules with exactly the same atoms absorb light differently?

Answer 4

Different covalent bonds vibrate at different, characteristic frequencies. These vibrations can exist in different forms, such as stretching, bending, and rocking.

Molecules that contain the same atoms but different functional groups will absorb light at their specific characteristic frequencies. Their spectra will not necessarily overlap.

Question 5

What determines the frequency of an IR vibration?

Answer 5

They are determined by the characteristics of a bond:

• number of electron pairs
• polarity of the bond
• masses of the atoms involved

Question 6

What qualities characterize bonds with high IR vibration frequencies?

Answer 6

• double and triple bonds
• polar bonds
• bonds that include lighter atoms

Remember, IR vibration frequencies are determined by the characteristics of the bond.

Question 8

What qualities characterize bonds with low IR vibration frequencies?

Answer 8

• single bonds
• nonpolar bonds
• bonds that include heavier atoms

Remember, IR vibration frequencies are determined by the characteristics of the bond.

Question 9

How can a molecule be identified using an IR spectrum?

Answer 9

A molecule is identified via characteristic peaks in its spectrum.

Though functional groups may have many absorption peaks across the full spectrum, certain ranges are important to know.

Question 10

Which functional group yields the IR peak shown below?

Answer 10

hydroxyl (-OH) functional group

Hydroxyl groups always give a broad absorption peak in the range of 3100-3500 cm^-1.

Question 12

Which functional group yields the IR peak shown below?

Answer 12

carbonyl (C=O) functional group

Carbonyl groups always give a sharp absorption peak around 1700 cm^-1.

Question 13

Which functional group yields the IR peak shown below?

Answer 13

amine (N-H) functional group

Amine groups always give a sharp absorption peak in the range of 3100-3500 cm^-1.

Question 14

What functional group must be present in a molecule with the IR spectrum shown below?

Answer 14

carbonyl functional group

Carbonyl groups always give a sharp absorption peak around 1700 cm^-1. The graph above is the spectrum of propanone.

Question 15

What functional group must be present in a molecule with the IR spectrum shown below?

Answer 15

hydroxyl functional group

Hydroxyl groups always give a broad absorption peak in the range of 3100-3500 cm^-1. The graph above is the spectrum of propan-1-ol.

Question 17

What functional group must be present in a molecule with the IR spectrum shown below?

Answer 17

amine functional group

Amine groups always give a sharp absorption peak in the range of 3100-3500 cm^-1. The graph above is the spectrum of 1-aminobutane.

Question 18

What functional group must be present in a molecule with the IR spectrum shown below?

Answer 18

hydroxyl functional group

Hydroxyl groups always give a broad absorption peak in the range of 3100-3500 cm^-1. The graph above is the spectrum of ethanol.

Question 19

What is the fingerprint region of an IR spectrum?

Answer 19

The area of the spectrum between 500 and 1450 cm^-1.

Every molecule’s fingerprint region is unique, but the signal in this area tends to be complex.

Question 20

What region of the IR spectroscopy spectrum can generally be disregarded?

Answer 20

The fingerprint region, which covers the range from 500 cm^-1 to 1450 cm^-1, can be disregarded.

The fingerprint region often does not contain distinct characteristic peaks.

Question 21

What can UV-visible spectroscopy identify about an organic molecule?

Answer 21

It can identify a molecule’s electronic energy levels.

Electrons bound to different molecules will have different excited states. These molecules will absorb photons of light that correspond to the difference between the ground and excited energy levels, which exist in the visible and near-UV regions of the spectrum.

Question 22

What features characterize the organic molecules that display signals in UV-vis spectroscopy?

Answer 22

It must have nonbonding electrons that can be excited without breaking a bond.

The most common examples are:

• conjugated molecules
• molecules with double and triple bonds
• molecules with nonbonding pi electrons
• molecules that contain transition metals

Question 23

What does the color of an organic molecule indicate about the frequency of light that it absorbs?

Answer 23

Molecules are complementary in color to the light that they absorb.

For example, if a molecule is illuminated with white light and absorbs green light, it must reflect light from the remainder of the spectrum, namely red. The molecule will appear reddish in color.

Question 24

What color of light must be absorbed by a molecule that appears reddish in color?

Answer 24

The molecule must absorb green light.

More broadly, the absorbed light must have a frequency around the yellow/green/blue area of the spectrum.

A molecule that absorbs green light will reflect red, making it appear reddish in color.

Question 25

What color of light must be absorbed by a molecule that appears greenish in color?

Answer 25

The molecule must absorb red light.

A molecule that absorbs red light will reflect light in the blue/green/yellow area of the spectrum, causing it to appear green in color.

Question 26

What does a mass spectrometer measure?

Answer 26

It measures the path curvature of molecular fragments from a sample. This is then related to a “mass-to-charge ratio” for each fragment.

The mass-to-charge ratio can then be used to calculate molecular mass.

Question 28

Briefly describe how a mass spectrometer works.

Answer 28

It bombards a vapor sample with sufficiently high-energy electrons to both fragment and ionize the sample.

The charged ions and fragments are then accelerated using an electric field and bent through a curved detector using a magnetic field. The radius of curvature for the ions depends on their mass and charge, allowing total mass to be calculated.

Question 29

A student is looking for a laboratory technique that will help him separate two components of a sample. What conditions must be satisfied for mass spectrometry to be a good choice?

Answer 29

Mass spectrometry is **never** a good separation technique. It is used for analysis, not separation / purification. ## Footnote Be careful to distinguish separation techniques from analytic ones. Mass spectrometry, for example, destroys the molecule that is being analyzed, so it would not be used to separate components of a mixture for later use. Actual separation techniques include extraction and distillation.

Question 30

What does the "NMR" stand for in **NMR spectroscopy**?

Answer 30

Nuclear Magnetic Resonance ## Footnote Although there are multiple types of this process, only proton (H⁺) NMR is tested. NMR operates by exposing a molecule in the solvent phase to a large, permanent magnetic field. It then measures its resonant absorptions of electromagnetic radiation.

Question 31

At the molecular level, what does H⁺ NMR spectroscopy measure?

Answer 31

It measures the environment of the protons, or hydrogen atoms, in a molecule. ## Footnote Hydrogens bound to different atoms, and in different configurations, will respond differently to magnetic fields. This concept forms the essence of H⁺ NMR spectroscopy.

Question 32

What determines the **chemical shift** of a proton in NMR spectroscopy?

Answer 32

The chemical shift of a proton depends on how **deshielded** it is by the other atoms in the molecule. ## Footnote Deshielding generally refers to the proton's proximity to electronegative groups. The less electron density an atom retains, the more deshielded it is, and the further downfield its chemical shift will be. Resonance structures and highly electronegative atoms tend to deshield protons.

Question 33

A proton near a certain functional group displays an NMR peak of 9.5 ppm. Would this peak be considered to be **upfield** or **downfield**?

Answer 33

This peak would be considered to be **downfield**. NMR peaks are relative, but the more downfield a peak is shifted, the higher its value will be. 9.5 ppm is significantly higher than a characteristic alkane peak around 0-4 ppm. ## Footnote Downfield shifts are the result of deshielding, usually due to proximity to electronegative groups. 9.5 ppm is near the characteristic shift for an aldehyde.

Question 34

A certain NMR spectrum displays multiple distinct peaks. What does this show about the molecule?

Answer 34

The molecule contains non-identical protons. Signals in an NMR spectrum represent different chemical shifts due to different proton environments. ## Footnote Identical protons will display signals at the same point, such as the protons in methane. In contrast, a molecule with many different proton environments will have multiple peaks, such as butanoic acid (4 peaks).

Question 35

A certain NMR signal has an integrated area three times that of another peak. What does this show about the protons involved?

Answer 35

The set of equivalent protons corresponding to the larger peak must contain three times as many protons as the other. The area of an NMR peak is proportional to the number of identical protons with the given chemical shift. ## Footnote Identical protons will have signals at the same point, and their signals will add up to a single peak in the measured spectrum. Integrated area is often given if it is necessary, but peak height can also be used as a valid approximation.

Question 36

In what range is the NMR chemical shift of a proton bound to an **alkane** (sp³-hybridized)?

Answer 36

between **0 and 4 ppm** ## Footnote For example, the protons on ethane have an NMR value of about 0.86.

Question 37

In what range is the NMR chemical shift of a proton bound to an **alkene** (sp²-hybridized) carbon?

Answer 37

between **4 and 7 ppm** ## Footnote For example, the protons on ethene have an NMR value of about 5.35.

Question 38

In what range is the NMR chemical shift of a proton bound to an **aromatic** carbon?

Answer 38

between **6 and 8 ppm** ## Footnote For example, the protons on benzene have an NMR value of about 7.28.

Question 39

By what amount does an adjacent electronegative atom usually affect the NMR chemical shift of a proton?

Answer 39

a downfield shift of **up to 3 ppm** ## Footnote For example, a proton in methane has a peak at about 0.25 ppm, while the chemical shift of a proton in chloromethane is around 3.0 ppm. The electronegative chlorine atom draws electron density towards itself, deshielding the other protons in the molecule by 2.75 ppm.

Question 40

In what range is the NMR chemical shift of a proton bound to an **aldehydic** (CHO) carbon?

Answer 40

a downfield chemical shift between **8.5 and 11 ppm**. ## Footnote Simply remember this value as around 9.5 ppm. For example, the protons on formaldehyde have an NMR value of about 9.61.

Question 41

In what range is the NMR chemical shift of a **carboxylic acid** (COOH) proton?

Answer 41

a downfield chemical shift between **10 and 12.5 ppm** ## Footnote For example, the carboxylic acid proton on acetic acid has an NMR value of about 11.8.

Question 42

What types of protons are likely present in the molecule whose NMR spectrum appears below?

Answer 42

This molecule has only one peak in the range for aromatic protons, so all protons are likely part of an aromatic structure. ## Footnote This is the NMR spectrum of benzene, a common organic molecule.

Question 43

What types of protons are likely present in the molecule whose NMR spectrum appears below?

Answer 43

This molecule has two unique peaks in the sp³-hybridized range, probably corresponding to alkane protons. It also contains a single proton in the aldehydic range. ## Footnote This is the NMR spectrum of propanal, an aldehyde.

Question 44

What does **spin-spin splitting** look like in an NMR spectrum?

Answer 44

It results in peaks that look jagged. A peak that displays splitting will look like multiple peaks packed extremely close together. ## Footnote However, such a peak will still only refer to one proton or set of equivalent protons.

Question 45

In proton NMR, how can one determine the amount of splitting of a single peak?

Answer 45

Each unique proton's peak is split into (n+1) subpeaks, where n is the number of protons bound to adjacent carbons. ## Footnote "Adjacent" refers to carbons next to the carbon to which the proton in question is bound.

Question 46

With regard to splitting, what name is given to the blue peak (far right) in the NMR spectrum below, and how many adjacent protons does it represent?

Answer 46

The blue peak is a doublet, meaning that the adjacent carbon is bound to **one** proton. ## Footnote Since the peak is split into a doublet (2 subpeaks), the (n+1) rule states that a single adjacent proton must be present (n = 1). To recall the n+1 rule, remember that a peak corresponding to a proton with zero adjacent protons will be a singlet. The spectrum shown above is of propene.