MOLECULAR ORBITAL THEORY AND UV SPECTROSCOPY

Molecular orbital (MO) theory describes covalent bond formation as a combination of atomic orbitals to form molecular orbitals. MOs represent regions of space in a molecule where electrons spend > 90% of their time, traveling in wave-like motion. In the H2 molecule 2 singly occupied 1s atomic orbitals combine to produce 2 molecular orbitals... 1. A bonding MO, i.e., an additive combination - by constructive interference of in-phase waves. 1. An antibonding MO, i.e., a subtractive combination - by destructive interference of out-ofphase-waves. node

H H-H Antibonding MO (empty) 2*

1s

1s

H-H bonding MO (filled) H H E=h

The bonding MO (denoted 1) is lower in energy because most of the electron density is between the excited state ground In the * both 1s electrons reside in 1 . H nuclei, thus holding the atoms together. state ground state, transition The antibonding MO (denoted 2* ) is higher in energy because most of the electron density is outside the region between the nuclei. The diagram shows a region of zero electron density (a node) between the two nuclei. The positively charged nuclei thus repel and bonding is unfavorable. In the ground state, 2* is empty, however, if EM radiation of the same energy as the energy gap between 1 and 2* strikes the molecule, one or both of the bonding electrons may be excited (promoted) to the 2* orbital. Once excited, the molecule may split, ionize or reradiate the energy and return to the ground state. According to MO theory, the following are true... 1. The number of MO's must equal the number of atomic orbitals which combined to produce them. 2. Bond order of a molecule =

# e's in bonding MO's - # e's in antibonding MO's 2

3. Bond order > 0 produces a stable molecule. Bond order = 0 means no bonds formed between atoms. Bond order < 0 means that the molecule is unstable (decomposes). 1

Molecular Orbital Description of Alkenes: Ethylene (C2H4) The C-C sigma () bond in ethylene results from the overlap of two 2sp2 atomic orbitals producing two MOs (one 1 bonding and one 2* antibonding). The C-C pi () bond in ethylene results from the side-to-side overlap of two 2p atomic orbitals producing two MOs (one 1 bonding and one 2* antibonding).

ethylene
2
*

2* 2* 2*

E
2p 2sp2 2p 2sp2 1

C
E=h

1 ground state

* transition

1 excited state

1 is called a HOMO (Highest Occupied Molecular Orbital) and 2* is called a LUMO (Lowest Unoccupied Molecular Orbital). HOMO to LUMO electronic transitions always occur with lower energy (longer wavelength) radiation than any other electronic transition in a molecule. In the case of ethylene, E for this transition is 173 kcal/mol (corresponding to radiation of = 165 m, in the vacuum UV). [Use E = N h c/ to convert] Most other alkenes and alkynes, and nonconjugated polyenes and polyynes display a similar HOMO LUMO energy gap, e.g., 1-octene max = 177 m, 1-octyne max = 185 m, cyclohexene max = 182 m. This absorption band is called an E band (Ethylenic). In molecules with conjugated unsaturation, this E is less and decreases as the extent of unsaturation increases, e.g., 1,3-butadiene max = 217 m, 1,3,5-hexatriene max = 274 m.

Molecular Orbitals of Conjugated Systems: In unsaturated compounds, the HOMO LUMO excitation is generally a * transition (or n * transition). The and * MOs are not involved. As a result, MO diagrams of unsaturated compounds are simplified by drawing only the and * MOs and the Greek letter (psi) is used instead of to identify the various MOs. These are named Huckel MO diagrams.
1 node

4*

3 nodes 0 bonding interactions

2*

+ -

+
LUMO

C2pz C2pz + + E
(K band, ca. 220 m)

2 nodes 1 bonding interaction

unbonded p orbitals

HOMO

1 node 2 bonding interactions

+ -

+ 1 1,3-butadiene
0 nodes 3 bonding interactions

constructive interference overlap of waves ethylene

Opposite signs of adjacent Atomic Orbitals (AO's) corresponds to an antibonding interaction ("negative overlap") between 2 atoms and a 'node' (region of zero electron density) exists between the atoms. Same signs of adjacent AO's corresponds to a bonding interaction ("positive overlap"). In 1,3-butadiene, 1 and 2 have more bonding interactions than antibonding (nodes) and so are bonding MOs. 3* and 4* have more antibonding interactions (nodes) than bonding and thus are antibonding MOs. In its ground state electron configuration, 1,3-butadiene has 2 filled bonding MOs and all antibonding MOs are empty. The bond order of the system is 2 and the compound is stable. Note that E for the HOMO LUMO transition in 1,3-butadiene is smaller that for ethylene. As a result 1,3-butadiene (and other conjugated unsaturated compounds) absorb at relatively low energy, in the Near UV (e.g., 217 m) rather than in the high-energy Far UV (Vacuum UV, < 200 m). The absorption band arising from * transitions in conjugated polyenes is called a K band. Draw a Huckel MO diagram for 1,3,5-hexatriene showing the number of nodes in each MO and show the HOMO LUMO transition. As in the previous examples, use the Aufbau Principle, Hunds Rule, and the Pauli Exclusion Principle to determine the ground state electron configuration.

Comparing a conjugated diene (1,3-butadiene) with an unconjugated diene (1,4-pentadiene) shows why the conjugated diene is more stable. In a conjugated diene, there is a favorable bonding interaction between C2 and C3 whereas the nonconjugated diene has a node in this region. In the conjugated diene, the electrons are spread out (delocalized) over the entire system rather than localized between two specific nuclei. Charge delocalization always leads to lower energy and greater stability of a compound.
3 bonding Conjugate unsaturated cpds., e.g., polyenes & polyynes are analyzed in the near UV2in the lab. bonding 0 nodes 1 node

Molecular Orbital Description of Aromatics

interactions

interactions

Huckels Rule: Planar monocyclic systems in which each atom contributes a p orbital to the system will be strongly stabilized (aromatic) when the number of electrons in the system = (4n + 2) and n is an integer, i.e., when the number of electrons = 2, 6, 10, 14, etc. This can be confirmed by constructing a Huckel MO diagram. For monocyclic conjugated systems it is easiest to use a Frost Circle for this. A regular polygon of n sides is drawn in a circle with one corner at the lowest point. The points at which the corners of the polygon touch the circle define the energy levels of the MOs. Consider benzene. 6* 4* 5* 6*
LUMO

4* 5*
B band 260 m
6 p atomic orbitals

3 1 benzene

2 1

HOMO

The Frost Circle gives us the energy levels of the MOs. Using the Aufbau Principle, Hunds Rule, and the Pauli Exclusion Principle we determine the ground state electron configuration. The Bond Order of the system is calculated to be 3 so we conclude that the compound is stable. We see that benzene satisfies Huckels Rule for monocyclics and this confirms that it is aromatic. The HOMO LUMO transition is easily identified as 2 or 3 4* or 5*. In fact, 3 different * transitions are found in benzene (and related compounds), i.e., two E bands [E1 = 184 m (log = 4.78), E2 = 204 m (log = 3.90)] and a B band (Benzenoid) at 256 m (log = 2.30) which we would expect to correspond to the HOMO LUMO transition. Draw Huckel MO diagrams and determine which of the following compounds are aromatic. 1. cyclobutadiene 2. cyclopentadiene 3. cyclopentadienyl cation 4

4. cyclopentadienyl anion 5. cycloheptatrienyl cation 6. pyridine 7. pyrrole

Without drawing a Huckel MO diagram, use Huckels Rule to predict aromaticity in naphthalene.

Molecular Orbital Diagrams of Compounds Containing Nonbonding Electrons: Elements from Group VII A (halogens, e.g., Cl, Br, I), Group VI A (chalcogens, e.g., O, S), and Group V A (pnicogens, e.g., N, P) carry nonbonding electron pairs into the organic compounds they form. Nonbonding electrons are not involved in the formation of bonding or antibonding MOs since they are not directly involved in bonding, however, these nonbonding electrons can be excited (promoted) to unfilled MO when radiation of the correct frequency is present. Methyl Chloride (CH3Cl): We can draw a MO diagram for the C-Cl bond. Place the nonbonding 3s and 3p electrons at approximately the same energy level as the unbonded atoms. (Halogens do not hybridize when forming single bonds). methyl chloride CH 3Cl 2* antibonding MO E

C 2sp 3

3pz

Cl
3s 3p x 3p y

n
3 pairs nonbonding electrons

1 bonding MO From the MO diagram of methyl chloride, it can be seen that promotion of a nonbonding electron to the antibonding orbital (an n * transition) requires less energy than the * HOMO LUMO transition. Despite this fact, most saturated compounds containing heteroatoms still require Far-UV irradiation to cause excitation (E is still large). In methyl chloride, for example, the n * transition occurs at 173 m (log = 2.30). Exceptions: A few heteroatoms in saturated cpds undergo n * transitions in the near UV, e.g., Br (200 210 m), I (255 - 260 m), SH (230 m).

In unsaturated compounds containing heteroatoms, n * transitions are also possible. In many such compounds, E is sufficiently low such that absorption in the Near UV is possible. Acetone, for example, shows an n * absorption band at 188 m (log = 3.27) and also an n * absorption band at 279 m (log = 1.17). Absorption bands produced by n * transitions are called R bands. (German for 'radical' since a free radical is formed when one 'n' electron is promoted). Draw a MO diagram for the C=O bond in acetone showing all MOs and the n electrons and the possible electron transitions. Summary of UV Absorption Bands Band --E K B E1 E2 --R Transition * * * * * * n * n * Example
hexane C2H4, 1,4-pentadiene 1,3-pentadiene benzenes benzenes benzenes CH3NH2, CH3OH, CCl4 acetone, MEK

Cause/Source
alkanes (satd HCs) unconjugated, unsaturated cpds. conjugated systems double bonds in benzenoids double bonds in benzenoids double bonds in benzenoids most heteroatoms in saturated cpds. heteroatoms in unsaturated cpds.

( m) < 200 <200 210 -250 230 -280 180 - 190 ~ 200 160 - 190 > 250

log max

variable 3.7 - 4.7 2.3 - 3.3 variable variable 2.3 - 4.0 1.0 -1.7

ULTRAVIOLET (UV) SPECTROSCOPY The wavelengths of visible and UV radiation are generally accepted as follows ... Category IR Visible Near (Quartz) UV Far (Vacuum) UV X-rays Wavelength (m) 800 - 10 400 - 800 200 - 400 10 - 200 10 10-3
6

Wavelength ( m) .80 - 1000

(2.5 25 m = mid IR)

With respect to sunscreens and tanning formulas, the UV spectrum is divided into A, B, and C regions. Category Wavelength (m) Health Effects
least dangerous - causes loss of collagen* & decreases # of blood vessels UVA 315 - 400 causes sunburn and tanning (causes melanocytes to produce melanin) UVB 290 - 315 dangerous - causes skin cancer UVC 100 - 290 * collagen is protein contained in the connective tissues and bones.

The portion of the UV spectrum of most interest to organic chemists is 200 - 400 m, the Near UV or 'Quartz UV. Samples can be analyzed in quartz cells without interference in this range. Glass cells cannot be used since glass absorbs UV. Atmospheric oxygen absorbs below 200 m. The lower end can be extended to 185 m by flushing oxygen from the system and pressurizing with nitrogen. To work below 185 m requires evacuation of the instrument, and hence the name Vacuum UV. When electromagnetic radiation in the UV and visible regions passes through a compound containing multiple bonds, a portion of the radiation is usually absorbed by the compound. Whereas IR absorption causes low energy mechanical transitions (vibration, rotation), high energy UV/VIS absorption induces electronic transitions ( *, *, n *, etc.). For this reason, UV/VIS spectroscopy is also called electronic spectroscopy. Another difference is the convention used for describing the radiation. IR is usually reported in units of frequency (i.e., wavenumbers, cm-1 ) but UV and VIS are reported in units of wavelength (i.e., nanometers, m). 1 m = 109 m Almost all organic compounds absorb in the IR, however relatively few organic compounds absorb in the UV / VIS regions, i.e., primarily only unsaturated compounds. IR spectroscopy is valuable qualitatively, i.e., for determining the identity and/or structure of an organic compound but is poor as a method of quantitative analysis. UV and VIS spectroscopy are of limited qualitative value, i.e., they can be used to detect the presence of some unsaturated groups in organics. However UV and VIS spectroscopy are excellent methods of quantitative analysis for unsaturated compounds. IR spectra are very complex (many sharp absorption bands) but UV and VIS spectra are relatively simple. They contain a few very broad bands (often spanning ~ 50 m or more). Sharp bands are not obtained because at room temperature many modes of thermally induced vibration and rotation are occurring and the electronic absorption is superimposed upon these many closely spaced energy levels.

}
E

E2 (Electronic Energy Level 2) Vibrational energy levels

2*

}
7

E1 (Electronic Energy Level 1) Vibrational energy levels

Obtaining a UV Spectrum: 1. To measure the UV spectrum of a compound, the sample is dissolved in a solvent that does not absorb above 200 m, e.g., methanol, 95% ethanol, or cyclohexane because they do not have electrons (so no * or n * transitions occur in the solvent). 2. The sample solution is placed in the sample cell holder and, if a double beam instrument is used, a blank solution containing solvent only is placed in the reference cell holder. Quartz cells, 1 cmsquare are commonly used. These require about 3 mL solution. 3. The UV spectrometer is a scanning instrument which sequentially emits the full range of UV radiation and plots a graph (called a UV spectrum) of absorbance versus wavelength. Absorbance is sometimes called Optical Density (O.D.). The highest points on the spectrum are absorption maxima. A wavelength at which absorption is maximum is called the max (pronounced lambda max). Values of max can be read from the graph and used to verify or identify the compound present. 4. Quantitative analysis can be carried out if pure standards are available. The standard and sample are weighed to 4 decimal places and made up to volume in a small volumetric flask. Aliquots are then removed and additional dilutions made as required until the desired concentration has been achieved. The absorbance of the sample and standard are read on the same instrument, at the same wavelength, at the same time and temperature, and with the same solvent. The absorbance of the standard solution is used to calculate the molar extinction coefficient ( ) of the compound which is then used to determine the concentration (purity) of the sample using the Beer-Lambert equation. Note that literature values of (e.g., from CRC Handbook) are of great value in determining the concentration of standard solution to prepare, i.e., preparing a standard solution with an absorbance of 0.2 - 0.7 with 0.5 being the goal. However, the literature values of are not reproducible enough to be used to directly calculate the purity of the recovered sample. fluctuates significantly with all the variables listed above and so sample and standard are always run simultaneously. One limitation of quantitative UV analysis arises from the great width of UV absorption bands. It is not uncommon that absorption bands from impurities overlap absorption bands from the compound under study. Since these absorbances are additive, erroneously high sample purity is occasionally encountered (e.g., 110% purity??!!). This type of error can be minimized or avoided by purifying the sample thoroughly before analysis and/or choosing a wavelength at which the sample absorbs very strongly (very high ). The relative error of interference is likely to be much less. Beer -Lambert Equation: The absorbance, A, of the solution at a particular wavelength is given by Beers law ... where c = concentration in moles per liter I A = log r = l c l = path length through the cell in cm. (usually 1.0 cm) Is = molar absorptivity or molar extinction coefficient of compound Ir = intensity of radiant energy through the reference (blank) Is = intensity of radiant energy through the sample solution. If the sample absorbs light at a particular wavelength, the sample beam (Is) is less intense than the reference beam (Ir), and the ratio Ir / Is is greater than 1. The absorbance (the logarithm of the ratio) is therefore greater than zero when the sample absorbs and equal to zero when it does not. Note that absorbance has no units. What are the units of ?

In the dilutions shown below, calculate the concentration (in mg/L) and the mass of solute (in mg) in each flask. Show all dilution factors. Do the dilution calculations based on both mass and concentration. 4.00 g

50 mL 25 mL

1000 mL

100 mL

500 mL

By Mass:

By Conc.:

0.80 g

25 mL 10 mL

200 mL
100 mL 50 mL

By Mass:

By Conc.:

PREPARING DILUTIONS FOR UV SPECTROPHOTOMETRY In order to analyze a sample by UV spectrophotometry, it must be diluted to an appropriate concentration in a non-interfering solvent. As in visible spectrophotometry, the Beer - Lambert Law applies, i.e., A = l c or A = a b c By rearranging and inserting units, the molar absorptivity, , is found to have units of .... = A/l c = 1/(cm) (mol/L) = L/(mol cm) = L mol-1 cm-1 For quantitative analysis, e.g., determination of purity of your final product, a dilution with an absorbance close to 0.5 is prepared (0.2 - 0.7 is the most accurate absorbance range in spectrophotometry) and its absorbance is measured at a single wavelength - at a max of the compound. For qualitative analysis, e.g., confirmation of identity of a compound, a dilution is scanned over the whole Near UV range (200 - 400 m). The dilution is prepared so that the absorbance of all peaks is as high as possible without any of them exceeding the maximum range of the spectrophotometer.
Note: [Beckman DU65 reads 0 3 A], [Carey 100 reads 0 3 A], and the [Lambda 4A reads 0 3 A units].

Check the CRC Handbook and the Spectral Atlas for max and (or log ) values of the compound under study For example, consider m-nitroaniline .... CRC Handbook max 236 275 374 log 4.21 3.64 3.17 16218 4365 1479 max 233 --371 Spectral Atlas 12000 --1090

Be aware that if you prepare a dilution of your sample with an absorbance of 0.5 at = 371 m, the absorbance at = 233 m for the same dilution will be very high (off scale of the spectrophotometers), i.e., ...

at = 233 m 12000 = = 11 so (A = 0.5 @ = 371 m) 11 = (5.5A @ = 233 m) at = 371 m 1090

This is not a problem since you will be measuring the A of your dilution at a single for a purity determination, in this example, at 371 m.
Alternately, you could prepare a dilution with an absorbance of 0.5 at = 233 m. In this case the absorption at = 371 would be only be 0.045 A, i.e., 11 times less than at = 233 m. Both methods are acceptable and each has its own advantage Reading at the lower (371m) requires fewer dilutions to prepare a solution. This saves time and reduces the chances of dilution and handling errors. Reading at the higher (223 m) requires more dilution and so takes longer and increases the opportunity for dilution errors. However, interferences (from contaminants) have less effect when the larger dilution is employed.

10

Dilution Calculations: for single reading at 371m (aiming for A = 0.5 given that = 1090) Conc. required: c= A 0.5 = = 4.587 10 4 mol / L -1 -1 l (1090 L mol cm ) (1 cm)
too much solvent !!

c = 4.587 10 4 mol / L (13813 g / mol) = 0.0634 g / L . or Using a 25 mL volumetric flask: 25 0.0634g = 0.001584 g / 25mL 1000 or 63.4 mg / L Select a reasonable weight, e.g., 0.10 g into 25 mL volumetric: 0.1000 g = 63 too concentrat ed 0.001584 g Try to use 25 mL volumetrics for further dilution:
63 dilution in just 1 step 0.10 g 63 dilution in 2 steps this solution must be diluted ca. 63 to give A 0.5

63.4 mg / L
too little sample to weigh and transfer accurately

? mL

0.10 g

? mL

? mL

25 mL

25 mL

25 mL

25 mL

25 mL

Transfer volume is too small. Accuracy suffers.

These dilutions give reasonable accuracy.

11

After determining the necessary weights and dilutions required to prepare a solution with A 0.5, prepare the both the standard solution and a recovered-sample solution simultaneously as per your calculations. For the purpose of the lab, it is preferred that students work together and share a single standard solution. Beware: Sample and standard solutions must be prepared in the same way and read together on the same instrument, at the same time, etc. in order to obtain accurate values. Calculation of the molar absorptivity ( ): Remember that the obtained from the literature although useful for dilution preparation cannot be used to calculate the purity of your sample. You must calculate using standard solution measurements and Beers Law, A = l c Calculation of the purity of your sample: This can be done in several ways 1. Use determined in the previous step (from the standard solution) and again use Beers law. Input the absorbance of your sample solution and solve for the molar concentration of your sample solution. From the molar concentration and the mass (which you originally weighed out) calculate the purity of the sample. 2. Use Beers law to calculate another value of using your sample solution data. The ratio of ( sample to standard) 100 % will give a % purity of your sample. Sample and standard weights do not have to be identical. sample % Purity = 100% s tan dard Note: Solvents must be transparent in the UV region used, e.g., butanol, cyclohexane, dodecane, ethyl ether, glycerol, hexane, IPA, MeOH, 2-methylhexanol, toluene

12

Source of UV Absorption: Terminology you need to learn: Chromophore A covalently bonded, unsaturated group responsible for electronic absorption, e.g., C=C, C=O, NO2, etc. Auxochrome A saturated group with nonbonded electrons which, when attached to a chromophore, alters the wavelength and intensity of absorption, e.g., -OH, -NH2, -Cl, etc. Bathochromic Shift The shift of absorption to a lower energy (longer ) due to substitution or solvent effect (a red shift). Hypsochromic Shift The shift of absorption to a higher energy (shorter ) due to substitution or solvent effect (a blue shift). Hyperchromic Effect An increase in absorption intensity. Hypochromic Effect An decrease in absorption intensity.

As discussed at length in the unit on Molecular Orbital theory, absorptions in the Near UV arise from electronic transitions, primarily n * and * transitions. The student is expected to become familiar with the UV absorption characteristics of the major classes of organic compounds, i.e., hydrocarbons, alkenes, alkynes, polyenes, conjugated polyenes, carbonyl compounds, aromatics, and nitro groups. A brief summary follows .... Auxochromes in satd HC derivatives: n * usually at < 200 m, e.g., ROH, RNH2, RCl. Exceptions: [R-Br and R-I: n * at > 200 m] and [RSH, RSSH absorb at > 200m] Non conjugated alkenes and alkynes (E band chromophores) : * at < 200 m Conjugated polyenes (K band chromophores): a) conjugated dienes: * at > 200 m, e.g., acyclic @ 214 m and up for substituents, homoannular @ 253 m and up, heteroannular @ > 253m. b) conjugated enynes & diynes: * at > 200 m Carbonyl Chromophores: (aldehydes, ketones, esters, acids, amides, acyl chlorides, anhydrides) a) non-conjugated: * at < 200 m (E), n * at > 200 m (R), many. b) conjugated: * intense at > 200 m (K), n * at = 300-330 m (R) Aromatic Chromophores: a) all substituted benzenes: E2 -band @ 200 - 250 m & B-bands @ 255-280 m b) benzenes with conjugated groups: K-band (intense) @ 220-250 m c) conjugated substituents with non-bonded e-'s: R-band (weak) @ 273-330 m Note: e-donating groups shift max to longer (causes a bathochromic shift) e-withdrawing groups shift max to shorter (causes a hypsochromic shift) additional fused rings shift max to longer heterocycles, such as pyridine, furan, pyrrole, thiophene, also absorb above 200 m Miscellaneous chromophores (on aliphatics): Some absorb @ > 200 m, e.g., nitro, nitrates, nitrites, nitriles, azo cpds., sulfones, sulfoxides

13

Homework: 1. For each of the following compounds put a check mark in the box or boxes which describe an electronic excitation which cause a moderate to strong absorption of radiation in the 200 to 400 m wavelength range. COMPOUND CH3CH2OH aniline CH2 = CH2 CH2= CH-CH=CH2 CH2= CH-CH2-CH=CH2 CH3NO2 O CH3 = CH- C - CH3 1. A student dissolved 0.1000 g of a UV-absorbing compound (M.W. = 160 g/mol) in methanol in a 50 mL volumetric flask. He then pipetted 1.0 mL of this solution into a 25 mL volumetric flask and diluted to the mark with methanol. The absorbance at 290 m was 0.600. Calculate the molar extinction coefficient () at this wavelength. * n * * none

14

2. Complete the following table.

COMPOUND STRUCTURE Type of UV Transition (and Band) max ( m) log10 max E (kcal/mol)

ethylene

CH2=CH2

* (E)

165 177 182 185 178 223 217 274 334

4.19 4.10 3.88 3.30 4.23 3.36 4.32 4.55 5.10

173

1-octene

cyclohexene

1-octyne

1,4-pentadiene

1,3-pentadiene

1,3-butadiene

(E)-1,3,5-hexatriene

(3E, 5E, 7E)1,3,5,7,9decapentaene

15

Additional Problems: 1. A beam of UV radiation has an energy of 6.83 105 J/mol of photons. Given that... Planks constant (h) = 6.62 10-34 J s the speed of light (c) = 3.00 1010cm/s Avogadros Number = 6.02 1023 /mole Calculate ... a) its wavelength in m ................................ b) its frequency in Hz .............................

2.

A beam of UV radiation has a wavelength of 150 m. Given that... Planks constant = 6.62 10-34 J s the speed of light = 3.00 1010cm/s Avogadros Number = 6.02 1023/mole Calculate ... a) its frequency in Hz ............................. b) the energy of 1 photon in Joules ................................ c) the energy of 1 mole of photons in kcal .........

4.184 Joule = 1.00 cal

.................... 3. A beam of UV radiation has a frequency of 1.5 1016 Hz Given that... Planks constant = 6.62 10-34 J s the speed of light = 3.00 1010cm/s Avogadros Number = 6.0225 1023/mole Calculate ... a) its wavelength in m ............................. b) the energy of 1 mole of photons in kJ ............................. 4.184 Joule = 1.00 cal

N ..

16

4.

For pyridine, C5H5N: a) Use a Frost circle and draw a Huckel M.O. diagram of its system showing the relative energy levels of all its molecular orbitals. b) Label (name) all the molecular orbitals. c) Show the ground state electronic configuration of the molecular orbitals d) State the Bond Order of the system ............................... e) State whether this species is nonaromatic or aromatic ................................... f) Label the HOMO and LUMO molecular orbitals g) Name the lowest type of energy electronic transition which can occur. .........................

5.

For cyclopentadienyl anion, a) Use a Frost circle and draw a Huckel M.O. diagram of its system showing the relative energy .. levels of all its molecular orbitals. b) Label (name) all the molecular orbitals. c) Show the ground state electronic configuration of the molecular orbitals d) State the Bond Order of the system ............................... e) State whether this species is nonaromatic, aromatic or antiaromatic ................................... f) Label the HOMO and LUMO molecular orbitals g) Name the lowest type of energy electronic transition which can occur. .........................

17

6. Fill in all the empty cells in the following table for UV electronic transitions ...
example of compound absorption band letter has no letter K CH3CHCl2 1-hexene Near -CH2CH3 Near Far methyl ethyl ketone Near Far has no letter transition type * indicate if near or far UV region

7.

In the following compound circle all groups that would give rise to absorption in the near UV only. For each group circled, fill in a row of information, i.e., name the type of transition (e.g., etc.) and the absorption band letter (e.g., B, E1, E2, etc). Fill in as many rows of info as *, needed and indicate which row corresponds to which group by drawing an arrow from the circled group to the matching row in the table. electronic transition type absorption band letter

O C C CH2 CH2Br NH2

8. For each of the following compounds put a check mark in the box or boxes which describe an electronic excitation which cause a moderate to strong absorption of radiation in the 200 to 400 m wavelength range. 18

COMPOUND azobenzene m-nitroaniline decane 1,3-butadiene 9.

n *

none

A pure organic liquid (M.W. = 100 g/mol, = 0.80 g/mL) has a molar extinction coefficient () of 50 in methanol at = 225 m. Calculate the volume (in mL) of the liquid which must be pipetted into a 50 mL volumetric flask, which after dilution to the mark will give an absorbance of 2.0 at the stated wavelength

10. Calculate the molar extinction coefficient () of an organic solid (MW = 200 g/mol) given the following data and include the units of . 0.1000 g was dissolved in 50 mL methanol a 5 mL aliquot was diluted into a 25 mL volumetric flask this solution gave an absorbance of 0.70 when read at 250 m in a 1.0 cm cell

19

11. A student dissolves 0.1100 g of her recovered product (MW=75.00g/mol) to volume with methanol in a 25
mL volumetric flask. She wishes to dilute this solution such that the final dilution will have an absorbance near 0.5 ( = 14,500 at the chosen wavelength) using a 1.0 cm cell. Calculate the dilution factor necessary to dilute this solution to an absorbance of 0.50 . Assuming that only 25 mL flasks can be used and only the following volumetric pipets are available (1.0, 2.0, 3.0, 4.0, 5,0, 10.0 and 15.0 mL), report the aliquots used for each dilution she should use to obtain a final solution whose absorbance is between 0.40 and 0.60. Report the aliquots used for each subsequent dilution in the following format: x mL 25mL, y mL 25mL, etc, etc. as many times as needed to reach the final dilution. Report the final expected absorbance based on these dilutions.

20

12. Calculate the absorbance expected on the final dilution described below given that the MW of the compound is 150 g/mol and its molar absorptivity is 105 0.1000 g was dissolved in methanol in a 25 mL volumetric flask a 20 mL aliquot (from the 1st flask) was diluted into a 50 mL volumetric flask a 10 mL aliquot (from the 2nd flask) was then diluted in a 25 mL volumetric flask the absorbance of this solution is to be read in a 1.0 cm cell

13. A student prepares dilutions of her pure standard and recovered sample as follows: She dissolves 0.1000g pure standard in a 25 mL volumetric, then transfers a 1 mL aliquot into a 50mL volumetric flask. The absorbance of the final solution is 0.600 She carries out the same dilutions on her recovered product but her initial weight was 0.1098g and the absorbance of the final dilution was 0.540 Knowing MW = 70.0 g/mol, calculate the molar absorptivity of the compound and include the units of . ..... Calculate the %wt purity of the recovered product. . Show your work for partial marks in the event of errors.

21

Answers to Some of the Additional Problems from Pages 16-21:

1. a) 175m 3. a) 20 m 4. d) BO = 3 5. d) BO = 3 9. 0.25 mL

b) 1.71 1015 s-1 c) 190 kcal/mol b) 5980 kJ e) aromatic e) aromatic g) n * f) *

2. a) 2.00 1015 s-1 b) 1.32 10-18 J/photon

10. = 350 L cm-1 mol-1 11. DF = 1700 12. A = 0.45 13. = 525 L mol-1 cm-1 Purity = 82.0% Dilutions = (225mL), (225mL), (225mL) Final A = 0.44

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