Answers to Assignment #10

1.

According to the Beer-Lambert law,

A=lc
where A = absorbance (no units)
= molar absorptivity (?)
l = path length (cm), typically 1cm cells are used.
c = concentration (moles per litre)
The units of are
(a) cm.mol.L-1

2.

(b) L.mol-1.cm-1

(c) no units

(d) none of the above

It is common to report spectroscopic properties of a compound using the expression max

(). Using the spectrum in Figure 1, how would you report the peak labelled Y?
(a) 600 (2)
(b) 2.5 x 10-3 (600)
(c) 600 (2.5 x 10-3)
(d) 600 (800)

Figure 1: UV-Vis for questions 2, 1013.

3.

What does tell you about your molecule?

(i) not a lot
(ii) how likely a particular transition is going to occur
(iii) if you are going to get a big peak
(a) i
(b) ii
(c) iii
(d) ii + iii

4.

Which answer best represents the boundary between the uv region and the visible region?
(a) 200 nm
(b) 350 nm (c) 500 nm
(d) 650 nm
(e) 800 nm

5.

Which wavelength represents the highest energy transition?

(a) 200 nm (b) 350 nm
(c) 500 nm
(d) 650 nm
(e) 800 nm

6.

In a spectrum, the position of a peak is described by max. This is the wavelength at which
the peak has maximum height. If the spectrum of a compound is recorded at different
concentrations, what will change?
(a) absorbance
(b) max
(c) (d) absorbance & max
(e) max &

7.

If the concentration is not given, the absorbance scale is not very useful. The size of the
peak may then be measured in units of log . If a peak measures 3.1 on the log scale,
what is the value of ? Round your answer to one significant figure and choose the best
answer.
(a) 1
(b) 100
(c) 1000

8.

Ligand to metal charge transfer transitions cause the solution to be intensely coloured.
Which of the three answers best represents the typical value of that you might expect?
(a) 1
(b) 100
(c) 1000

9.

n 6 * transitions typically have a value of closest to which answer?

(a) 50
(b) 500
(c) 5000

-------------------------------------------------------------------------------------------------------------------True or false?
Figure 1 is the spectrum of a pure compound dissolved in the only solvent in which it is soluble.
If this solution is prepared again at a different concentration, describe the following statements
as true (T) or false (F):
10.

Peak X will always be smaller than peak Y, regardless of the concentration. True

11.

The ratio of the (peak height of X) : (peak height Y) will always remain the same, for
every concentration checked. True

12.

In more concentrated solutions, max for peak X will move towards max for peak Y. False

13.

In weaker solutions, max for peak Y will move towards max for peak X. False

--------------------------------------------------------------------------------------------------------------------

The spectrum in Figure 2 was found in the UVVis spectrometer. There was a labeled flask
containing the remains of a solution.
Unfortunately, the label had three different
concentrations written on it. Please answer the
following questions 14 - 17:

Figure 2: UV-Vis spectrum for questions 14-17

14.

If the contents of the flask are colourless, what value is W likely to take?
(a) W = 100 (b) W = 250 (c) W = 400 (d) W = 550

15.

If the concentration on the label is read as 2.6 x 10-2 M and W is 300 nm, which transition
do you think is responsible for the peak?
(a) n 6 *
(b) 6 *
(c) d 6 d
(d) L 6 M charge transfer.

16.

If the concentration on the label is read as 5 x 10-2 M and W is 605 nm, which transition
do you think is responsible for the peak?
(a) n 6 *
(b) 6 *
(c) d 6 d
(d) L 6 M charge transfer.

17.

What colour is the solution in question 16? Green-blue

---------------------------------------------------------------------18.

Fact: Transition metal complexes are coloured.

Fact: Organic compounds are typically colourless.
Fact: tetraphenylporphyrin (at right) is a beautiful
purple colour.
Why?
Extensive conjugation

19.

If the concentration of the solution in Figure 3 is

known to be 1.8 x 10-3 M, would you say that the
spectrum is caused by
(i) n 6 * (ii) 6 * (iii) L 6 M
(iv) d 6 d (v) 6 * (vi) n 6 *

Tetraphenylporphyrin

Choose one of the following answers:

(a) i + ii (b) iii + v (c) ii + iv
(d) v + vi (e) iv + vi

20.

A molecule shows an electronic spectrum. Put a check mark (T) next to the following
compounds which might be responsible for this output (you can choose more than one
answer):
(g) phenolphthalein T
(a) an alkane
(d) aromatic T
(b) an alkene T
(e) a transition metal complex T
(c) a conjugated alkene T (f) sodium chloride

Answer multiple choice questions 21-33, using choices:

wavelengths, (nm): a) <200
b) 210-280
c) 290-380
d) 450-550
e) 550-700
molar absorbtivity, (Lmol-1cm-1): a) <1
b) 1-50
c) 100-900
d) >1000
shifts: a) bathochromic
b) hypsochromic
c) hyperchromic
d) hypochromic
transitions:
a) n6*
b) 6*
c) n6*
d) d-d
e) charge transfer

ORGANIC

contains
lone pairs
(ie: N, O, P, S, X)

contains
-bonds
- *
allowed
> 1000
= 190 nm + 30 each
unit of conjugation

n - *
forbidden
< 50
= 280 nm + 30 each
unit of conjugation

INORGANIC
strong colours

Charge Transfer
allowed
> 1000
: use the
colour wheel

weak colours

d-d
forbidden
< 50
: use the
colour wheel

Yellow
550 nm
Green
500 nm

Orange
600 nm

Blue
450 nm

Red
670 nm
Violet
400 nm

21.
22.
23.
24.
25.
26.

Where would you expect to find the n63*

for H2C=CH-CH=CH-CH=CH-OH?
C
max = 280 + 30 + 30 = 340 nm
What would be the value for this transition?
B
Forbidden, < 50 Lmol-1cm-1
Where would you expect to find the 63* for H2C=CH-CH=CH-CH=CH-OH?
B
max = 190 + 30 + 30 = 250 nm
What would be the value for this transition?
D
Allowed, > 10,000 Lmol-1cm-1
What transition is responsible for the strong band that is observed below 200 nm when
the vacuum UV of H2C=CH-CH=CH-CH=CH-OH is recorded?
C
vacuum UV below 200 nm, n6*
If NaOH was added to H2C=CH-CH=CH-CH=CH-OH how would you expect the max to
shift?
A
Deprotonation of an alcohol extends the conjugation and the max increases,
bathochromic shift.

27.

28.
29.
30.
31.
32.
33.

If NaOH was added to H2C=CH-CH=CH-CH=CH-OH how would you expect the to

shift?
C
Deprotonation of an alcohol extends the conjugation and the increases,
hyperchromic shift.
If a glass of tomato juice appears red, what wavelength would it absorb if you recorded
its UV-Vis spectrum?
D
Absorbs green at 500 nm.
If a laser pointer appears red, what wavelength does it emit?
E
Emits red at 670 nm.
What transition is responsible for the intense red color of Mo(CO)4(phenanthroline)?
E
Intense colors are due to charge transfer transitions.
What would be the value for this transition?
D
CT are allowed, > 10,000 Lmol-1cm-1
What transition is responsible for the pale red color of Mn3+ in solution?
D
Pale colors are due to d-d transitions.
What would be the value for this transition?
B
d-d are forbidden, < 50 Lmol-1cm-1