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FOCUS 1 Online Cumulative Example

You are working in a laboratory investigating the properties of semiconductor nanomateri-
als. In your research you must synthesize CdSe nanocrystals by the reaction of CdO with
Se in high-temperature solutions. A solution of Se is prepared by dissolving 152.6 mg of
selenium metal in 25.0 mL of 1-octadecene solvent. In a separate flask, 64.2 mg of CdO is
dissolved in 3.00 mL of oleic acid and 50.0 mL of 1-octadecene at 225 8C.
(a) Write the electron configurations of Cd and Se.
(b) Based on the data in Appendix 2D, which element has (i) the higher ionization
energy (I1); (ii) the greater electron affinity (Eea); (iii) the larger atomic radius (r)?
(c) CdSe can be considered a binary ionic compound. Based on the electron affinities
you found in (b), which element is more likely to form an anion in this compound?
Predict the charge on the ions each element is likely to form.
(d) The final product requires a 1:1 mole ratio of Cd:Se. What volume of the selenium
solution must be added to the CdO solution?
(e) A sample of the material you prepared was found to emit light at 546 nm when it
is excited with UV radiation. An electron in a nanocrystal can be treated as an electron
trapped in a one-dimensional box and the emitted light is due to an electronic transi-
tion from the n 5 2 to the n 5 1 energy level. What is the diameter of the nanocrystals
in your sample? Note that the effective mass (me*) of an electron in CdSe (the mass to
use in the energy expression) is me* 5 0.090me. The mass of the electron is given in
the table inside the back cover of your textbook.
(f) What is the wavelength of radiation required to excite an electron in the nanocrys-
tals from n 5 1 to n 5 3?
ANTICIPATE For part (b), you should anticipate that Se has the higher electron affinity
because it lies higher and more to the right than cadmium in the periodic table. For part (c)
you should predict that Se forms 22 ions because it is in the same group as oxygen and sul-
fur. There is no way to predict the answers for parts (d)–(f), but you might know that CdSe
nanocrystals that emit visible radiation have diameters in the range 1–10 nm.
PLAN For parts (a)–(c), use the tables in Appendix 2D and the periodic table. For part
(d), determine the amount of Se required to react with Cd and then find the molar con-
centration of Se in solution to determine the volume of solution required. For parts (e)
and (f), use Eq. 4 in Topic 1C in the form En11 2 En 5 (2n 1 1)h2/8me*L2.

SOLVE

(a) Cd is in Group 12, Period 5 and Se is in Group 16, Period 4. The electron configurations
are therefore:

Cd: 3 Kr4 4d105s2

Se: 3 Ar4 3d104s24p4

(b) From Appendix 2D,

I1/(kJ?mol21) Eea/(kJ?mol21) r/pm

Cd: 868 ,0 149
Se: 941 1195 117

(i) Se has the greater first ionization energy; (ii) Se has the greater electron affinity;
(iii) Cd has the greater atomic radius.

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2 Focus 1 Online Cumulative Example

(c) Use the periodic table and Appendix 2D.

Selenium is in Group 16 and has a positive electron affinity, so it is S

likely to form anions with a charge of 22. Cadmium has a negative Se Kr
electron affinity and is likely to form cations. To maintain electri-
cal neutrality in CdSe, Cd will form 12 ions: Te

Se22, Cd21

(d) Determine the amount of Cd present in 64.2 mg of CdO.

1 mmol CdO 1 mmol Cd 1 mmol

64.2 mg 3 3 5 0.499 p mmol Cd
128.41 mg 1 mmol CdO 64.2 mg 128.4 mg

0.499… mmol

The concentration of Se in solution is:

1 mmol
×
1 mmol 1
156.2 mg 3 3 5 79.12 p mmol?L21 156.2 mg
78.96 mg 0.025 L 78.96 mg
2.0 mmol

25 mL

Because 1 mmol Cd ≏ 1 mmol Se, you need 0.500 mmol Se. The
volume of solution required is: 0.499… mmol L
×
0.499 mmol
0.499 p mmol Se 3 5 6.32 3 1023 L 5 6.32 mL
79.12 mmol?L21 79.12… mmol

6.32 mL

(e) First, convert the wavelength of the photons to energy by using E ⫽ hc/␭:

h c
6447448 6447448
6.626 07 3 10 234
J?s 3 2.997 92 3 108 m?s21
E5
546424
14
3 1029
43
m
546 nm
5 3.63 p 3 10219 J
and equate this energy to the energy difference DE 5 En11 2 En, between states of the
electron.

Use Eq. 4 from Topic 1C and solve for the length of the box, L with
n 5 1.
n=2
From Eq. 4 in Topic 1C, 546 nm
(2n 1 1)h2 1/2 n=1
L5a b x
8me*¢E 0
L = 2.34… nm
Set n⫽1
} 3 3 (6.626 07 3 10234 J?s) 2 1/2
5 a b
8 3 (0.090 3 9.109 38 3 10231 kg) 3 (3.63 p 3 10219 J)
14444444244444443
me*

5 2.34 p 3 1029 m, which rounds to 2.35 nm

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Focus 1 Online Cumulative Example 3

(f) Using Eq. 4 in Topic 1C for En 2 En12 for n 5 1 gives

energy of energy of
level n⫹2 level n
6447448 6447448
Set n⫽1
(n 1 2) 2h2 n2h2 h 2 } h2
En12 2 En 5 2 2 2 5 (4n 1 4) 5
8me* L 8me* L 8me* L2 me* L2
h2 (6.626 07 3 10234 J?s) 2
¢E 5 5
me* L2 0.090 3 9.109 38 3 10231 kg 3 (2.34 p 3 1029 m) 2
14444444244444443
me*

5 9.70 p 3 10 219
J

Convert the energy to wavelength by using ␭ 5 hc/E:

n=3
8
(6.626 07 3 10 234
J?s) 3 (2.997 92 3 10 m?s ) 21
205 nm
l5
9.70 p 3 10219 J
5 2.05 3 1027 m n=1
0 x
or 205 nm L

EVALUATE As predicted, Se forms anions of charge 22 and Cd forms cations of

charge 12. The diameter of the nanocrystal is in the range 1–10 nm, as anticipated.