Edison A.

Limbaga October 18, 2022

Problem Set # 4
Subject: CER E 201
Instructor: Assoc. Prof. Lori-Ann I. Cabalo

A. Given the following experimentally determined information:

Composition = 𝐶𝑒𝑂2
Space Group = 𝐹𝑚3̅𝑚
𝑎 = 5.411 Å ≈ 5.411 𝑥 10−8 𝑐𝑚
Density = 7.13 𝑔⁄𝑐𝑚3
Sum of 𝐶𝑒 − 𝑂 Ionic Radii = 2.35 Å
Crystal Structure of 𝐶𝑒𝑂2 (Appendix 1 Figure 1)

Determine the following quantities:

a. The number of formula units per unit cell (Z);

Solution:

Using the general formula in calculating the density of a unit cell:

𝒏𝑴
𝑷=
𝑵𝑽
𝑤ℎ𝑒𝑟𝑒, 𝑃 = 𝑑𝑒𝑛𝑠𝑖𝑡𝑦
𝑛 = 𝑓𝑜𝑟𝑚𝑢𝑙𝑎 𝑢𝑛𝑖𝑡𝑠
𝑀 = 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡
𝑁 = 𝐴𝑣𝑜𝑔𝑎𝑑𝑟𝑜 ′ 𝑠 𝑁𝑢𝑚𝑏𝑒𝑟
𝑉 = 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙

Molecular Weight of 𝐶𝑒𝑂2 ;

𝑔
𝐶𝑒 = 140.12
𝑚𝑜𝑙
𝑔
𝑂 = 2 (16.00 )
𝑚𝑜𝑙
𝑔
𝑀𝑊 = 188.12
𝑚𝑜𝑙

Unit cell volume (Cubic);

𝑉 = 𝑎3 = (5.411 𝑥 10−8 𝑐𝑚)3 = 1.58 𝑥 10−22 𝑐𝑚3

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 Deriving the formula above;
𝑃𝑁𝑉
𝑛=
𝑀

(7.13 𝑔⁄𝑐𝑚3 )(6.022 𝑥 1022 )(1.58 𝑥 10−22 𝑐𝑚3 )

𝑛= 𝑔
188.12
𝑚𝑜𝑙

𝒏 = 𝟑. 𝟔 ≈ 𝟒 𝒇𝒐𝒓𝒎𝒖𝒍𝒂 𝒖𝒏𝒊𝒕𝒔

b. The Wyckoff positions of the 𝐶𝑒 and 𝑂 ions;

Since the calculated formula unit is equal to 4, (4 times the number atoms)
then there should be 4 atoms for 𝐶𝑒 and 8 atoms for 𝑂 with a total of 12
atoms in the unit cell.

Based from Appendix 1 Table 1 Wyckoff Positions of Group 𝐹𝑚3̅𝑚 (# 225).

From the multiplicities of the special positions in space group 𝐹𝑚3̅𝑚 we see
that 𝐶𝑒 must occupy either the 4a or 4b positions. Base from the crystal
structure of 𝐶𝑒𝑂2 , we can clearly see it occupying 4a (0,0,0) position. And to
maintain 8 oxygen ions in the unit cell it must reside at 8c.

Thus, the Wyckoff positions of the 𝐶𝑒 and 𝑂 ions are;

Coordinates
Wyckoff Site
Atom Multiplicity (0,0,0) + (0,1/2,1/2) +
Letter Symmetry
(1/2,0,1/2) + (1/2,1/2,0)+
O 8 c 4̅3𝑚 (1/4,1/4,1/4)
(1/4,1/4,3/4)
Ce 4 a 𝑚3̅𝑚 (0,0,0)

c. The coordination environments of both ions,

A single 𝐶𝑒 ion is coordinated with 8 oxygen ions forming an octahedral,

while a single 𝑂 ion is coordinated with 4 cerium ions forming a tetrahedral.
As seen in Appendix 1 Figure 1.

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 d. The 𝐶𝑒 − 𝑂 distance;
Solution:
Using the general Wyckoff positions above;

𝐷 (𝐶𝑒 − 𝑂) = 5.411 𝑥√ [(0 − 0.25)2 + (0 − 0.25)2 + (0 − 0.25)2 = 𝟐. 𝟑𝟒Å

For the percent difference between the experimental and calculated ionic
distances between 𝐶𝑒 − 𝑂;
𝟐. 𝟑𝟓Å − 𝟐. 𝟑𝟒Å
% 𝑑𝑖𝑓𝑓𝑒𝑟𝑒𝑛𝑐𝑒 = 𝑥 100% = 𝟎. 𝟒𝟑%
𝟐. 𝟑𝟓Å

References:
[1] Wyckoff Positions of Space Groups. (n.d.). Retrieved October 18, 2022, from

https://www.cryst.ehu.es/cgi-bin/cryst/programs/nph-wp-list

[2] Crystallography Open Database: Information card for entry 9009008. (n.d.). Retrieved

October 18, 2022, from http://www.crystallography.net/cod/9009008.html

[3] Vedantu. (2022, April 27). The Density of a Unit Cell. VEDANTU. Retrieved October 18,

2022, from https://www.vedantu.com/chemistry/density-of-a-unit-cell

[4] Tilley, R. J. D. (2006, August 25). Crystals and Crystal Structures (1st ed.). Wiley.

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 Appendix I

Cerium atom

Oxygen atom

Figure 1 Crystal Structure of 𝐶𝑒𝑂2

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10/17/22, 4:47 PM Wyckoff Positions of Space Groups

Bilbao Crystallographic Server WYCKPOS Wyckoff Positions Help

Table 1
Wyckoff Positions of Group Fm-3m (No. 225)

Wyckoff Site Coordinates

Multiplicity

letter symmetry (0,0,0) + (0,1/2,1/2) + (1/2,0,1/2) + (1/2,1/2,0) +

(x,y,z) (-x,-y,z) (-x,y,-z) (x,-y,-z)
(z,x,y) (z,-x,-y) (-z,-x,y) (-z,x,-y)
(y,z,x) (-y,z,-x) (y,-z,-x) (-y,-z,x)
(y,x,-z) (-y,-x,-z) (y,-x,z) (-y,x,z)
(x,z,-y) (-x,z,y) (-x,-z,-y) (x,-z,y)
(z,y,-x) (z,-y,x) (-z,y,x) (-z,-y,-x)
192 l 1
(-x,-y,-z) (x,y,-z) (x,-y,z) (-x,y,z)
(-z,-x,-y) (-z,x,y) (z,x,-y) (z,-x,y)
(-y,-z,-x) (y,-z,x) (-y,z,x) (y,z,-x)
(-y,-x,z) (y,x,z) (-y,x,-z) (y,-x,-z)
(-x,-z,y) (x,-z,-y) (x,z,y) (-x,z,-y)
(-z,-y,x) (-z,y,-x) (z,-y,-x) (z,y,x)
(x,x,z) (-x,-x,z) (-x,x,-z) (x,-x,-z)
(z,x,x) (z,-x,-x) (-z,-x,x) (-z,x,-x)
(x,z,x) (-x,z,-x) (x,-z,-x) (-x,-z,x)
96 k ..m
(x,x,-z) (-x,-x,-z) (x,-x,z) (-x,x,z)
(x,z,-x) (-x,z,x) (-x,-z,-x) (x,-z,x)
(z,x,-x) (z,-x,x) (-z,x,x) (-z,-x,-x)
(0,y,z) (0,-y,z) (0,y,-z) (0,-y,-z)
(z,0,y) (z,0,-y) (-z,0,y) (-z,0,-y)
(y,z,0) (-y,z,0) (y,-z,0) (-y,-z,0)
96 j m..
(y,0,-z) (-y,0,-z) (y,0,z) (-y,0,z)
(0,z,-y) (0,z,y) (0,-z,-y) (0,-z,y)
(z,y,0) (z,-y,0) (-z,y,0) (-z,-y,0)
(1/2,y,y) (1/2,-y,y) (1/2,y,-y) (1/2,-y,-y)
48 i m.m 2 (y,1/2,y) (y,1/2,-y) (-y,1/2,y) (-y,1/2,-y)
(y,y,1/2) (-y,y,1/2) (y,-y,1/2) (-y,-y,1/2)
(0,y,y) (0,-y,y) (0,y,-y) (0,-y,-y)
48 h m.m 2 (y,0,y) (y,0,-y) (-y,0,y) (-y,0,-y)
(y,y,0) (-y,y,0) (y,-y,0) (-y,-y,0)
(x,1/4,1/4) (-x,3/4,1/4) (1/4,x,1/4) (1/4,-x,3/4)
48 g 2.m m (1/4,1/4,x) (3/4,1/4,-x) (1/4,x,3/4) (3/4,-x,3/4)
(x,1/4,3/4) (-x,1/4,1/4) (1/4,1/4,-x) (1/4,3/4,x)
32 f .3m (x,x,x) (-x,-x,x) (-x,x,-x) (x,-x,-x)
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10/17/22, 4:47 PM Wyckoff Positions of Space Groups

(x,x,-x) (-x,-x,-x) (x,-x,x) (-x,x,x)

(x,0,0) (-x,0,0) (0,x,0) (0,-x,0)
24 e 4m. m
(0,0,x) (0,0,-x)
(0,1/4,1/4) (0,3/4,1/4) (1/4,0,1/4) (1/4,0,3/4)
24 d m.m m
(1/4,1/4,0) (3/4,1/4,0)
8 c -43m (1/4,1/4,1/4) (1/4,1/4,3/4)
4 b m-3m (1/2,1/2,1/2)
4 a m-3m (0,0,0)

Wyckoff position and site symmetry group of a specific point

Specify the point by its relative coordinates (in fractions or decimals)

Variable parameters (x,y,z) are also accepted

x=
     y =
     z =

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