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Physical Chemistry: A Molecular Approach

Donald A. McQuarrie, John D. Simon

Chapter 29

Solids and Surface Chemistry - all with Video Answers

Educators


Chapter Questions

01:53

Problem 1

Polonium is the only metal that exists as a simple cubic lattice. Given that the length of a side of the unit cell of polonium is $334.7 \mathrm{pm}$ at $25^{\circ} \mathrm{C}$, calculate the density of polonium.

Adriano Chikande
Adriano Chikande
Numerade Educator
02:54

Problem 2

Consider the packing of hard spheres of radius $R$ in a primitive cubic lattice, a facecentered cubic lattice, and a body-centered cubic lattice. Show that $a$, the length of the unit cell, and $f$, the fraction of the volume of the unit cell occupied by the spheres, are given as listed.
\begin{tabular}{lcc}
Unit cell & $a$ & $f$ \\
\hline Primitive cubic & $2 R$ & $\pi / 6$ \\
Face-centered cubic & $4 R / \sqrt{2}$ & $\pi \sqrt{2} / 6$ \\
Body-centered cubic & $4 R / \sqrt{3}$ & $\pi \sqrt{3} / 8$
\end{tabular}

Adriano Chikande
Adriano Chikande
Numerade Educator
01:16

Problem 3

Tantalum forms a body-centered cubic unit cell with $a=330.2 \mathrm{pm}$. Calculate the crystallographic radius of a tantalum atom.

Adriano Chikande
Adriano Chikande
Numerade Educator
01:14

Problem 4

Nickel forms a face-centered cubic unit cell with $a=351.8 \mathrm{pm}$. Calculate the crystallographic radius of a nickel atom.

Adriano Chikande
Adriano Chikande
Numerade Educator
02:25

Problem 5

Copper, which crystallizes as a face-centered cubic lattice, has a crystallographic radius of $127.8 \mathrm{pm}$. Calculate the density of copper.

Adriano Chikande
Adriano Chikande
Numerade Educator
02:16

Problem 6

Europium, which crystallizes as a body-centered cubic lattice, has a density of $5.243 \mathrm{~g} \cdot \mathrm{cm}^{-3}$ at $20^{\circ} \mathrm{C}$. Calculate the crystallographic radius of a europium atom at $20^{\circ} \mathrm{C}$.

Adriano Chikande
Adriano Chikande
Numerade Educator
01:39

Problem 7

Potassium crystallizes as a body-centered cubic lattice, and the length of a unit cell is $533.3 \mathrm{pm}$. Given that the density of potassium is $0.8560 \mathrm{~g} \cdot \mathrm{cm}^{-3}$, calculate the Avogadro constant.

Adriano Chikande
Adriano Chikande
Numerade Educator
01:30

Problem 8

Cerium crystallizes as a face-centered cubic lattice, and the length of a unit cell is $516.0 \mathrm{pm}$. Given that the density of cerium is $6.773 \mathrm{~g} \cdot \mathrm{cm}^{-3}$, calculate the Avogadro constant.

Adriano Chikande
Adriano Chikande
Numerade Educator
01:58

Problem 9

Given that the density of $\mathrm{KBr}$ is $2.75 \mathrm{~g} \cdot \mathrm{cm}^{-3}$ and that the length of an edge of a cubic unit cell is $654 \mathrm{pm}$, determine how many formula units of KBr there are in a unit cell. Does the unit cell have a $\mathrm{NaCl}$ or a CsCl structure? (See Figure 29.18.)

Adriano Chikande
Adriano Chikande
Numerade Educator
01:45

Problem 10

Crystalline potassium fluoride has the $\mathrm{NaCl}$ type of structure shown in Figure $29.18 \mathrm{a}$. Given that the density of $\mathrm{KF}(\mathrm{s})$ is $2.481 \mathrm{~g} \cdot \mathrm{cm}^{-3}$ at $20^{\circ} \mathrm{C}$, calculate the unit cell length and the nearest-neighbor distance in KF(s). (The nearest-neighbor distance is the shortest distance between the centers of any two adjacent ions in the lattice.)

Adriano Chikande
Adriano Chikande
Numerade Educator
01:36

Problem 11

The crystalline structure of sodium chloride can be described by two interpenetrating face-centered cubic structures (see Figure 29.18a) with four formula units per unit cell. Given that the length of a unit cell is $564.1 \mathrm{pm}$ at $20^{\circ} \mathrm{C}$, calculate the density of $\mathrm{NaCl}(\mathrm{s})$. The literature value is $2.163 \mathrm{~g} \cdot \mathrm{cm}^{-3}$.

Adriano Chikande
Adriano Chikande
Numerade Educator
01:16

Problem 12

Determine the Miller indices of each set of lines shown in the figure below.

Adriano Chikande
Adriano Chikande
Numerade Educator
01:28

Problem 13

Determine the Miller indices of each set of lines shown in the figure below.

Adriano Chikande
Adriano Chikande
Numerade Educator
03:09

Problem 14

Sketch the following planes in a two-dimensional square lattice: (a) 01 , (b) 21 , (c) $1 \overline{1}$,
(d) 32 .

Adriano Chikande
Adriano Chikande
Numerade Educator
01:33

Problem 15

What is the relation between the 11 planes and the $1 \overline{1}$ planes of a two-dimensional square lattice?

Adriano Chikande
Adriano Chikande
Numerade Educator
01:09

Problem 16

What is the relation between the $1 \overline{1}$ planes and the $\overline{1} 1$ planes of a two-dimensional square lattice?

Adriano Chikande
Adriano Chikande
Numerade Educator
02:48

Problem 17

In this problem, we will derive a two-dimensional version of Equation 29.2. Using the figure below, show that
$$
\tan \alpha=\frac{b / k}{a / h} \quad \text { and } \quad \sin \alpha=\frac{d}{a / h}
$$

Adriano Chikande
Adriano Chikande
Numerade Educator
01:53

Problem 18

Determine the Miller indices of the four planes shown in the figure below.

Adriano Chikande
Adriano Chikande
Numerade Educator
01:48

Problem 19

Sketch the following planes in a three-dimensional cubic lattice: (a) 011, (b) $1 \overline{10}$, (c) $211,($ d) 222

Adriano Chikande
Adriano Chikande
Numerade Educator
01:14

Problem 20

Determine the Miller indices of the plane that intersects the crystal axes at (a) $(a, 2 b, 3 c)$,
(b) $(a, b,-c)$, and (c) $(2 a, b, c)$.

Adriano Chikande
Adriano Chikande
Numerade Educator
02:19

Problem 21

Calculate the separation between the (a) 100 planes, (b) 111 planes, and (c) $12 \overline{1}$ planes in a cubic lattice whose unit cell length is $529.8 \mathrm{pm}$.

Adriano Chikande
Adriano Chikande
Numerade Educator
02:40

Problem 22

The distance between the 211 planes in barium is $204.9 \mathrm{pm}$. Given that barium forms a body-centered cubic lattice, calculate the density of barium.

Adriano Chikande
Adriano Chikande
Numerade Educator
01:17

Problem 23

Gold crystallizes as a face-centered cubic crystal. Calculate the surface number density of gold atoms in the 100 planes. Take the length of the unit cell (Figure $29.3$ ) to be $407.9 \mathrm{pm}$.

Adriano Chikande
Adriano Chikande
Numerade Educator
01:54

Problem 24

Chromium crystallizes as a body-centered cubic structure with a density of $7.20 \mathrm{~g} \cdot \mathrm{cm}^{-3}$ at $20^{\circ} \mathrm{C}$. Calculate the length of a unit cell and the distance between successive 110,200 , and 111 planes.

Adriano Chikande
Adriano Chikande
Numerade Educator
01:13

Problem 25

A single crystal of $\mathrm{NaCl}$ is oriented such that the incident X-rays are perpendicular to the a axis of the crystal. The distance between the spots corresponding to diffraction from the 000 and 100 planes is $14.8 \mathrm{~mm}$, and the detector is located $52.0 \mathrm{~mm}$ from the crystal. Calculate the value of $a$, the length of the unit cell along the a axis. Take the wavelength of the X-radiation to be $\lambda=154.433 \mathrm{pm}$.

Adriano Chikande
Adriano Chikande
Numerade Educator
03:03

Problem 26

Silver crystallizes as a face-centered cubic structure with a unit cell length of $408.6 \mathrm{pm}$. The single crystal of silver is oriented such that the incident X-rays are perpendicular to the c axis of the crystal. The detector is located $29.5 \mathrm{~mm}$ from the crystal. What is the distance between the diffraction spots from the 001 and 002 planes on the face of the detector for (a) the $\lambda=154.433$-pm line of copper, and (b) the $\lambda=70.926$-pm line of a molybdenum X-ray source? Which X-ray source gives you the best spatial resolution between the diffraction spots?

Adriano Chikande
Adriano Chikande
Numerade Educator
01:35

Problem 27

The X-ray diffraction angles for the first-order diffraction spot from the 111 planes of a cubic crystal with $a=380.5 \mathrm{pm}$ are observed to be $\alpha=18.79^{\circ}, \beta=0^{\circ}$, and $\gamma=0^{\circ} .$ How is the crystal oriented? Take the wavelength of the X-radiation to be $\lambda=154.433 \mathrm{pm}$.

Adriano Chikande
Adriano Chikande
Numerade Educator
01:33

Problem 28

The unit cell of topaz is orthorhombic with $a=839 \mathrm{pm}, b=879 \mathrm{pm}$, and $c=465 \mathrm{pm}$. Calculate the values of the Bragg $\mathrm{X}$-ray diffraction angles from the $110,101,111$, and 222 planes. Take the wavelength of the $\mathrm{X}$-radiation to be $\lambda=154.433 \mathrm{pm}$.

Adriano Chikande
Adriano Chikande
Numerade Educator
02:44

Problem 29

In this problem, we will derive the Bragg equation, Equation 29.12. William and Lawrence Bragg (father and son) assumed that X-rays are scattered by successive planes of atoms within a crystal (see the following figure).
Each set of planes reflects the X-rays specularly; that is, the angle of incidence is equal to the angle of reflection, as shown in the figure. The X-radiation reflected from the lower plane in the figure travels a distance $P Q R$ longer than the $\mathrm{X}$-radiation reflected by the upper layer. Show that $P Q R=2 d \sin \theta$, and argue that $2 d \sin \theta$ must be an integral number of wavelengths for constructive interference and hence a diffraction pattern to be observed.

Adriano Chikande
Adriano Chikande
Numerade Educator
01:41

Problem 30

The smallest observed Bragg diffraction angle of the third-order reflection from the 111 planes of a potassium crystal is $\theta=6.613^{\circ}$ when $\mathrm{X}$-radiation of wavelength $\lambda=70.926 \mathrm{pm}$ is used. Given that potassium exists as a body-centered cubic lattice, determine the length of the unit cell and the density of the crystal.

Adriano Chikande
Adriano Chikande
Numerade Educator
01:33

Problem 31

The crystalline structure of $\mathrm{CuSO}_{4}(\mathrm{~s})$ is orthorhombic with unit cell dimensions of $a=488.2 \mathrm{pm}, b=665.7 \mathrm{pm}$, and $c=831.6 \mathrm{pm}$. Calculate the value of $\theta$, the first-order Bragg diffraction angle, from the 100 planes, the 110 planes, and the 111 planes if $\mathrm{CuSO}_{4}(\mathrm{~s})$ is irradiated with $\mathrm{X}$-rays with $\lambda=154.433 \mathrm{pm}$.

Adriano Chikande
Adriano Chikande
Numerade Educator
01:43

Problem 32

One experimental method of collecting X-ray diffraction data, (called the powder method) involves irradiating a crystalline powder rather than a single crystal. The various sets of reflecting planes in a powder will be essentially randomly oriented so that there will always be planes oriented such that they will reflect the monochromatic X-radiation. The crystallites whose particular $h k l$ planes are oriented at the Bragg diffraction angle, $\theta$, to the incident beam will reflect the beam constructively. In this problem, we will illustrate the procedure that can be used for indexing the planes that give rise to observed reflections and consequently leads to the determination of the type of unit cell. This method is limited to cubic, tetragonal, and orthorhombic crystals (all unit cell angles are $90^{\circ}$ ). We will illustrate the method for a cubic unit cell.
First, show that the Bragg equation can be written as
$$
\sin ^{2} \theta=\frac{\lambda^{2}}{4 a^{2}}\left(h^{2}+k^{2}+l^{2}\right)
$$
for a cubic unit cell. Then we tabulate the diffraction-angle data in order of increasing values of $\sin ^{2} \theta$. We then search for the smallest sets of $h, k$, and $l$ that are in the same ratios as the values of $\sin ^{2} \theta$. We then compare these values of $h, k$, and $l$ with the allowed values given in Problem 29-38 to determine the type of unit cell.

Lead is known to crystallize in one of the cubic structures. Suppose that a powder sample of lead gives Bragg reflections at the following angles: $15.66^{\circ}, 18.17^{\circ}, 26.13^{\circ}$, $31.11^{\circ}, 32.71^{\circ}$, and $38.59^{\circ}$, using $\mathrm{X}$-radiation with $\lambda=154.433 \mathrm{pm}$. Now form a table of increasing values of $\sin ^{2} \theta$, divide by the smallest value, convert the resulting values to integer values by multiplying by a common integer factor, and then determine the possible values of $h, k$, and $l$. For example, the first two entries in such a table are listed below.
\begin{tabular}{cccc}
& Division by & Conversion to & Possible value \\
$\sin ^{2} \theta$ & $0.0729$ & integer value & of $h k l$ \\
\hline $0.0729$ & 1 & 3 & 111 \\
$0.0972$ & $1.33$ & 4 & 200
\end{tabular}
Complete this table, determine the type of cubic unit cell for lead, and determine its length.

Mayukh Banik
Mayukh Banik
Numerade Educator
07:31

Problem 33

The X-ray powder diffraction patterns of $\mathrm{NaCl}(\mathrm{s})$ and $\mathrm{KCl}(\mathrm{s})$, both of which have the structures given in Figure $29.18 \mathrm{a}$, are shown below.

Given that $\mathrm{NaCl}$ and $\mathrm{KCl}$ have the same crystal structure, explain the differences between the two sets of data. Realize that the value of $f_{\mathrm{K}^{+}}$is almost equal to $f_{\mathrm{Cl}^{-}}$because $\mathrm{K}^{+}$and $\mathrm{Cl}^{-}$are isoelectronic.

Shazia Naz
Shazia Naz
Numerade Educator
05:31

Problem 34

Iridium crystals have a cubic unit cell. The first six observed Bragg diffraction angles from a powered sample using $\mathrm{X}$-rays with $\lambda=165.8 \mathrm{pm}$ are $21.96^{\circ}, 25.59^{\circ}, 37.65^{\circ}, 45.74^{\circ}$, $48.42^{\circ}$, and $59.74^{\circ}$. Use the method outlined in Problem 29-32 to determine the type of cubic unit cell and its length.

Alex M
Alex M
Numerade Educator
01:33

Problem 35

The density of tantallum at $20^{\circ} \mathrm{C}$ is $16.69 \mathrm{~g} \cdot \mathrm{cm}^{-3}$, and its unit cell is cubic. Given that the first five observed Bragg diffraction angles are $\theta=19.31^{\circ}, 27.88^{\circ}, 34.95^{\circ}, 41.41^{\circ}$, and $47.69^{\circ}$, find the type of unit cell and its length. Take the wavelength of the X-radiation to be $\lambda=154.433 \mathrm{pm}$.

Adriano Chikande
Adriano Chikande
Numerade Educator
01:33

Problem 36

The density of silver at $20^{\circ} \mathrm{C}$ is $10.50 \mathrm{~g} \cdot \mathrm{cm}^{-3}$, and its unit cell is cubic. Given that the first five observed Bragg diffraction angles are $\theta=19.10^{\circ}, 22.17^{\circ}, 32.33^{\circ}, 38.82^{\circ}$, and $40.88^{\circ}$, find the type of unit cell and its length. Take the wavelength of the X-radiation to be $\lambda=154.433 \mathrm{pm}$.

Adriano Chikande
Adriano Chikande
Numerade Educator
08:35

Problem 37

Derive an expression for the structure factor of a primitive cubic unit cell and a facecentered cubic unit cell. Show that there will be observed reflections for a primitive unit cell for all integer values of $h, k$, and $l$ and reflections for a face-centered-cubic unit cell only if $h, k$, and $l$ are either all even or all odd.

Hafiz Shahzaib
Hafiz Shahzaib
Numerade Educator
00:49

Problem 38

Use the results of the previous problem and Example $29-9$ to verify the entries in the following table.
\begin{array}{cl}
\hline & \text { Cubic lattice type for which } \\
\text { Miller indices (hkl) } & \text { a reflection is observed } \\
\hline 100 & \mathrm{pc} \\
110 & \mathrm{pc} & \\
111 & \mathrm{pc} & \mathrm{fcc} & \\
200 & \mathrm{pc} & \mathrm{fcc} & \mathrm{bcc} \\
210 & \mathrm{pc} & & \\
211 & \mathrm{pc} & & \mathrm{bcc} \\
220 & \mathrm{pc} & \mathrm{fcc} & \mathrm{bcc} \\
300 & \mathrm{pc} & & \\
221 & \mathrm{pc} & & \\
310 & \mathrm{pc} & & \mathrm{bcc} \\
311 & \mathrm{pc} & \mathrm{fcc} & \\
222 & \mathrm{pc} & \mathrm{fcc} & \mathrm{bcc} \\
320 & \mathrm{pc} & & \\
321 & \mathrm{pc} & & \mathrm{bcc} \\
400 & \mathrm{pc} & \mathrm{fcc} & \mathrm{bcc} \\
\hline
\end{array}

Chai Santi
Chai Santi
Numerade Educator
01:41

Problem 39

The X-ray diffraction pattern of a cubic crystalline substance shows data that correspond to reflections from the $110,200,220,310,222$, and 400 planes. What type of cubic unit cell does the substance have? (Hint: See the table in Problem 29-38.)

Adriano Chikande
Adriano Chikande
Numerade Educator
03:11

Problem 40

Chromium is either a face-centered cubic or a body-centered cubic crystalline solid. Given that it has the following observed successive values of $d: 203.8 \mathrm{pm}, 144.2 \mathrm{pm}$, $117.7 \mathrm{pm}, 102.0 \mathrm{pm}, 91.20 \mathrm{pm}$, and $83.25 \mathrm{pm}$, determine the type of cubic unit cell, the length of the unit cell, and the density. (Hint: See the table in Problem 29-38.)

Prashant Bana
Prashant Bana
Numerade Educator
02:48

Problem 41

In this problem, we will derive the structure factor for a sodium chloride-type unit cell. First, show that the coordinates of the cations at the eight corners are $(0,0,0),(1,0,0),(0,1,0)$, $(0,0,1),(1,1,0),(1,0,1),(0,1,1,)$, and $(1,1,1)$ and those at the six faces are $\left(\frac{1}{2}, \frac{1}{2}, 0\right),\left(\frac{1}{2}, 0, \frac{1}{2}\right)$ $\left(0, \frac{1}{2}, \frac{1}{2}\right),\left(\frac{1}{2}, \frac{1}{2}, 1\right),\left(\frac{1}{2}, 1, \frac{1}{2}\right)$, and $\left(1, \frac{1}{2}, \frac{1}{2}\right)$. Similarly, show that the coordinates of the anions along the 12 edges are $\left(\frac{1}{2}, 0,0\right),\left(0, \frac{1}{2}, 0\right),\left(0,0, \frac{1}{2}\right),\left(\frac{1}{2}, 1,0\right),\left(1, \frac{1}{2}, 0\right),\left(0, \frac{1}{2}, 1\right),\left(\frac{1}{2}, 0,1\right),\left(1,0, \frac{1}{2}\right)$, $\left(0,1, \frac{1}{2}\right),\left(\frac{1}{2}, 1,1\right),\left(1, \frac{1}{2}, 1\right)$, and $\left(1,1, \frac{1}{2}\right)$ and those of the anion at the center of the unit cell are $\left(\frac{1}{2}, \frac{1}{2}, \frac{1}{2}\right)$. Now show that
$$
\begin{aligned}
F(h k l)=& \frac{f_{+}}{8}\left[1+e^{2 \pi i h}+e^{2 \pi i k}+e^{2 \pi i l}+e^{2 \pi i(h+k)}+e^{2 \pi i(h+l)}+e^{2 \pi i(k+l)}+e^{2 \pi i(h+k+l)}\right] \\
&+\frac{f_{+}}{2}\left[e^{\pi i(h+k)}+e^{\pi i(h+l)}+e^{\pi i(k+l)}+e^{\pi i(h+k+2)}+e^{\pi i(h+2 k+l)}+e^{\pi i(2 h+k+l)}\right] \\
&+\frac{f_{-}}{4}\left[e^{\pi i h}+e^{\pi i k}+e^{\pi i l}+e^{\pi i(h+2 k)}+e^{\pi i(2 h+k)}+e^{\pi i(k+2 l)}+e^{\pi i(h+2 l)}+e^{\pi i(2 h+l)}+e^{\pi i(2 k+l)}\right.
\end{aligned}
$$
$$
\begin{aligned}
&\left.\quad+e^{\pi i(h+2 k+2 l)}+e^{\pi i(2 h+k+2 l)}+e^{n i(2 h+2 k+l)}\right]+f_{-} e^{\pi i(h+k+l)} \\
&=f_{+}\left[1+(-1)^{h+k}+(-1)^{h+l}+(-1)^{k+l}\right] \\
&\quad+f_{-}\left[(-1)^{h}+(-1)^{k}+(-1)^{l}+(-1)^{h+k+l}\right]
\end{aligned}
$$
Finally, show that
$$
F(h k l)=4\left(f_{+}+f_{-}\right)
$$
if $h, k$, and $l$ are all even; that
$$
F(h k l)=4\left(f_{+}-f_{-}\right)
$$
if $h, k$, and $l$ are all odd, and that $F(h k l)=0$ otherwise.

Dr.  Satish  Ingale
Dr. Satish Ingale
Numerade Educator
04:23

Problem 42

Show that
$$
\begin{array}{ll}
F(h k l)=f_{+}+f_{-} & \begin{array}{l}
\text { if } h, k, \text { and } l \text { are all even } \\
\text { or just one of them is even }
\end{array} \\
=f_{+}-f_{-} & \begin{array}{l}
\text { if all are odd } \\
\text { or just one is odd }
\end{array}
\end{array}
$$
for the CsCl(s) crystal structure shown in Figure $29.18 \mathrm{~b} .$ Cesium bromide and cesium iodide have the same crystal structure as cesium chloride. Compare the expected diffraction patterns of cesium chloride and cesium iodide. Recall that $\mathrm{Cs}^{+}$and $\mathrm{I}^{-}$are isoelectronic.

Arpit Gupta
Arpit Gupta
Numerade Educator
01:08

Problem 43

In this problem, we will prove that a crystal lattice can have only one-, two-, three-, four-, and six-fold axes of symmetry. Consider the following figure, where $P_{1}, P_{2}$, and $P_{3}$ are three lattice points, each separated by the lattice vector a.

If the lattice has $n$-fold symmetry, then both a clockwise and a counter-clockwise rotation by $\phi=360^{\circ} / n$ about the point $P_{2}$ will lead to the points $P_{1}^{\prime}$ and $P_{2}^{\prime}$, which must be lattice points (because of the fact that the lattice has an $n$-fold axis of symmetry). Show that the vector distance $P_{1}^{\prime} P_{2}^{\prime}$ must satisfy the relation
$$
2 \mathbf{a} \cos \phi=N \mathbf{a}
$$
where $N$ is a positive or negative integer. Now show that the only values of $\phi$ that satsify the above relation are $360^{\circ}(n=1), 180^{\circ}(n=2), 120^{\circ}(n=3), 90^{\circ}(n=4)$, and $60^{\circ}(n=6)$, corresponding to $N=2,-2,-1,0$, and 1, respectively.

Carson Merrill
Carson Merrill
Numerade Educator
02:44

Problem 44

The von Laue equations are often expressed in vector notation. The following figure illustrates the X-ray scattering from two lattice points $P_{1}$ and $P_{2}$.

Let $\mathrm{s}_{0}$ be a unit vector in the direction of the incident radiation and $\mathrm{s}$ be a unit vector in the direction of the scattered X-radiation. Show that the difference in the path lengths of the waves scattered from $P_{1}$ and $P_{2}$ is given by
$$
\delta=P_{1} A-P_{2} B=\mathbf{r} \cdot \mathbf{s}-\mathbf{r} \cdot \mathbf{s}_{0}=\mathbf{r} \cdot \mathbf{S}
$$
where $\mathbf{S}=\mathbf{s}-\mathbf{s}_{0}$. Because $P_{1}$ and $P_{2}$ are lattice points, $\mathbf{r}$ must be expressible as $m \mathbf{a}+$ $n \mathbf{b}+p \mathbf{c}$, where $m, n$, and $p$ are integers, and $\mathbf{a}, \mathbf{b}$, and $\mathbf{c}$ are the unit cell axes. Show that the fact that $\delta$ must be an integral multiple of the wavelength $\lambda$ leads to the equations
$$
\begin{aligned}
&\mathbf{a} \cdot \mathbf{S}=h \lambda \\
&\mathbf{b} \cdot \mathbf{S}=k \lambda \\
&\mathbf{c} \cdot \mathbf{S}=l \lambda
\end{aligned}
$$
where $h, k$, and $l$ are integers. These equations are the von Laue equations in vector notation.

Adriano Chikande
Adriano Chikande
Numerade Educator
02:44

Problem 45

We can derive the Bragg equation from the von Laue equations derived in the previous problem. First show that $\mathbf{S}=\mathbf{s}-\mathbf{s}_{0}$ bisects the angle between $\mathbf{s}_{0}$ and $\mathbf{s}$ and is normal to the plane from which the X-radiation would be specularly reflected (the angle of incidence equals the angle of reflection). Now show that the distance from the origin of the $\mathbf{a}, \mathbf{b}$, and c axes to the $h k l$ plane is given by
$$
d=\frac{\mathbf{a}}{h} \cdot \frac{\mathbf{S}}{|\mathbf{S}|}=\frac{\mathbf{b}}{k} \cdot \frac{\mathbf{S}}{|\mathbf{S}|}=\frac{\mathbf{c}}{l} \cdot \frac{\mathbf{S}}{|\mathbf{S}|}=\frac{\lambda}{|\mathbf{S}|}
$$
Last, show that $|\mathbf{S}|=\left[\left(\mathbf{s}-\mathbf{s}_{0}\right) \cdot\left(\mathbf{s}-\mathbf{s}_{0}\right)\right]^{1 / 2}=[2-2 \cos 2 \theta]^{1 / 2}=2 \sin \theta$, which leads to the Bragg equation $d=\lambda / 2 \sin \theta$

Adriano Chikande
Adriano Chikande
Numerade Educator
03:45

Problem 46

The enthalpy of adsorption for $\mathrm{H}_{2}$ adsorbed on a surface of copper is $-54.4 \mathrm{~kJ} \cdot \mathrm{mpl}^{-1} .$ The activation energy for going from the physisorbed state to the chemisorbed state is $29.3 \mathrm{~kJ} \cdot \mathrm{mol}^{-1}$, and the curve crossing between these two potentials occurs at $V(z)=$ $21 \mathrm{~kJ} \cdot \mathrm{mol}^{-1}$. Draw a schematic representation similar to that in Figure $29.20$ for the case of $\mathrm{H}_{2}$ interacting with copper.

Amit Srivastava
Amit Srivastava
Numerade Educator
05:49

Problem 47

In Section $25-4$, we showed that the collision frequency per unit area is (Equation $25.48$ )
$$
z_{\mathrm{coll}}=\frac{\rho\langle u\rangle}{4}
$$
Use Equation 1 and the ideal-gas law to show that $J_{N}$, the number of molecules striking a surface of unit area $\left(1 \mathrm{~m}^{2}\right)$ in one second, is
$$
J_{N}=\frac{P N_{\mathrm{A}}}{(2 \pi M R T)^{1 / 2}}
$$
where $M$ is the molar mass of the molecule, $P$ is the pressure of the gas, and $T$ is the temperature. How many nitrogen molecules will strike a $1.00-\mathrm{cm}^{2}$ surface in $1.00 \mathrm{~s}$ at $298.1 \mathrm{~K}$ and a gas pressure of $1.05 \times 10^{-6} \mathrm{~Pa}$ ?

Bruce Edelman
Bruce Edelman
Numerade Educator
01:50

Problem 48

One langmuir corresponds to an exposure of a surface to a gas at a pressure of $1.00 \times 10^{-6}$ torr for 1 second at $298.15 \mathrm{~K}$. Define one langmuir in units of pascals instead of torr. How many nitrogen molecules will strike a surface of area $1.00 \mathrm{~cm}^{2}$ when exposed to $1.00$ langmuir? (See Problem 29-47.)

CA
Chi-Chung Ai
Numerade Educator
02:13

Problem 49

If the density of surface sites is $2.40 \times 10^{14} \mathrm{~cm}^{-2}$ and every molecule that strikes the surface adsorbs to one of these sites, determine the fraction of a monolayer created by the exposure of a $1.00-\mathrm{cm}^{2}$ surface to $1.00 \times 10^{-4}$ langmuir of $\mathrm{N}_{2}(\mathrm{~g})$ at $298.15 \mathrm{~K}$.

Nikhil Choudhary
Nikhil Choudhary
Numerade Educator
01:50

Problem 50

For conducting surface experiments it is important to maintain a clean surface. Suppose that a $1.50-\mathrm{cm}^{2}$ surface is placed inside a high-vacuum chamber at $298.15 \mathrm{~K}$ and the pressure inside the chamber is $1.00 \times 10^{-12}$ torr. If the density of the surface sites is $1.30 \times 10^{16} \mathrm{~cm}^{-2}$ and we assume that the only gas in the chamber is $\mathrm{H}_{2} \mathrm{O}$ and that each of the $\mathrm{H}_{2} \mathrm{O}$ molecules that strike the surface adsorbs to one surface site, how long will it be until $1.00 \%$ of the surface sites are occupied by water?

Adriano Chikande
Adriano Chikande
Numerade Educator
01:26

Problem 51

Use the results of Example 29-12 to determine the rate of desorption of $\mathrm{CO}$ from palladium at $300 \mathrm{~K}$ and $500 \mathrm{~K}$.

Lottie Adams
Lottie Adams
Numerade Educator
02:13

Problem 52

The following data were obtained for the adsorption of $\mathrm{N}_{2}(\mathrm{~g})$ to a piece of solid graphite at $197 \mathrm{~K}$. The tabulated volumes are the volumes that the adsorbed gas would occupy at $0.00^{\circ} \mathrm{C}$ and one bar
\begin{tabular}{c|ccccc}
$P /$ bar & $3.54$ & $10.13$ & $\underline{16}: 92$ & $\underline{26.04}$ & $\underline{29}: 94$ \\
\hline$V / 10^{-4} \mathrm{~m}^{3}$ & 328 & 456 & 497 & 527 & 536
\end{tabular}
Determine the values of $V_{\mathrm{m}}$ and $b$ using the Langmuir adsorption isotherm. The total mass of the carbon solid is $13.25 \mathrm{~g}$. Determine the fraction of the carbon atoms that are accessible as binding sites if you assume that each surface atom can adsorb one $\mathrm{N}_{2}$ molecule.

Madi Sousa
Madi Sousa
Numerade Educator
01:55

Problem 53

The first-order surface reaction
$$
\mathrm{A}(\mathrm{g}) \Longrightarrow \mathrm{A}(\mathrm{ads}) \Longrightarrow \mathrm{B}(\mathrm{g})
$$
has a rate of $1.8 \times 10^{-4} \mathrm{~mol} \cdot \mathrm{dm}^{-3} \cdot \mathrm{s}^{-1}$. The surface has a dimension of $1.00 \mathrm{~cm}$ by $3.50 \mathrm{~cm}$. Calculate the rate of reaction if the dimensions of the two sides of the surface were each doubled. [Assume that $\mathrm{A}(\mathrm{g})$ is in excess.]

David Collins
David Collins
Numerade Educator
05:00

Problem 54

Consider the reaction scheme
$$
\mathrm{A}(\mathrm{g})+\mathrm{S} \stackrel{k_{1}}{\Longrightarrow} \mathrm{A}-\mathrm{S} \stackrel{k_{2}}{\longrightarrow} \mathrm{P}(\mathrm{g})
$$
for which the rate law is
$$
v=k_{2} \theta_{\mathrm{A}}
$$
where $\theta_{\mathrm{A}}$ is the fraction of surface sites occupied by A molecules. Use the Langmuir adsorption isotherm (Equation 29.35) to obtain an expression for the reaction rate in terms of $K_{c}$ and $[\mathrm{A}]$. Under what conditions will the reaction be first order in the concentration of A?

Oluwapelumi Kolawole
Oluwapelumi Kolawole
Numerade Educator
02:34

Problem 55

Consider a surface-catalyzed bimolecular reaction between molecules A and B that has a rate law of the form
$$
v=k_{3} \theta_{\mathrm{A}} \theta_{\mathrm{B}}
$$
where $\theta_{\mathrm{A}}$ is the fraction of surface sites occupied by reactant $\mathrm{A}$ and $\theta_{\mathrm{B}}$ is the fraction of surface sites occupied by reactant B. A mechanism consistent with this reaction is as follows:
$\mathrm{B}(\mathrm{g})+\mathrm{S}(\mathrm{s}) \stackrel{\stackrel{k_{a}^{\mathrm{B}}}{\Longleftrightarrow}}{\stackrel{k_{\mathrm{d}}^{\mathrm{B}}}} \mathrm{B}-\mathrm{S}(\mathrm{s}) \quad$ (fast equilibrium)
$\mathrm{A}-\mathrm{S}(\mathrm{s})+\mathrm{B}-\mathrm{S}(\mathrm{s}) \stackrel{k_{3}}{\Longrightarrow}$ products
Take $K_{\mathrm{A}}$ and $K_{\mathrm{B}}$ to be the equilibrium constants for Equations 1 and 2 , respectively. Derive expressions for $\theta_{\mathrm{A}}$ and $\theta_{\mathrm{B}}$ in terms of $[\mathrm{A}],[\mathrm{B}], K_{\mathrm{A}}$, and $K_{\mathrm{B}} .$ Use your results to show that the rate law can be written as
$$
v=\frac{k_{3} K_{\mathrm{A}} K_{\mathrm{B}}[\mathrm{A}][\mathrm{B}]}{\left(1+K_{\mathrm{A}}[\mathrm{A}]+K_{\mathrm{B}}[\mathrm{B}]\right)^{2}}
$$

Aadit Sharma
Aadit Sharma
Numerade Educator
01:12

Problem 56

Reconsider the surface-catalyzed bimolecular reaction in Problem $29-55 .$ If $\mathrm{A}(\mathrm{g}$ ) and $\mathrm{B}(\mathrm{g})$ do not compete for surface sites, but instead each molecule uniquely binds to a different type of surface site, show that the rate law is given by
$$
v=\frac{k_{3} K_{\mathrm{A}} K_{\mathrm{B}}[\mathrm{A}][\mathrm{B}]}{\left(1+K_{\mathrm{A}}[\mathrm{A}]\right)\left(1+K_{\mathrm{B}}[\mathrm{B}]\right)}
$$

Hast Aggarwal
Hast Aggarwal
Numerade Educator
03:52

Problem 57

In this problem we derive Equation $29.45$, the rate law for the oxidation reaction $2 \mathrm{CO}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{~g}) \longrightarrow 2 \mathrm{CO}_{2}(\mathrm{~g})$ assuming that the reaction occurs by the Langmuir-Hinshelwood mechanism. The overall rate law for this mechanism is
$$
v=k_{3} \theta_{\mathrm{Co}} \theta_{\mathrm{o}_{2}}
$$

Marissa Turner
Marissa Turner
Numerade Educator
03:52

Problem 58

In this problem we derive Equation $29.46$, the rate law for the oxidation reaction $2 \mathrm{CO}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{~g}) \longrightarrow 2 \mathrm{CO}_{2}(\mathrm{~g})$ assuming that the reaction occurs by the Eley-Rideal mechanism. The overall rate law for this mechanism is
$$
v=k_{3} \theta_{\mathrm{O}_{2}}[\mathrm{CO}]
$$
Assuming that both $\mathrm{CO}(\mathrm{g})$ and $\mathrm{O}_{2}(\mathrm{~g})$ compete for adsorption sites, show that
$$
v=\frac{k_{3} K_{\mathrm{O}_{2}}^{1 / 2}\left[\mathrm{O}_{2}\right]^{1 / 2}[\mathrm{CO}]}{1+K_{\mathrm{O}_{2}}^{1 / 2}\left[\mathrm{O}_{2}\right]^{1 / 2}+K_{\mathrm{CO}}[\mathrm{CO}]}
$$
Use the relationship between $K_{c}$ and $b$ and the ideal-gas law to show that this equation is equivalent to Equation $29.46$.

Marissa Turner
Marissa Turner
Numerade Educator
03:27

Problem 59

The hydrogenation of ethene on copper obeys the rate law
$$
v=\frac{k\left[\mathrm{H}_{2}\right]^{1 / 2}\left[\mathrm{C}_{2} \mathrm{H}_{4}\right]}{\left(1+K\left[\mathrm{C}_{2} \mathrm{H}_{4}\right]\right)^{2}}
$$
where $k$ and $K$ are constants. Mechanistic studies show that the reaction occurs by the Langmuir-Hinshelwood mechanism. How are $k$ and $K$ related to the rate constants for the individual steps of the reaction mechanism? What can you conclude about the relative adsorption of $\mathrm{H}_{2}(\mathrm{~g})$ and $\mathrm{C}_{2} \mathrm{H}_{4}$ (g) to the copper surface from the form of the observed rate law?

Adriano Chikande
Adriano Chikande
Numerade Educator
04:06

Problem 60

The iron-catalyzed exchange reaction
$$
\mathrm{NH}_{3}(\mathrm{~g})+\mathrm{D}_{2}(\mathrm{~g}) \longrightarrow \mathrm{NH}_{2} \mathrm{D}(\mathrm{g})+\mathrm{HD}(\mathrm{g})
$$
obeys the rate law
$$
v=\frac{k\left[\mathrm{D}_{2}\right]^{1 / 2}\left[\mathrm{NH}_{3}\right]}{\left(1+K\left[\mathrm{NH}_{3}\right]\right)^{2}}
$$
Is this rate law consistent with either the Eley-Rideal or Langmuir-Hinshelwood mechanisms? How are $k$ and $K$ related to the rate constants of the individual steps of the mechanism you chose? What does the rate law tell you about the relative adsorption of $\mathrm{D}_{2}(\mathrm{~g})$ and $\mathrm{NH}_{3}(\mathrm{~g})$ to the iron surface?

Adriano Chikande
Adriano Chikande
Numerade Educator
02:12

Problem 61

Consider the surface-catalyzed exchange reaction
$$
\mathrm{H}_{2}(\mathrm{~g})+\mathrm{D}_{2}(\mathrm{~g}) \longrightarrow 2 \mathrm{HD}(\mathrm{g})
$$
Experimental studies show that this reaction occurs by the Langmuir-Hinshelwood mechanism by which both $\mathrm{H}_{2}(\mathrm{~g})$ and $\mathrm{D}_{2}(\mathrm{~g}$ ) first dissociatively chemisorb to the surface. The rate-determining step is the reaction between the adsorbed $\mathrm{H}$ and $\mathrm{D}$ atoms. Derive an expression for the rate law for this reaction in terms of the gas-phase pressures of $\mathrm{H}_{2}(\mathrm{~g})$ and $\mathrm{D}_{2}(\mathrm{~g}$ ). (Assume ideal-gas behavior.)

Bhumika Jayee
Bhumika Jayee
Numerade Educator
02:48

Problem 62

LEED spectroscopy records the intensities and locations of electrons that are diffracted from a surface. For an electron to diffract, its de Broglie wavelength must be less than twice the distance between the atomic planes in the solid (see Section 29-9). Show that the de Broglie wavelength of an electron accelerated through a potential difference of $\phi$ volts is given by
$$
\lambda / \mathrm{pm}=\left(\frac{1.504 \times 10^{6} \mathrm{~V}}{\phi}\right)^{1 / 2}
$$

Mirza  Aslam Beig
Mirza Aslam Beig
Numerade Educator
07:55

Problem 63

-63. The distance between the 100 planes of a nickel substrate, whose surface is a 100 plane, is $351.8 \mathrm{pm}$. Calculate the minimum accelerating potential so that electrons can diffract from the crystal. Calculate the kinetic energy of these electrons.

Jonathan Ibarra
Jonathan Ibarra
Numerade Educator
01:14

Problem 64

-64. The distance between the 111 surface of silver and the second layer of atoms is $235 \mathrm{pm}$, the same as in the bulk. If electrons with a kinetic energy of $8.77 \mathrm{eV}$ strike the surface, will an electron diffraction pattern be observed?

Averell Hause
Averell Hause
Carnegie Mellon University
06:46

Problem 65

Figure $29.28$ shows the relative rates of ammonia synthesis for five different surfaces of iron. Iron crystallizes as a body-centered cubic structure. Draw a schematic representation of the atomic arrangement of the 100,110, and 111 surfaces. (Hint: See Figure 29.9.) Determine the center-to-center distance between nearest neighbor atoms on the surface in units of $a$, the dimension of the unit cell.

Amna Khalid
Amna Khalid
Numerade Educator
00:53

Problem 66

The Freundlich adsorption isotherm is given by
$$
V=k P^{a}
$$
where $k$ and $a$ are constants. Can the data in Problem 29-52 be described by the Freundlich adsorption isotherm? Determine the best-fit values of $k$ and $a$ to the data.

Nikhil Choudhary
Nikhil Choudhary
Numerade Educator
01:05

Problem 67

Show that if $\theta \ll 1$, the Langmuir adsorption isotherm reduces to the Freundlich adsorption isotherm (Problem 29-66) with $k=b V_{m}$ and $a=1$.

Narayan Hari
Narayan Hari
Numerade Educator
01:15

Problem 68

Multilayer physisorption is often described by the $B E T$ adsorption isotherm
$$
\frac{P}{V\left(P^{*}-P\right)}=\frac{1}{c V_{\mathrm{m}}}+\frac{(c-1) P}{V_{\mathrm{m}} c P^{*}}
$$
where $P^{*}$ is the vapor pressure of the adsorbate at the temperature of the experiment, $V_{\mathrm{m}}$ is the volume corresponding to a monolayer of coverage on the surface, $V$ is the total volume adsorbed at pressure $P$, and $c$ is a constant. Rewrite the equation for the BET adsorption isotherm in the form
$$
\frac{V}{V_{\mathrm{m}}}=f\left(P / P^{*}\right)
$$
Plot $V / V_{m}$ versus $P / P^{*}$ for $c=0.1,1.0,10$, and $100 .$ Discuss the shapes of the curves.

Ramesh Singh
Ramesh Singh
Numerade Educator
View

Problem 69

The energy of adsorption, $E_{\text {ads }}$, can be measured by the technique of temperature programmed desorption (TPD). In a TPD experiment, the temperature of a surface with bound adsorbate is changed according to the equation
$$
T=T_{0}+\alpha t
$$
where $T_{0}$ is the initial temperature, $\alpha$ is a constant that determines the rate at which the temperature is changed, and $t$ is the time. A mass spectrometer is used to measure the concentration of molecules that desorb from the surface. The analysis of TPD data depends on the kinetic model for desorption. Consider a first-order desorption process
$$
\mathrm{M}-\mathrm{S}(\mathrm{s}) \stackrel{k_{\mathrm{d}}}{\Longrightarrow} \mathrm{M}(\mathrm{g})+\mathrm{S}(\mathrm{s})
$$
Write an expression for the rate law for desorption. Use Equation 1 , Equation $29.37$, and your rate law to show that your rate law can be written as
$$
\frac{d[\mathrm{M}-\mathrm{S}]}{d T}=-\frac{[\mathrm{M}-\mathrm{S}]}{\alpha}\left(\tau_{0}^{-1} e^{-E_{\mathrm{at}} / R T}\right)
$$
With increasing temperature, $d[\mathrm{M}-\mathrm{S}] / d t$ initially increases, then reaches a maximum, after which it decreases. Let $T=T_{\max }$ be the temperature corresponding to the maximum rate of desorption. Use Equation 2 to show that at $T_{\max }$
$$
\frac{E_{\text {ads }}}{R T_{\max }^{2}}=\frac{\tau_{0}^{-1}}{\alpha} e^{-E_{a b} / R T_{\max }}
$$

Lainey Roebuck
Lainey Roebuck
Numerade Educator
01:21

Problem 70

Show that Equation 3 of Problem $29-69$ can be written as
$$
2 \ln T_{\max }-\ln \alpha=\frac{E_{\text {ads }}}{R T_{\max }}+\ln \frac{E_{\text {ads }}}{R \tau_{0}^{-1}}
$$
What are the slope and intercept of a plot of $\left(2 \ln T_{\max }-\ln \alpha\right)$ versus $1 / T_{\max } ?$ 'The maximum desorption rates of CO from the 111 surface of palladium as a function of the rate of heating of the palladium surface are given below. Determine the values of $E_{a d s}$
and $\tau_{0}^{-1}$ from these data. Use the results to determine $k_{d}$, the desorption rate constant, at $600 \mathrm{~K}$
\begin{tabular}{cc}
$\alpha / \mathrm{K} \cdot \mathrm{s}^{-1}$ & $T_{\max } / \mathrm{K}$ \\
\hline $26.0$ & 500 \\
$20.1$ & 496 \\
$16.5$ & 493 \\
$11.0$ & 487
\end{tabular}

Amit Srivastava
Amit Srivastava
Numerade Educator
02:19

Problem 71

At a heating rate of $10 \mathrm{~K} \cdot \mathrm{s}^{-1}$, the maximum rate of desorption of $\mathrm{CO}$ from a Pd(s) surface occurs at $625 \mathrm{~K}$. Calculate the value of $E_{\text {ads }}$, assuming that the desorption is a first-order process and that $\tau_{0}=1.40 \times 10^{-12}$ s. (See Problems $29-69$ and $29-70)$

Ramesh Singh
Ramesh Singh
Numerade Educator