198 CHAPTER 5 LIQUIDS AND SOLIDS

5.30 The surface of glass contains many ∫OH groups that are Melting Electrical Solubility
bonded to the silicon atoms of SiO2, which is the major Substance Appearance point, ºC conductivity in water
component of glass. If the glass is treated with Si(CH3)3Cl A hard, white 800 only when soluble
(chlorotrimethylsilane), a reaction takes place to eliminate HCl dissolved
and attach the Si atom to the oxygen atom: in water
B lustrous, 1500 high insoluble
(surface of glass)∫OH ' Si(CH3)3Cl ¡
malleable
(surface of glass)∫OSi(CH3)3 ' HCl
C soft, yellow 113 none insoluble
How will this rearrangement affect the interaction of liquids with
the glass surface? 5.38 Three unknown substances were tested in order to classify
them. The following table shows the results of the tests. Use
5.31 The height, h, of a column of liquid in a capillary tube can Table 5.4 to classify substances X, Y, and Z as metallic, ionic,
be estimated by using h # 2,/gdr, where , is the surface tension, network, or molecular solids.
d is the density of the liquid, g is the acceleration of free fall, and
r is the radius of the tube. Which will rise higher in a tube that is Melting Electrical Solubility
0.15 mm in diameter at 25°C, water or ethanol? The density of Substance Appearance point, ºC conductivity in water
water is 0.997 g$cm%3 and that of ethanol is 0.79 g$cm%3. See
X brittle, white 146 none soluble
Table 5.3.
Y very hard, 1600 none insoluble
5.32 The expression for the capillary rise in Exercise 5.31 assumes colorless
that the tube is vertical. How will the expression be modified when Z hard, orange 398 only when soluble
the tube is held at an angle ) (theta) to the vertical? dissolved
in water
Classification of Solids
5.33 Glucose, benzophenone (C6H5COC6H5), and methane Solid Metallic Structures
are examples of compounds that form molecular solids. The 5.39 Iron crystallizes in a bcc structure. The atomic radius of iron
structures of glucose and benzophenone are given here. is 124 pm. Determine (a) the number of atoms per unit cell; (b) the
(a) What types of forces hold these molecules in a molecular coordination number of the lattice; (c) the length of the side of the
solid? (b) Place the solids in order of increasing melting unit cell.
point.
5.40 The metal polonium (which was named by Marie Curie after
her homeland, Poland) crystallizes in a primitive cubic structure,
H HO O
with an atom at each corner of a cubic unit cell. The atomic
H CH
HO 2 C radius of polonium is 167 pm. Sketch the unit cell and determine
HO O (a) the number of atoms per unit cell; (b) the coordination number
H H OH of an atom of polonium; (c) the length of the side of the unit cell.
OH
5.41 Calculate the density of each of the following metals from
H
Benzophenone the data given: (a) aluminum, fcc structure, atomic radius 143 pm;
Glucose (b) potassium, bcc structure, atomic radius 227 pm.
5.42 Calculate the density of each of the following metals from
5.34 Chloromethane (CH3Cl), methane, and acetic acid the data given: (a) strontium, fcc structure, atomic radius 215 pm;
(CH3COOH) form molecular solids. (a) What types of forces (b) europium, bcc structure, atomic radius 204 pm.
hold these molecules in a molecular solid? (b) Place the solids in
order of increasing melting point. 5.43 Calculate the atomic radius of each of the following elements
from the data given: (a) platinum, fcc structure, density 21.450 g·cm%3;
5.35 Classify each of the following solids as ionic, network, (b) tantalum, bcc structure, density 16.654 g·cm%3.
metallic, or molecular: (a) quartz, SiO2; (b) limestone, CaCO3;
(c) dry ice, CO2; (d) sucrose, C12H22O11; (e) polyethylene, a 5.44 Calculate the atomic radius of each of the following elements
polymer with molecules consisting of chains of thousands of from the data given: (a) silver, fcc structure, density 10.500 g·cm%3;
repeating ∫CH2CH2∫ units. (b) chromium, bcc structure, density 7.190 g·cm%3.
5.36 Classify each of the following solids as ionic, network, 5.45 The density of rhodium is 12.42 g·cm%3 and its atomic radius
metallic, or molecular: (a) iron pyrite (fool’s gold), FeS2; is 134 pm. Is the metal close-packed or body-centered cubic?
(b) octane (a component of gasoline), C8H18; (c) cubic boron
5.46 The density of vanadium is 6.11 g·cm%3 and its atomic radius
nitride (a compound with a structure similar to that of diamond,
is 132 pm. Is the metal close-packed or body-centered cubic?
but with alternating boron and nitrogen atoms), BN; (d) calcium
sulfate (gypsum), CaSO4; (e) the chromium plating on a 5.47 One form of silicon has density of 2.33 g·cm%3 and
motorcycle. crystallizes in a cubic lattice with a unit cell edge of 543 pm.
(a) What is the mass of each unit cell? (b) How many silicon atoms
5.37 Three unknown substances were tested in order to classify
does one unit cell contain?
them. The following table shows the results of the tests. Use
Table 5.4 to classify substances A, B, and C as metallic, ionic, 5.48 Krypton crystallizes with a face-centered cubic unit cell of
network, or molecular solids. edge 559 pm. (a) What is the density of solid krypton? (b) What is

the atomic radius of krypton? (c) What is the volume of one
krypton atom? (d) What percentage of the unit cell is empty space
if each atom is treated as a hard sphere?
5.49 What percentage of space is occupied by close-packed
cylinders of length l and radius r?
5.50 Calculate the radius of the cavity formed by three circular
disks of radius r that lie in a close-packed planar arrangement.
Check your answer experimentally by using three compact disks
and measuring the radius of the cavity that they form.
Nonmetallic Solids
5.51 Indium arsenide crystallizes in the sphalerite structure
(Fig. 5.45). (a) What are the coordination numbers of the indium
and arsenide ions? (b) What is the formula of indium arsenide?
5.52 Uranium carbide crystallizes in the rock-salt structure
(Fig. 5.41). (a) What are the coordination numbers of the uranium
and carbide ions? (b) What is the formula of uranium carbide?
5.53 Calculate the number of cations, anions, and formula units
per unit cell in each of the following solids: (a) the cesium chloride
unit cell shown in Fig. 5.43; (b) the rutile (TiO2) unit cell shown
here. (c) What are the coordination numbers of the ions in rutile?
O Ti
5.54 Calculate the number of cations, anions, and formula units
per unit cell in each of the following solids: (a) the rock-salt unit
cell shown in Fig. 5.41; (b) the fluorite (CaF2) unit cell shown here.
(c) What are the coordination numbers of the ions in fluorite?
Ca
F (at centers of small cubes)
5.55 An oxide of rhenium crystallizes with a cubic unit cell that
has a rhenium cation at each corner and an oxide ion at the center
of each edge of the crystal. (a) Determine the coordination
numbers of the two ions. (b) Write the formula of the oxide.
5.56 When an oxide of uranium crystallizes the uranium cations
form an expanded cubic close-packed array with an oxide ion in
each tetrahedral hole. (a) Determine the coordination numbers of
the two ions. (b) Write the formula of the oxide.
EXERCISES 199
5.57 Use radius ratios to predict the coordination number of the
cation in (a) RbF; (b) MgO; (c) NaBr. (See Fig. 1.48.)
5.58 Use radius ratios to predict the coordination number of the
cation in (a) KBr; (b) LiBr; (c) BaO. (See Fig. 1.48.)
5.59 Estimate the density of each of the following solids from the
ionic radii given in Fig. 1.48: (a) calcium oxide (rock-salt structure,
Fig. 5.41); (b) cesium bromide (cesium chloride structure,
Fig. 5.43).
5.60 Calculate the density of each of the following solids:
(a) magnesium oxide (rock-salt structure, Fig. 5.41), distance
between centers of Mg2' and O2% ions is 212 pm; (b) calcium
sulfide (cesium chloride structure, Fig. 5.43), distance between the
centers of the Ca2' and S2% ions is 284 pm.
5.61 Graphite forms extended two-dimensional layers (see
Fig. 5.23). (a) Draw the smallest possible rectangular unit cell for
a layer of graphite. (b) How many carbon atoms are in your unit
cell? (c) What is the coordination number of carbon in a single
layer of graphite?
5.62 The ammonium ion can be represented by a sphere of radius
151 pm. Use radius ratios to predict the type of lattice structure
found in (a) NH4F; (b) NH4I.
5.63 If the edge length of a fcc unit cell of RbI is 732.6 pm, how
long would the edge of a cubic single crystal of RbI be that
contains 1.00 mol RbI?
5.64 The edge length of the fcc unit cell of NaCl is 562.8 pm.
(a) How many unit cells are present in a single crystal of NaCl
(table salt) that is a cube with edges 1.00 mm in length? (b) What
amount (in moles) of NaCl is present in this crystal?
5.65 Why do long hydrocarbon molecules that do not have
multiple bonds, such as decane, CH3(CH2)8CH3, not form liquid
crystals?
5.66 Consider the structure of p-azoxyanisole (14). (a) Using the
VSEPR model, draw a picture that represents the shape of the
molecule and predict the CNN bond angles. (b) What features of
the bonding of this molecule give rise to its rodlike nature? (c) Use
your conclusions in part (b) to design another simple organic
molecule that is composed only of C, H, N, and O and might be
likely to form rodlike, liquid crystalline materials.
5.67 When long surfactant molecules having a polar headgroup
and a nonpolar “tail” are placed into water, micelles are formed in
which the nonpolar tails aggregate, with the polar headgroups
pointing out toward the solvent. Inverse micelles are similar but
have the nonpolar regions pointing outward. How can inverse
micelles be produced?
5.68 p-Azoxyanisole (14) has a liquid crystalline range of
approximately 117° to 137°C. How might this molecule be
modified to lower the melting point of the solid and make it more
suitable for lower-temperature applications (near room
temperature, for example)?
5.69 Two solutes were used to study diffusion in liquids,
methylbenzene, which is a small molecule that can be
approximated as a sphere, and a liquid crystal that is long and
rodlike. The two solutes were found to move and rotate in all
directions to the same extent in benzene. In a liquid crystal solvent
the methylbenzene again moved and rotated to the same extent in
all directions, but the liquid crystal solute moved much more
200 CHAPTER 5 LIQUIDS AND SOLIDS

rapidly along the long axis of the molecule than it did in a
“sideways” mode, perpendicular to the long axis. It also was found
to rotate more rapidly around the long axis than perpendicular to
it. Explain this behavior.
5.70 The molecular structures of many common liquid crystals
are long and rodlike. In addition, they contain polar groups.
Explain how both characteristics of liquid crystals contribute to
their anisotropic nature.
Integrated Exercises
5.71 Draw the Lewis structure of (a) NI3 and (b) BI3, name the
molecular shape, and indicate whether each can participate in
dipole–dipole interactions.
5.72 Draw the Lewis structure of (a) CF4, (b) SF4, name the
molecular shape, and indicate whether each can participate in
dipole–dipole interactions.
5.73 (a) Calculate the surface areas of the isomers 2,2-
dimethylpropane and pentane. Assume that 2,2-dimethylpropane
is spherical with a radius of 254 pm and that pentane can be
approximated by a rectangular prism with dimensions 295 pm "
692 pm " 766 pm. (b) Which has the larger surface area?
(c) Which do you expect to have the higher boiling point?
5.74 (a) Calculate the ratio of potential energies for an ion–ion
interaction for Li' and for K' with the same anion. (b) Repeat the
ratio calculation, but for an ion–dipole interaction between Li'
and K' and a water molecule. (c) What do these numbers indicate
about the relative importance of the hydration of salts of lithium
compared with those of potassium?
5.75 All noble gases except helium crystallize with ccp structures
at very low temperatures. Find an equation relating the atomic
radius to the density of a ccp solid of given molar mass and apply
it to deduce the atomic radius of each of the following noble
gases, given the density of each (in g·cm%3): Ne, 1.20; Ar, 1.40;
Kr, 2.16; Xe, 2.83; Rn, 4.4 (estimated).
5.76 All the alkali metals crystallize with bcc structures. (a) Find a
general equation relating the metallic radius to the density of a bcc
solid of an element in terms of its molar mass and use it to deduce
the atomic radius of each of the following elements, given the
density of each (in g·cm–3): Li, 0.53; Na, 0.97; K, 0.86; Rb, 1.53;
Cs, 1.87. (b) Find a factor for converting the density of a bcc
element into the density that it would have if it crystallized in a
ccp structure. (c) Calculate what the densities of the alkali metals
would be if they were ccp. (d) Which, if any, would float on water?
oxidation states that they can have. For example, a titanium oxide
with formula TiO1.18 is known. (a) Calculate the average oxidation
state of titanium in this compound. (b) If the compound has both
Ti2' and Ti3' ions present, what fraction of the titanium ions will
be in each oxidation state?
5.80 Uranium dioxide, UO2, can be further oxidized to give a
nonstoichiometric compound UO2'x, where 0 ) x ) 0.25. See
Exercise 5.79 for a description of nonstoichiometric compounds.
(a) What is the average oxidation state of uranium in a compound
with composition UO2.17? (b) If we assume that the uranium exists
in either the '4 or the '5 oxidation state, what is the fraction of
uranium ions in each?
5.81 Are the following statements true or false? (a) If there is an
atom present at the corner of a unit cell, there must be the same
type of atom at all the corners of the unit cell. (b) A unit cell must
be defined so that there are atoms at the corners. (c) If one face of
a unit cell has an atom in its center, then the face opposite that
face must also have an atom at its center. (d) If one face of a unit
cell has an atom in its center, all the faces of the unit cell must also
have atoms at their centers.
5.82 Are the following statements true or false? (a) Because
cesium chloride has chloride ions at the corners of the unit cell
and a cesium ion at the center of the unit cell, it is classified as
having a body-centered unit cell. (b) The density of the unit cell
must be the same as the density of the bulk material. (c) When x-
rays are passed through a single crystal of a compound, the x-ray
beam will be diffracted because it interacts with the electrons in
the atoms of the crystal. (d) All the angles of a unit cell must be
equal to 90°.
5.83 For each of the two-dimensional arrays shown here, draw a
unit cell that, when repeated, generates the entire two-dimensional
lattice.
(a) (b)

5.77 Metals with bcc structures, such as tungsten, are not close
packed. Therefore, their densities would be greater if they were to
5.84 For each of the two-dimensional arrays shown here, draw a unit
change to a ccp structure (under pressure, for instance). What
cell that, when repeated, generates the entire two-dimensional lattice.
would the density of tungsten be if its structure were ccp rather
than bcc? Its actual density is 19.3 g·cm%3.
5.78 An oxide of niobium has a unit cell in which there are oxide
ions at the middle of each edge and niobium ions at the center of
each face. What is the empirical formula of this oxide?
5.79 A number of metal oxides are known to form
nonstoichiometric compounds, in which the ratios of atoms that
make up the compound cannot be expressed in small whole
numbers. In the crystal structure of a nonstoichiometric
compound, some of the lattice points where one would have
expected to find atoms are vacant. Transition metals most easily
form nonstoichiometric compounds because of the number of (a) (b)

5.85 Buckminsterfullerene is an allotrope of carbon in which the
carbon atoms form nearly spherical molecules of 60 atoms each
(see Section 15.12). In the pure compound the spheres pack in
a cubic close-packed array. (a) The length of a side of the face-
centered cubic cell formed by buckminsterfullerene is 142 pm.
Use this information to calculate the radius of the
buckminsterfullerene molecule treated as a hard sphere. (b) The
compound K3C60 is a superconductor at low temperatures. In this
compound the K' ions lie in holes in the C60% face-centered cubic
lattice. Considering the radius of the K' ion and assuming that
the radius of C60– is the same as for the C60 molecule, predict in
what type of holes the K' ions lie (tetrahedral, octahedral, or
both) and indicate what percentage of those holes are filled.
5.86 A reflection from a cubic crystal was observed at a glancing
angle of 12.1° when x-rays of wavelength 152 pm were used.
(a) What is the separation of layers causing this reflection? (b) At
what glancing angle would you detect the reflection arising from
planes at twice the layer separation? Refer to Major Technique 3
on x-ray diffraction, which follows this set of exercises.
5.87 Glass is composed mainly of silica, SiO2, with various oxides
added to change the properties. The property differences are
substantial, and different amounts of added oxide compounds
produce glasses with very different applications derived from these
properties. Often the added material is B2O3 and the products
are called borosilicate glasses. From standard reference sources,
determine how the properties of glass change as the amount of
B2O3 is increased.
5.88 In an aqueous solution, solute molecules or ions require a
certain amount of time to migrate through the solution. The rate
of this migration sets an upper limit on how fast reactions can
take place, because no reaction can take place faster than the ions
can be supplied. This limit is known as the diffusion-controlled
rate. It has been found that the diffusion rate for hydrogen ions is
about three times as fast as that for other ions in aqueous solution.
Explain why this is so.
5.89 Iron corrodes in the presence of oxygen to form rust, which
for simplicity can be taken to be iron(III) oxide. If a cubic block of
iron of side 1.5 cm reacts with 15.5 L of oxygen at 1.00 atm and
25°C, what is the maximum mass of iron(III) oxide that can be
produced? Iron metal has a bcc structure, and the atomic radius of
iron is 124 pm. The reaction takes place at 298 K and 1.00 atm.
5.90 Real gases and vapors have intermolecular interactions.
Recall that one equation of state for a real gas is the van der Waals
equation, which is expressed in terms of two parameters, a and b.
(a) For each of the following pairs of gases, decide which
substance has the larger van der Waals a parameter: (i) He and Ne;
(ii) Ne and O2; (iii) CO2 and H2; (iv) H2CO and CH4; (v) C6H6
and CH3(CH2)10CH3. (b) For each of the following pairs of gases,
decide which substance has the larger van der Waals b parameter:
(i) F2 and Br2; (ii) Ne and F2; (iii) CH4 and CH3CH2CH3;
(iv) N2 and Kr; (v) CO2 and SO2.
5.91 A commonly occurring mineral has a cubic unit cell in which
the metal cations, M, occupy the corners and face centers. Inside the
unit cell, anions, A, occupy all the tetrahedral holes created by the
cations. What is the empirical formula of the MmAa compound?
5.92 Tetrahedral and octahedral interstitial holes are formed by the
vacancies left when anions pack in a ccp array. (a) Which hole can
accommodate the larger ions? (b) What is the size ratio of the
largest metal cation that can occupy an octahedral hole to the
EXERCISES 201
largest that can occupy a tetrahedral hole while maintaining the
close-packed nature of the anion lattice? (c) If half the tetrahedral
holes are occupied, what will be the empirical formula of the
compound MxAy, where M represents the cations and A the anions?
5.93 The density of cesium chloride is 3.988 g·cm%3. Calculate the
percentage of empty space in a cesium chloride lattice with the
ions treated as hard spheres.
5.94 Use information from Exercise 5.54 to calculate the
percentage of empty space in a calcium fluoride lattice with the
ions treated as hard spheres. The density of CaF2 is 3.180 g·cm%3.
5.95 (a) If a pure element crystallizes with a primitive cubic lattice,
what percentage of the unit cell is empty space? (b) How does this
percentage compare with that of empty space in an fcc unit cell?
5.96 Many ionic compounds are considered to pack in such as
way that the anions form a close-packed lattice in which the metal
cations fill holes or interstitial sites left between the anions. These
lattices, however, may not necessarily be as tightly packed as
the label “close-packed” implies. The radius of an F% ion is
approximately 133 pm. The edge distances of the cubic unit cells
of LiF, NaF, KF, RbF, and CsF, all of which pack in the rock-salt
structure, are 568 pm, 652 pm, 754 pm, 796 pm, and 850 pm,
respectively. Which of these lattices, if any, can be thought to be
based on close-packed arrays of F% ions? Justify your conclusions.
5.97 Due to its strong hydrogen bonds, in the vapor state hydrogen
fluoride is found as short chains and rings. Draw the Lewis structure
of an (HF)3 chain and indicate the approximate bond angles.
5.98 Consider a metallic element that crystallizes in a cubic
close-packed lattice. The edge length of the unit cell is 408 pm. If
close-packed layers are deposited on a flat surface to a depth (of
metal) of 0.125 mm, how many close-packed layers are present?
5.99 “Graphite bisulfates” are formed by heating graphite with a
mixture of sulfuric and nitric acids. In the reaction, the graphite
planes are partially oxidized. There is approximately one positive
charge for every 24 carbon atoms, and the HSO4% anions are
distributed between the planes. (a) What effect is this oxidation
likely to have on the electrical conductivity? (b) What effect would
you expect it to have on the x-ray diffraction pattern observed for
this material? Refer to Major Technique 3 on x-ray diffraction,
which follows this set of exercises.
5.100 Using the density of calcium fluoride (CaF2, found in nature
as the mineral fluorite), which is known to be 3.180 g·cm%3, and the
information given in Exercise 5.54, calculate (a) the edge length of
the unit cell and (b) the Ca–F separation in fluorite. (c) Compare
this value to that expected from the ionic radii tabulated in Fig. 1.48.
5.101 The following diagram shows two lattice planes from which
two parallel x-rays are diffracted. If the two incoming x-rays are in
phase, show that the Bragg equation 2d sin ) # n! is true when n
is an integer. Refer to Major Technique 3 on x-ray diffraction,
which follows this set of exercises.
1
X-rays
2
6
Lattice layer 1
d
Lattice layer 2
202 CHAPTER 5 LIQUIDS AND SOLIDS
5.102 X-rays generated from a copper target have a wavelength of
154 pm. If an x-ray beam of this type is passed through a single
crystal of NaBr, a diffracted beam is observed when the incident
x-ray beam is at an angle of 7.42° to the surface of the crystal.
What is the minimum spacing between the planes in the crystal
that give rise to this diffracted beam? Refer to Major Technique 3
on x-ray diffraction, which follows this set of exercises.
5.103 The unit-cell edge length of lithium fluoride is 401.8 pm.
What is the smallest angle at which the x-ray beam generated from
a molybdenum source (! # 71.07 pm) must strike the planes
making up the faces of the unit cell for the beam to be diffracted
from those planes? Refer to Major Technique 3 on x-ray
diffraction, which follows this set of exercises.
5.104 Could electrons be used for diffraction studies of molecules?
The energy of an electron accelerated through a potential
difference V (in volts) is eV. What potential difference is needed to
accelerate electrons from rest so that they have a wavelength of
100 pm? Hint: Use the de Broglie relation and the fact that
acceleration of an electron to an energy eV gives it a kinetic energy
of 12 mev2. Refer to Major Technique 3 on x-ray diffraction, which
follows this set of exercises.
5.105 Could neutrons be used for diffraction studies of molecules?
The average kinetic energy of neutrons in a beam at a temperature T
is 12kT, where k is Boltzmann’s constant. What temperature is needed
to achieve a wavelength of 100. pm for a neutron? Refer to Major
Technique 3 on x-ray diffraction, which follows this set of exercises.
5.106 Calculate the Coulomb potential energy at a point a distance
r from a dipole composed of charges Q and ∫Q separated by a
distance l in the arrangement shown in the diagram. Use the fact
that l ) r to expand the expression 1/(1 ' x) into 1 % x ' · · · and
identify the magnitude of the dipole moment as % # Ql. Show that
the potential energy is proportional to 1/r 2 (as in Eq. 2).
r
l
'Q %Q
Chemistry Connections
5.107 Ethylammonium nitrate, CH3CH2NH3NO3, was the
first ionic liquid to be discovered. Its melting point of 12°C
was reported in 1914 and it has since been used as a
nonpolluting solvent for organic reactions and for facilitating the
folding of proteins.
(a) Draw the Lewis structure of each ion in ethylammonium
nitrate and indicate the formal charge on each atom (in the cation,
the carbon atoms are attached to the N atom in a chain:
C∫C∫N).
(b) Assign a hybridization scheme to each C and N atom.
(c) Ethylammonium nitrate cannot be used as a solvent for some
reactions because it can oxidize some compounds. Which ion is
more likely to be the oxidizing agent, the cation or anion? Explain
your answer.
(d) Ethylammonium nitrate can be prepared by the reaction of
gaseous ethylamine, CH3CH2NH2, and aqueous nitric acid.
Write the chemical equation for the reaction. What type of
reaction is this?
(e) 2.00 L of ethylamine at 0.960 atm and 23.2°C was bubbled into
250.0 mL of 0.240 M HNO3(aq) and 4.10 g of ethylammonium
nitrate was produced. What were the theoretical and percentage
yields of the salt?
(f) Suggest ways in which the forces that hold ethylammonium
nitrate ions together in the solid state differ from those that hold
together salts such as sodium chloride or sodium bromide.
(g) Low-melting salts in which the cation is inorganic and the
anion organic have been prepared. Explain the trend in melting
point seen in the following series: sodium acetate (NaCH3CO2),
324°C; sodium propanoate (NaCH3CH2CO2), 285°C; sodium
butanoate (NaCH3CH2CH2CO2), 76°C; and sodium pentanoate
(NaCH3CH2CH2CH2CO2), 64°C.
 MAJOR TECHNIQUE 3 X-RAY DIFFRACTION
A great deal of our knowledge about the interior of solids has
come from x-ray diffraction. This important technique is
used to determine the arrangement of atoms in solid compounds
and to measure bond lengths and angles. Almost all recent
advances in molecular biology have stemmed from the applica-
tion of this technique to determine the structures of molecules
such as proteins and nucleic acids.
The Technique
When two or more waves pass through the same region of space,
the phenomenon of interference is observed as an increase or a
decrease in the total amplitude of the wave (recall Fig. 1.20).
Constructive interference, an increase in the total amplitude of
the wave, occurs when the peaks of one wave coincide with the
peaks of another wave. If the waves are electromagnetic radia-
tion, the increased amplitude corresponds to an increased inten-
sity of the radiation. Destructive interference, a decrease in the
total amplitude of the waves, occurs when the peaks of one wave
coincide with the troughs of the other wave: it results in a reduc-
tion in intensity.
The phenomenon of diffraction is interference between
waves that arises when there is an object in their path. One of
the earliest demonstrations of interference was the Young’s slit
experiment, in which light passes through two slits and gives rise
to a pattern on a screen (see Fig. 1.19). If we were presented with
the pattern and were told the wavelength of the light and the dis-
tance of the detection screen from the screen containing the slits,
it would be possible to work out the spacing of the two slits. An
x-ray diffraction experiment is a more elaborate version of the
Young’s slit experiment. The regular layers of atoms in a crystal
act as a three-dimensional collection of slits and give rise to a
diffraction pattern that varies as the crystal is rotated and the
“slits” are brought into a new arrangement. The task for the
x-ray crystallographer is to use the diffraction pattern to deter-
mine the spacing and arrangement of the “slits” that gave rise to
it. This enormously complex task is universally carried out on
computers.
Why x-rays? Diffraction occurs when the wavelength of the
radiation is comparable to characteristic spacings within the
object causing the diffraction. Therefore, to obtain diffraction
patterns from layers of atoms, we need to use radiation with a
wavelength comparable to the spacing of the layers. The separa-
tion between layers of atoms in a crystal is about 100 pm, and so
electromagnetic radiation of that wavelength, which corre-
sponds to the x-ray region, must be used.
Experimental Techniques
X-rays are generated by accelerating electrons to very high speeds
and then letting them plunge into a metal target. This technique
generates two types of x-radiation. One type comes from the
bombarding electrons themselves. Because accelerating and decel-
erating charges emit electromagnetic radiation, the electrons gen-
erate radiation as they are brought to a standstill in the metal. The
radiation covers a wide range of frequencies, including that of
Angle 6
Detector
Diffracted
Incident ray
x-rays
6
FIGURE 1 In the powder diffraction technique, a sample is spread
on a flat plate and exposed to a beam of monochromatic (single-
frequency) x-rays. The diffraction pattern (inset) is recorded by moving
the detector to different angles.
x-rays. However, for current versions of x-ray diffraction, we need
a well-defined wavelength. Such radiation is generated by a second
mechanism. The fast electrons hit electrons occupying orbitals in
the inner shells of atoms and drive them out of the atom. That
collision leaves a gap in the atom, which is filled when an electron
in another shell falls into the vacancy. The difference in energy is
given out as a photon. Because the energy difference between
shells is so great, the photon has a very high energy, correspond-
ing to the x-ray region. When copper is used as the target, for
example, the x-radiation has a wavelength of 154 pm.
In the powder diffraction technique, a monochromatic (sin-
gle-frequency) beam of x-rays is directed at a powdered sample
spread on a support, and the diffraction intensity is measured as
the detector is moved to different angles (Fig. 1). The pattern
obtained is characteristic of the material in the sample, and it
can be identified by comparison with a database of patterns. In
effect, powder x-ray diffraction takes a fingerprint of the sam-
ple. It can also be used to identify the size and shape of the unit
cell by measuring the spacing of the lines in the diffraction pat-
tern. The central equation for analyzing the results of a powder
diffraction experiment is the Bragg equation
2d sin ) # !
which relates the angles ) (theta), at which constructive interfer-
ence occurs, to the spacing, d, of layers of atoms in the sample,
for x-rays of wavelength ! (lambda). The illustration in Exer-
cise 5.101 shows how the parameters ! and d relate to the crystal
dimensions.
EXAMPLE MT 3.1 Determining the spacing between
layers of atoms in a crystal
In an x-ray diffraction experiment on a single crystal of sodium
chloride, with the use of radiation from a copper source (! #
154 pm), constructive interference was observed at ) # 11.2°.
What is the spacing of the layers responsible for the diffraction?
PLAN Spacing between layers in a crystal can be obtained from
the Bragg equation.
(continued)
203