rl EXP
L! RIM NT
The Estimotion of Avogodro's Number
L
f The hypothesis, published in I8II, was perhaps
Purpose
L . Make an order-of-magnitude estimate of the size
of a carbon atom based on simple assumptions
(.- about thd spreading of a thin film of stearic acid on
a water surface.
r Estimate the number of atoms in a mole of
carbon (12.0 g C) using the estimated size of a
-f carbon atom and the density of the diamond form
of carbon.
Pre-Lob Preporotion
L John Dalton (L766-1844) was so taken with the
notion of atomism that he never quite grasped the
\- distinction between an atom and a molecule of an
element. The most stable form of many elements,
L such as oxygen, hydrogen, and the halogens, is not a
single atom but a diatomic molecule. Because Dalton
L believed that the smallest unit of an element must be
an atom, he had a hard time accepting Gay-Lussac's
data about the combining volumes of gases.
L The reconciliation between Dalton's theory and
Gay-Lussac's data was brought about by Amedeo
(-_ Carlo Avogadro (1776-L856). He accomplished this
by making the distinction between an atom and a
molecule of an element and by making the hypothe-
sis that equal volumes of gases contain equal num-
bers of molecules. For example, if you believe that
t hydrogen and chlorine are monoatomic and that
equal volumes of gases (at the same temperature and
pressure) contain equal numbers of atoms, then one
volume of hydrogen should react with one volume of
chlorine to form one volume of HCI:
('-_
H(g)+Cl(g)+HCl(g)
L But when you do the experiment, you will find that
two volumes of HCI are produced. Avogadro inter-
preted this result by assuming that the smallest unit
of hydrogen and chlorine is a diatomic molecule, not
an atom, and by writing the equation as follows:
I Hz(g)+C12(g)-2HCl(C)
Many subsequent experiments have proved that Avo-
i
gadro's explanation was correct.
T:
ahead of its time and went virtually unnoticed.
More than half a century passed before Stanislao
Cannizzaro (i826-I9I0) demonstrated the general
applicability of the hypothesis in an article pub-
lished in 1858. When he distributed it in pamphlet
form at the first international chemical congress at
Karlsruhe, Germany, in I860, the pamphlet so clearly
and completely discussed atoms, molecules, atomic
weights, and molecular weights that chemists were
convinced of his views and quietly incorporated
them into chemical thinking. Fifty years of ponder-
ing Dalton's atomic theory had created the right
moment for the acceptance of Avogadro's hypothe-
sis. Cannizzaro gave credit to Avogadro as well as to
Ampdre and Dumas, and no doubt it was Cannizzaro
who saved Avogadro's hypothesis from oblivion. As a
result, today we call the number of particles (atoms
or molecules) in a mole Avogadro's number.
How many particles are there in a mole? Avo-
gadro did not invent or use the concept of a mole
and never knew the number of particles in a mole. In
I865, a few years after Avogadro's death, the German
chemist Joseph Loschmidt (1821-1895) published an
article estimating the size of a molecule and,
although Loschmidt didn't present the calculation in
his paper, it is possible from the calculations he did
present to estimate the number of molecules in a
cubic centimeter of gas. This is only one simple step
away from determining the number of molecules in a
mole. For this reason, German chemists often called
the constant Loschmidt's number rather than
Avogadro's number, and the International Union of
Pure and Applied Chemistry (IUPAC) allows the use of
either the symbol No or I for Avogadro's number, to
honor the contributions of both men.
A French scientist, Jean Perrin (1870*1942), is
often given credit for determining the first value of
Avogadro's number in 1908. Perrin measured the verti-
cal distribution in the earth's gravitational field of
gamboge (a natural resin) particles suspended in water
and obtained values in the range 5.4 to 6.0 x 1023.
After the American physicist Robert Millikan
determined the charge of an electron around 191 5, a
more accurate value was obtained by dividing the
ro-r
to-2 The Estimotion of Avogodro's Number

charge of a mole of electrons (the Faraday constant) Su rface

by the charge of a single electron. More refined val- l.

ues have been obtained by accurate measurements

of silicon crystals by X-ray diffraction: dividing the
volume of one mole of silicon by the effective vol-
ume of a silicon atom yields Avogadro's number.
All of the refined measurements require sophisti-
cated and expensive equipment and great care in
l-
experimental technique and treatment of data. The
payoff is the most accurate value of Avogadro's num-
ber, N6, that we have to date: No : 6.02214086 x I023 Molecules
particles/mol. This is one of the numbers you will i
encounter in introductory chemistry that is worth FIGURE IO-l * The action of molecular forces at a
remembering. liquid surface creates a surface tension that
tends to minimize the surface area of the liquid.
The mole is a fundamental unit in the Interna-
tional System (SI) of units. A mole of carbon is pre-
cisely I2.000000 g of carbon-12, and Avogadro's
number is defined as the number of atoms in a mole
If the liquid is water, the surface tension is espe-
of carbon- I 2. cially strong because particularly strong intermolec-
ln this experiment, you will make an approxi- ular forces, called hydrogen bonds, exist between the
mate (order-of-magnitude) estimate of Avogadro's water molecules. (While strong for intermolecular
number by determining the amount of stearic acid bonds, these bonds are still considerably weaker
that it takes to form a single layer (called a mono- than the intramolecular covalent bonds that bind
layer) on the surface of water. By making simple atoms together in a molecule.) Hydrogen bonding
arises whenever a hydrogen atom that is attached to
assumptions about the way the stearic acid mole-
a highly electronegative atom, such as oxygen, has
cules pack together to form the monolayer, we can
access to an unbonded pair of electrons, such as
determine its thickness; from that thickness, we can
those of another oxygen atom.
estimate the size of a carbon atom. Knowing the size
Another property displayed by water is polarity.
of a carbon atom, we can compute its volume. If we
Polar molecules possess a separation of charge. In
know the volume occupied by a mole of carbon (in
ionic compounds, such as NaCl, there is a separation
the form of diamond), we can divide the volume of a
of a full unit charge, Na+ . . . Cl . Polar covalent mole-
mole of carbon by the volume of an atom of carbon
cules display a partial separation of charge, denoted
to get an estimate of Avogadro's number. The num-
ber won't be accurate to within lO% or even a factor
by delta, 6. An arrow is used to denote this charge
separation. This polarity, referred to as the dipole
of 2, but it will enable you to estimate to within
moment, is equal to the partial charge times the dis-
about a power of l0 the number of particles in a
tance separating the charges; it is represented by an
mole. That's better than chemists could do only 100
years ago. arrow pointing toward the negative end of the mole-
cule. Figure 10-2 displays the polar nature of the
water molecule.
Concepts of the experiment
Polar molecules attract each other. The negative
Matter can exist in three states: as a gas, liquid, or end of the dipole of one molecule is attracted to the
solid. The fact that a gas can be condensed to a liquid positive end of the dipole of another molecule. For \_
and a liquid frozen to a solid indicates that there are this reason, water dissolves formic acid, H-COOH,
attractive forces between all molecules. We can
schematically represent these forces at the surface of
a liquid by the arrows in Figure 10-1.In the interior of
<------f
6*
the liquid, the forces exerted on a given molecule are H
uniform in all directions. At the surface, however, it is
clear that there is a net force attracting each surface 52- 0
molecule inward. These molecules have higher ener-
H
gies than do interior molecules, thus giving rise to 6*
the force known as surface tension. It is because of
this force that liquid droplets are spherical. A spheri- FIGURE tO-2 {rne bond polarity and angular
cal shape presents the smallest surface area for a structure of a water molecule create a dipole
given volume. moment.
 The Estimotion of Avogodro's Nr*b", l lo-3
t

which has a dipole morhent, but it does not dissolve Surface area /
\ butane, CH3CH2CH2CHT, which has a nearly uniform
charge distribution. If a molecule possessing the
properties of both of these molecules is brought up
to the surface of water, the polar part of the mole-
cule will be attracted to the surface and the nonpo-
lar portion will be repelled. If the nonpolar part is
much larger than the polar portion, the molecule
will not dissolve in water but will simply stick to its
surface. Consequently, it will lower the energy of
the surface water molecules and of the adhering
molecules.
The molecule we will use in this experiment,
L stearic acid, behaves in just this way. Stearic acid has
a polar end consisting of a carboxyl group, -COOH, :t
Water

FIGURE IO-4 ii Magnified view of a stearic acid film

and a large nonpolar "tail" consisting of 16 methyl- (not to scale). The stearic acid molecules orient
\ ene groups, -CHz-, terminating in a methyl group, themselves vertically because of the attraction of
-CH3. Figure 10-3 is a reasonably accurate represen- their polar ends (the COOH groups) to the water
tation of this molecule. molecules at the water surface and the weak
Adding a limited number of stearic acid mole- attractive forces between their hydrocarbon tails.
cules to a water surface results in the formation of a The volume of the stearic acid monolayer is the
product of surface area times thickness (A x t),
monolayer, as illustrated in Figure 10-4. However,
after the surface is covered with a monolayer of
stearic acid molecules, the addition of more mole-
cules causes the stearic acid molecules to cluster in
H globular aggregates. The polar heads are attracted to
the polar water molecules and form a lens-shaped
-H surface, with the hydrocarbon tails pointing inward
H
to form an "oily" interior.
H H The properties of the water surface and the
H H stearic acid molecule permit us to perform what
amounts to a titration of the water surface. We can
H
add stearic acid molecules to the water surface until
H H a monolayer covers the entire surface. Further addi-
H
tion will cause a convex lens to form on the liquid
surface. At this point, the stearic acid molecules are
H
-H stacked on the water surface like a layer of cord-
H wood turned on end. If we know the area of the sur-
-H face of water and have a way of measuring the volume
H
-H of substance added to form the monolayer, we can cal-
H
-H culate the thickness, r, of the layer. This thickness
H equals approximately the length of the stearic acid
-H molecule.
H
-C -H
I
As we saw in Figure 10-3, this molecule consists
H
-C -H of 18 carbon atoms linked together. If we make the
H-C
I
simple assumption that the atoms are like little
-H cubes linked together (Figure 10-5), the edge length
H-C _H
I

of a cube of carbon is given by t/18. If we cube the

edge length, we have estimated the volume of a car-
bon atom. Now we have half the data needed to cal-
B
culate Avogadro's number.
The other necessary data require no experimental
'''"''-'''"'' ;:
work on your part. What we need is the volume of a
FIGURE I O-3 I rtre stearic acid molecule.
(A) space-filling model; (B) structural formula; mole of carbon. Diamond is pure carbon, and the
(C) schematic "matchstick" representation. density of diamond is known to be 3.51 g/cm3. You
ro-4 The Estimotion of Avogodro's Number
ti
FIGURE tO-5 ii ror purposes of our estimate, each
stearic acid molecule can be approximated as a
vertical stack of l8 carbon atoms with a total
height equal to the thickness, t, of the monolayer
film. Each carbon atom then has a diameter, s,
equal to %e of the film thickness. When the empty
space between the atoms is included, the gross
volume of each atom, V",o- = g3.
may recall that you can calculate the molar volume
of an element by dividing the molar mass (g/mol) by
its density (g/cm3). Verify this idea by looking at the
dimensions of this quotient.
If we assume that diamond consists of little cubes
of carbon atoms stacked together, an Avogadro's num-
ber of them would equal the volume of one mole. Avo-
gadro's number results from one final step:
molar volume (cm3, e)
atomic volume (cm ',/atom)
: number of atoms/mol
Experimentol Procedure
Special Supplies: 14-cm watch glass; centimeter rule
or meterstick; fine-tipped (50 drops/ml) polyethylene
transfer pipets; 1-mL all-polypropylene syringes (Norm-
ject Luer Slip I x 0.01 mL syringes are available from
Air-Tite Products Co., Inc., www.air-tite-shop.com, tel
8OO-23I 7762); pure Type I water, free of surface active
materials (preferably distilled or passed through a water
purifier); disposable rubber gloves (if students will
be cleaning their own watch glasses in 0.1 M NaOH in
50/50 methanol/water); I3 x I00 mm test tubes with
corks to fit.
Chemicals: Hexane, O.lO S/L stearic acid (purified
grade) solution in hexane. The exact weight/volume
\:
concentration of this solution will be provided by
your instructor. 0.1 M NaOH in 50,/50 methanol/water
(volume/volume, or v,/v), used for washtng the watch
glasses.
|$i$l|i NorEs To INSTRUCTOR .
A purified (98%) grade of stearic acid gives the best
results and is available commercially (Sigma-Aldrich).
Instead of using a dropper and counting drops,
we prefer to use a 1 mL all-polypropylene syringe so
that the volume of stearic acid solution in hexane
can be read directly. Using the syringe also mini
mizes evaporation of the hexane solvent. The Luer
tip of the syringe is fitted with a tip cut from a fine-
tipped polyethylene transfer pipet, as shown in Fig-
ure I-14 of the Introduction. Another device for dis-
pensing the stearic acid solution is described by
Lane et al. (1984). (See the Bibliography.)
The watch glasses should be soaked in the
methanolic NaOH solution in a polyethylene basin
overnight or at least for an hour or two before the
beginning of the laboratory period. The watch
glasses should then be rinsed in distilled water
before they are distributed to the students. Distilled
water (or Type I water produced by a Millipore Milli-Q
or Barnstead Nanopure purifier) is better for this
experiment than deionized water because deionized
water often contains organrc substances leached
from the organic resins used to deionize the water.
\__
SAFETY PRECAUTIONS:
I Hexane is flammable! There must
be no open flames in the laboratory while
hexane is being used.
If you clean your own watch glasses by
soaking them in methanolic NaOH, you
must wear rubber gloves to protect your
hands. As always, wear eye protection in
the laboratory.
/\ wAsrE coLrECroN:
':va\ At the end of the experiment, unused
hexane solvent and stearic acid in hexane
solution should be placed in a waste
container marked "Waste hexane/stearic acid
solution in hexane."
l
i-

\ Preparation of Eqaipment Stearic acid is a solid. It
is conveniently measured and applied to the water
I
surface by dropping a solution of stearic acid in
hexane onto the water. The hexane is insoluble in
water. Because it has a high vapor pressure, it rap-
idly evaporates, leaving a layer of stearic acid spread
on the water surface one molecule thick, called a
monolayer.
Because stearic acid is one of the fatty acids pres-
\- ent in soaps, you must not clean your watch glass
with soap. Any soap, grease, or dirt present can form
'\_
I
a film on the water that prevents the stearic acid
from spreading on the surface, leading to meaning-
\._ less results because not even the first drop will
spread.
Obtain a 14-cm watch glass. If it has not been
\ soaked in the methanolic NaOH solution described in
the Chemicals section, wash it thoroughly with
\r_ detergent. Rinse the detergent off completely under
a full stream of cold tap water for a minute, then
rinse thoroughly with distilled water. Repeat the
washing after each experiment, or obtain another
watch glass that has been soaked in methanolic
L NaOH. Handle the watch glass only by the edges,
being especially careful not to let anything touch the
inside of it. Be particularly careful to keep your fin-
gers (which are usually slightly greasy) off the glass.
L 7. Measuring the Volame of Stearic Acid Solution
Required to Cover the Water Sarface Obtain
(- about 3-4 mL 0.I0 g/L stearic acid solution in hexane
in a clean, dry I3 x 100 mm test tube. Keep the tube
L corked when not in use. Fill the clean watch glass to
the brim with distilled water. Carefully measure the
diameter of the water surface with a centimeter rule
i_ or meterstick. Cut off the tip of a fine-tipped poly-
ethylene transfer pipet about 25 mm from the tip
end and push the cut-off tip onto the Luer fitting on
the end of the syringe. Next, rinse and fill your
I-mL syringe with stearic acid solution, taking care
to eliminate bubbles in the solution inside the
syringe.
(._
Read and record the initial volume reading of the
syringe. Then add the stearic acid solution drop by
drop to the water surface. Initially, the solution will
spread across the entire surface, and it will continue
to do so until a complete monolayer of stearic acid
has been produced. As this point is approached, the
spreading will become slower and slower, until
\_ finally a drop will not spread out but will instead sit
on the surface of the water (looking like a little con-
tact lens). If this "lens" persists for about 30 s, you
can safely conclude that you have added I drop
more than is required to form a complete monolayer.
Now record the final volume reading of the syringe.
\r*
The Estimotion of Avogodro's Number ro-5
Thoroughly clean the watch glass (or get another
one), and repeat the experiment. Repeat until the
results agree to within 2 or 3 drops (0.04 mL).
When you have completed all of your measure-
ments, rinse your syringe with pure hexane, and dis-
pose of all the hexane-containing solutions in the
waste collection bottle provided.
2, Calcalating Avogadro's Number The calcula-
tion proceeds in several steps. First, we calculate the
volume of stearic acid solution in hexane required to
deliver enough stearic acid to form a monolayer. All
of the hexane evaporates, leaving only the thin
monolayer film of stearic acid, so we next calculate
the actual mass of pure stearic acid in the monolayer.
Then we calculate the thickness of the stearic
acid monolayer, using the known density of stearic
acid and the area of the monolayer. Assuming the
stearic acid molecules are stacked on end and are
tightly packed, and knowing that there are I8 carbon
atoms linked together in the stearic acid molecule,
we calculate the diameter and volume of a carbon
atom.
Finally, we calculate the volume of a mole of car-
bon atoms in diamond; dividing the molar volume
of carbon (diamond) by the volume of a single car-
bon atom, we obtain an estimate of Avogadro's
number.
W coNstDER rHIs W
The method we employed in this experiment is not
especially accurate. There are other experimental
ways to get values for Avogadro's number. For exam-
ple, if you divide the electric charge on a mole of
electrons (the Faraday constant) by the electric
charge on a single electron, you will obtain the num-
ber of electrons in a mole of electrons, which is Avo-
gadro's number. Try it, using values for the constants
found in Table 2 of the Appendix.
Because atoms are so small, the magnitude of
Avogadro's number is so large that it is almost
impossible to comprehend it. Try this exercise to get
a grip on it. First, imagine that you have 64 toy
alphabet blocks arranged in a cube, where each block
is itself a cube, 2 in. on an edge. The cube of 64
blocks would be 8 in. in three dimensions, with 4
blocks along each edge. Then flatten the cube into a
square containing 64 blocks. How large would the
square be, and how many blocks will be along its
edge? Finally, arrange the 64 blocks in a line. How
long would the line be?
Now that you have the idea, imagine an Avo-
gadro's number of tiny cubes, the edge length of
 r0-6 The Estimotion of Avogodro's Number

each tiny cube being about the size of a hydrogen Feinstein, H. [., Sisson, R. F., III., "The Estimation of
atom (1.00 x 10-10 m). If you had an Avogadro's Avogadro's Number Using Cetyl Alcohol as the
number of hydrogen atom cubes arranged into a Monolayer," J. Chem. Educ. 1982, 59,751.
large cube (like the alphabet blocks), what would the Hawthorne, R. M., Jr., "Avogadro's Number: Early Values
edge length of the cube be? If you then flattened the by Loschmidt and Others," J. Chem. Educ. 197O, 47,
cube into a square, what would the edge length of 7 51-755.
the square be? Finally, if you arranged the Avogadro's
Henry, P. S., "Evaluation of Avogadro's Number" (by the
number of tiny H-atom cubes into a line, how long
method of Perrin), J. Chem. Educ. 1966, 43,251.
would the line be? Compare it with the earth-to-sun
Uses Perrin's method.
distance of 93 million miles.
In the method we used, we made a number of Jensen, W. B., "How and When Did Avogadro's Name
simplifying assumptions. Some of these are dis- become Associated with Avogadro's NumberT"
cussed in the Consider This section of the Report J. Chem. Educ. 2OO7, 84, 223.
form, and their effects are quantitatively assessed. I(ing, L. C., Neilsen, E. K., "Estimation of Avogadro's
The cumulative effect of the simplifying assump- Number," J. Chem. Educ. 1958,35, 198.
tions is to cause the final result for Avogadro's num- Lane, C. A., Burton, D. E., Crabb, C. C., "Accurate
ber to be a factor of about three times too large. Molecular Dimensions from Stearic Acid
i.*]*r*iEwt*m!iilr&3*i5&i*l$tiirts'q*:ffii;tiiiiii*t&ilt!i:ira!!!i!ri,isrlit:*lli:al{lit!itli--,aef:.rer!!.:l Monolayers," J. Chem. Educ. 1984,61, 815.
Porterfield, W. W., Kruse, W., "Loschmidt and the
Discovery of the Small," J. Chem. Educ. LggS,
Bibliogrophy 72, 87 0-87 s .

Boorse, H. A., Motz, L. (eds.), "The Determination of Robinson, A. L., "Metrology: A More Accurate
Avogadro's Number," The World of the Atom, Basic Value for Avogadro's Number," Science L974,
Books, New York, I966, Vol. l, pp. 625-640. 185, rC37.
Describes Perrin's method. Slabaugh, W. H., "Determination of Avogadro's Number
Diemente, D., "Demonstrations of the Enormity of by Perrin's Law," J. Chem. Educ. L965,42,471.
Avogadro's Number," J. Chem. Educ. 1998, 75, Slabaugh, W. H., "Avogadro's Number by Four Methods,"
I 565-l 566. J. Chem. Educ. 1969, 46,40.

\-

\*
o REPORT I O
The Estimation of Avogadro's Number
u Name

Date Section
1l
', '" Locker Instructor_
\
lu

l- Doto ond Colculotions

Note: A number of calculations are required in this report. Show the calculations for only one of your trials, but
[.- give the results for both trials, those for trial 1 in the left blank and those for trial 2 in the right.

I l. Meosuring the volume of steoric ocid solution required lo cover the woter surfoce
Trial 1 Trial 2

(a) Record the diameter of the water surface: CM cm

(b) Record the volume of stearic acid solution required

to cover the surface: mL mL

(c) Record the concentration of the stearic acid solution o /l

c/L

2. Colculqfing Avogodro's number

(a\ Calculating the thickness of a monolayer of stearic acid
(i)Based on your part I data, what was the volume of stearic acid solution required to form a
monolayer?

mL mL

(ii)
Calculate the mass of stearic acid contained in that volume of stearic acid solution (the
concentration in grams per liter will be given to you):

o
b o
6

(iii)Calculate the volume, \1 of pure stearic acid in the monolayer on the water surface. The density of
solid stearic acid is 0.85 g/ml (or g/cm3):

mL (cm3) mL (cm3)
(iv) Calculate the area of the monolayer (A : ,f; r is the radius of the water surface)

cm2 cm2

(v) Calculate the thickness of the monolayer (t : volume/area: V,/A)

CM cm

\_,
to-7
 (

lbl Estimating the size and volume of a carbon atom

(i) A stearic acid molecule consists of 18 carbon atoms linked together. Assuming that the thickness, t,
of a monolayer is equal to the length of the stearic acid molecule, calculate the size of a carbon atom,
s: r/18:

cm CIn

(ii) Assuming that a carbon atom is a little cube, calculate the volume of a carbon atom, volume : s3:

%,o. cm3/atom cm3/atom

lcl Cqlculating the volume of a mole of carbon atoms i

(i) Calculate the molar volume of carbon (diamond) by using the density of diamond (3.51 g/cm3) and
the atomic mass of a mole of carbon:

V-nl cm3lmol cm3lmol

(ii) Is the volume of a mole of diamond the same as the actual volume of a mole of carbon atoms?

ld't Calculating Avogadro's number: Divide the volume of a mole of carbon atoms (diamond) calculated in 2(c)
by the volume of a single carbon atom calculated in 2(b).
(i) Calculate Avogadro's number from the appropriate ratio of volumes:

atoms/mol atoms,/mol
(ii) Calculate the average value of No from your results

Average atoms/mol
(el Express your results as a number x 1023. Are you within a power of 10 of the accepted value of 6.02 x 1023?

\*

ffiffiffi coNsrDER THrs ffiH.

Calculate an accurate value of Avogadro's number as the ratio of the electric charge on a mole of electrons
(Faraday's constant) divided by the charge on a single electron (see Table 2 of the Appendix). \=-

Calculate the edge length of a cube containing an Avogadro's number (6.02 x 1023) of hydrogen atoms stacked
to form a cube. Assume a hydrogen atom is equivalent to a tiny cube with edge length 1 x 10-10 m.

\-

Now imagine an Avogadro's number of hydrogen atoms formed into a square one atom-layer thick. What would
be the edge length of the square?

Finally, if an Avogadro's number of hydrogen atoms were arranged in a line, how long would the line be? Com
pare the length of this line with the distance from the earth to the sun, about 93 million miles.

ro-8
\-
 REPORT to SHEET 2

Name Date

In the method of estimating Avogadro's number that we used, there are a number of implicit assumptions:

(
l. We assume that the stearic acid molecules form a close-packed monolayer on the water surface.
2. We assume that the packing of stearic acid molecules is the same in the monolayer as in solid stearic acid.
I

3. We assume that carbon atoms are like little cubes stacked up in a linear fashion. A more accurate picture is
one in which the C atoms are more nearly spherical, having azigzag linkage with tetrahedral 109.5" C*C-C
bond angles, as shown in Figure t0-3(A). If we assume this structure instead of the linear one, show that the
size (diameter, s) of a carbon atom is linked to the thickness, t, of the monolayer by the expression.
\-_
s: tr-l * sin 54.75'- 0.8166, increasing the value of sby a factor of : 1.225
siL54.7i; tg,where
f OSTOO

t When this sine factor

(1.225)3 - 1.84.
is cubed, the calculated volume of a carbon atom is increased by a factor of

f_
4. We assumed that the volume of a carbon atom was equivalent to a cube of edge length s, giving a volume of
( s3. Show that if the volume of a sphere is given by the expression V -
tz n-r3, where r is the radius of the
:
sphere, the volume of a sphere inscribed in a cube will be equal to '/a x s3 0.524 s3, where s is the diameter
of the sphere inscribed in a cube of edge length s.
l._

I
L
t-
for assumptions 3 and 4 to the calculation of the
When we apply the two correction factors calculated
L volume of a carbon atom, we see that their effect is to approximately cancel one another, that is,
1.84x0.524:0.96.

\-
\
ro-9
 (

5. Finally, we assume that diamond consists of close-packed carbon atom cubes, whereas it actually has a
more open structure in which each carbon atom is surrounded by four other carbon atoms with tetrahedral
bond angles. In this structure, only about 34% of the volume of the unit cell is occupied by approximately
spherical carbon atoms. Thus, the actual volume of a mole of spherical carbon atoms is about 0.34 times the
volume of a mole of diamond.

If we incorporate this factor in the calculation of Avogadro's number, show that the calculated value of
Avogadro's number, based on the simple assumptions, would be reduced by about a factor of 3.

6. What do we mean by the size of an atom? There is good evidence that the electron clouds surrounding
isolated atoms do not have sharp, well-defined boundaries. That is, there is good reason to believe that atoms
aren't hard spheres like billiard balls. We can rather accurately measure the internuclear distance between two
atoms in a'Chemical bond. If the two atoms are the same, such as two carbon atoms, then we could define the
radius of a carbon atom as one-half the internuclear distance (the C-C distance), meaning that the diameter of
an atom would be equal to the internuclear C-C distance. Defined this way, the size (diameter) of a carbon
atom is 1.54 x 10-10 m. Compare this value with the value of s that you calculated.

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