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Solutions Science and Design of Engineering Materials
Solutions Science and Design of Engineering Materials
1.
Find:
Data:
Solution:
2.
Find:
Data:
Solution:
The electron configuration of the element that comes next in the series Si, Ge?
Periodic Table in Appendix A.
Examination of the Periodic Table shows that Si and Ge are both Group IVB elements. As
shown in Example Problem 2.2-1, have a valence electron configuration of the form xs2xp2
when x=3 for Si and x=4 for Ge. The next group IVB element in the series is Sn with an
electron configuration (from the Periodic Table) of [1s22s22p63s23p63d1O4s24p64d1O] 5s25p2.
Note that the valence electron configuration for Sn is also of the form xs2xp2 with x=5.
The similarity of their valence electron configurations suggests that Sn should display
properties similar to those of Si and Ge. This is true over a limited temperature range but there
are other factors (to be discussed in the next chapter) that explain why Sn also has some
properties that differ from those of the other two elements.
Comments:
3.
Find:
Data:
Solution:
Comments:
4.
Find:
Solution:
5.
Find:
Data:
Solution:
Comment:
6.
Find:
Data:
Solution:
7.
Find:
Describe the desirable environmental stability of a "gold standard".
Assumptions: You want the standard's critical properties to be invariant with time
Solution:
Comments:
Gold is one of the few metals whose pure metallic state is more thermodynamically table than
its oxide. Hence, gold does not oxidize. If it did, then it might gain or lose weight with time of
exposure to air.
This is why gold is found in nature as nuggets, whereas, for example, iron and aluminum are
found as oxides or sulfides.
8.
Find:
Solution:
9.
Find:
Given:
Data:
Assumptions:
Solution:
10.
Find:
Given:
Data:
Assumption:
Solution:
11.
Comments:
When the temperature increases from 10C to 20C, the rate increases by a factor of 3.19. In
contrast, a temperature increase from 40C to 50C results in a rate increase of 2.59. This
example illustrates the general result that a fixed change in temperature has a greater
influence on the reaction rate if the average temperature is low.
Find:
Solution:
Why are high quality electronic cable ends or contact points gold-coated?
You do not want the resistance of the connection to increase with time. Oxides are generally
good electrical insulators. Steel points rust and the oxide prevents them from working. Car
points, for example, need to be changed frequently.
In some electronic devices a slight impedance increase due to oxide formation can cause a
circuit to fail catastrophically, destroying a number of components.
Comments:
12.
Find:
Given:
Solution:
system. We know, however, that a ball can be moved uphill if energy is supplied to the system
(i.e. if it is carried uphill). Furthermore, it may remain at a higher elevation if there are activation
barriers associated with its return to the lowest energy position. Similar logic applies to the
reduction of Al203 to 2Al + 1.5 O2. If man supplies (thermal) energy, the metal can be extracted
from its ore and will remain in a metastable state. However, the metal will return to its more
stable oxide at a later time if conditions permit.
13.
Find:
Solution:
Primary
bond type
Ionic
Covalent
Metallic
14.
Find:
Data:
Electronegative
and
electropositive
Electronegeative (usually
with NVE > 3)
Electropositive (usually
with NVE 3)
Bonding
electrons shared
or transferred
If sharing occurs,
is it localized or
delocalized
Transferred
-------
Shared
Localized
Shared
delocalized
Assumptions:
Electronegativity
3.44
0.93
3.98
1.78
2.19
2.01
1.31
1.00
1.90
2.55
2.20
Percent ionic character of a bond is a function of the difference in the electronegativities of the
elements involved (See Appendix A for conversion table) .In a metal, the average number of
valence electrons is generally ~ 3. In a covalent solid the average number of valence electrons
is generally > 3.
Solution:
02, EN=O so that the bond is not ionic. Since 0 is an electronegative element and the average number of
valence electrons is 6, we predict a covalent bond.
NaF, EN = EN(F)-EN(Na) = 3.98-0.93 = 3.05. This AEN corresponds to a bond that is approximately
90% ionic.
InP, EN = EN(P)-EN(In) = 2.19-1.78 = 0.41. Since this bond is only about 4% ionic, we must examine the
average number of electrons, N~. Since N~ = (3+5)/2 = 4, we predict that the bond will be
covalent.
Ge, EN=O so the bond is not ionic. Ge is neither strongly electropositive or electronegative, but it does
have N~=4. Thus we predict covalent bonding.
Mg, AEN=O so the bond is not ionic. Mg is an electro- positive element with N~ =2. It will have metallic
bonds.
CaF2, EN = EN(F)-EN(Ca) = 3.98-1.0 = 2.98. This ~EN corresponds to a bond that is appproximately
89% ionic.
SiC, EN = EN(C)-EN(Si) = 2.55-1.90 = 0.65. Since this corresponds to a bond that is only ~10% ionic,
we must consider N~. The average number -of valence electrons is (4+4)/2 = 4 so the bond is
predicted to be covalent.
(CH2), AEN = 2.55-2.20 = 0.35 so the bond is not ionic. Although the average N~ in this compound is
(4+1)/2 = 2.5, the bond is predicted to be covalent because His a recognized exception to the
trend and is known to favor the formation of covalent bonds.
MgO, AEN = EN90)-EN(Mg) = 3.44-1.31 = 2.13 which corresponds to a bond that is ~68% ionic.
CaO, AEN = EN(O)-EN(Ca) = 3.44-1.0 = 2.44 which corresponds to a bond ~77% ionic
Comments:
Find:
Data:
Sketch:
Solution:
The 8 dots represent the electrons: 4 come from the central carbon and 1 from each of the 4
hydrogen. The electrons are localized between the atoms sharing the electrons.
16.
Find:
Data:
Solution:
17.
Find:
Solution:
15.
Comments:
18.
Find:
Reason why covalent bonds are restricted to electro- negative elements.
Assumptions: During bonding, atoms seek to obtain a filled valence electron shell.
Solution:
Electronegative elements generally have nearly filled valence shells and are seeking a few
additional electrons. If electropositive atoms are nearby, they can transfer electrons to the
electronegative atoms and an ionic bond is formed. If, however, only electronegative atoms are
present then the only way they can all acquire extra electrons is to share them. This is the
definition of a covalent bond.
Comments:
Hydrogen also forms covalent bonds.
19.
Find:
Given:
Data:
Assumptions:
Solution:
Comments:
20.
Find:
Solution:
21.
Comments:
Find:
Data:
Solution:
It is impossible to form ionic bonds in any pure element since there will be no difference in EN
values for identical atoms. In the case of Si-O, however, the difference in electronegativity is
1.54. This corresponds to a bond that is approximately 45% ionic and 55% covalent.
This type of primary bond is often described as a mixed ionic/covalent bond.
Can an ionic solid be a good electrical conductor? Assumptions: High electrical conductivity
requires a high density of mobile charge carriers.
In ionic solids there are usually few, if any, free electrons. Charge transport requires the motion
of comparatively large ions which is generally a more difficult process than electron motion. If,
however, an ionic solid had either a high free electron density or extremely mobile ions, then it
would be a good electrical conductor.
We will find some examples of materials with these characteristics in Chapter 10.
Physical significance of p<q in Equation 2.4-7.
Equation 2.4-7 states: FA+FR = O = A'/xpB'/xq.
This equation describes the competing forces of attraction and repulsion in a covalent bond.
Since the repulsive force is known to dominate at small separation distances (x0), we
require B'/xq A'/xpas x0. This is equivalent to requiring that xq xp (for x0) which is
satisfied if and only if q>p.
22.
Find:
Solution:
23.
Find:
Given:
Solution:
Identify which material shown in Fig. 2.5-1 has a higher melting temperature.
The slope of material A at zero force is greater than that of B.
The ease of separating atoms or molecules with heat is similar to the ease of separating atoms
with force. Hence, A has a higher melting temperature than does B.
24.
Find:
Relationship between xth and melting temperature.
Data:
xth (Al) = 25x10-6 C-1 and xth(SiC) = 4.3 x 10-6 C-1.
Assumptions: Melting temperature is related to the depth of the bond energy curve and thermal expansion
coefficient is related to the asymmetry of the curve.
Solution:
Since "deep" energy wells tend to be more symmetric, materials with high melting
temperatures tend to have low expansion coefficients. Thus, we expect SiC to have a higher
Tm than Al.
Comments:
This prediction is consistent with experiment - Tm(SiC) = 2700C and Tm (Al) = 660C.
25.
Find:
Solution:
Relationship between stiffness and thermal expansion. Assumptions: Stiffness is related to the
curvature (second derivative) of the bond energy curve at its minimum and expansion
coefficient is related to symmetry of the curve.
Bond energy curves that are sharply curved have large second derivatives and high stiffness.
However, such curves will also be relatively symmetric so they will exhibit low coefficients of
thermal expansion. In order to obtain a stiff material with a high expansion coefficient it would
require a tightly curved but asymmetric shape. This combination is difficult to achieve.
26.
Find:
Solution:
27.
Find:
Given:
Data:
Solution:
28.
29.
Find:
Solution:
Comments:
The bond energy curve is steeper to the right of Xo than to the left. This means that the
midpoints of the constant energy line segments shift to the left as energy (temperature)
increases.
Find:
Given:
Data:
Solution:
There is a problem with significant digits in this problem. The atomic spacing at 25C was
provided only to 2 decimal places. Better accuracy is required in the atomic spacings if better
accuracy in the calculated results are required.
30.
Find:
Solution:
Methods for measuring Youngs Modulus and coefficient of thermal expansion in the lab.
Youngs Modulus relates the stiffness or deflection of a material to the magnitude of the force
or load causing that deflection. The modulus of a material could be measured using either of
the methods sketched above, that is, by measuring the deflection of a cantilever beam or tne
change in length of an axially leaded rod. Coefficient of thermal expansion is measured by
observing the change in length of a sample resulting from a temperature change (see Equation
2.5-4).
31.
Find:
Given:
Data:
Solution:
Comments:
32.
33.
Find:
Sketch:
Comments:
In methane the C is in the center of the cube and the H are centered on the appropriate cube
corners. The bond angles are 109.5 and the bond lengths are all the same. In the ketone the
C is located within an equilateral triangle. The O bond and the other two single bonds are
planar, essentially 120 apart.
Find:
Solution:
34.
Find:
Data:
Contents:
as in Fig. 2.6-5.
35.
Find:
Solution:
36.
Find:
Given:
Solution:
Comment:
37.
Find:
Assumption:
Solution:
R + R = ap2
and
(r + R) = a/2
and
(R + R) = ap2/2
Dividing the first equation by the second gives:
r/R = (2/p2) - 1 = 0.414
Therefore, the radius ratio range for CN=4 is 0.225 (r/R) < 0.414.
38.
Find:
Given:
Solution:
B.
Anions are generally larger than their neutral counterparts because the added electrons
increase electron-electron mutual repulsion and decrease the relative magnitude of the
nuclear charge. Therefore, r(A-) > r(A). Using the inverse argument we predict r(B+) <
r(B).
If the compound is ionic we nust use an nfl ratio to predict the CX of the smaller ion (in
this case the anion).
r(A-)/R(B+) = 0.13/0.14= 0.929
From Table 2.6-1, this implies CN(A-} = 8. Since the anion:cation ratio is 2:1, the
coordination number for the cation is predicted to be CN(B+) =2[CN(A-) = 16. A CN of
16, however, is not possible. Therefore, the most likely values are CN(B+) = 12 and
CN(A-) = 6. Recall that lower CN values are always possible but are generally not
energetically favorable.
39.
Find:
Solution:
40.
Find:
Solution:
Comments:
41.
Find:
Structure of C2H6
Assumptions: This is a covalent compound
Solution/Sketch:
42.
Comments:
Find:
Solution:
Comment:
43.
Find:
Solution:
44.
Find:
Bond angle H-N-H in NH3
Assumptions: Covalent bonding with CN(N) = 3 and CN(H) = 1.
Sketch:
Solution:
The bond angle is close to the tetrahedral angle of 109.5 (see Figure 2.6-4 (a) and associated
text).
Comments:
See Example Problem 2.6-4.
45.
Find:
Solution:
46.
Find:
Predict which material has the higher Tm
Assumptions: For compounds with secondary bonds, the important factors are the relative strength of the
bonds and the size of the molecules (since larger molecules have a greater surface area over
which secondary bonds can occur).
Solutions:
A.
because the latter is permanent dipole while the former is too symmetric to have strong
secondary bonds.
B.
because the latter is permanent dipole while the former is too symmetric to have strong
secondary bonds.
C.
Although their structures are very similar, C~4H3o will have a higher T. than Cit, because it is a
larger molecule with more surface for secondary bond formation.
47.
Find:
Suggest whether natural polymers amides and cellulose - are moisture sensitive.
Given:
Solution:
Comments:
48.
Find:
Given:
Solution:
49.
Find:
Data:
Solution:
50.
Find:
Given:
Compare the bond strength of a permanent dipole to that of a primary ionic bond.
A primary bond involves complete transfer of whole charges. A secondary ionic bond may not
involve transfer of a whole charge.
The strength of an individual secondary bond can be significant. In charged polymer solutions,
for example, whole charges can be associated with individual atoms or groups of atoms. There
are, however, not as many of these charged species per unit volume as there are in an ionic
solid. An example of a charged polymer solution (a polyelectrolyte) is the natural polymer guar,
which is made from guar beans and is solubilized in water. Guar gum is used in synthetic, or
inexpensive, ice cream. It is the reason that cheap ice cream does not really melt.
The concerted action of secondary bonds is generally much weaker than that of the
primary bonds. Either the individual bonds are weak and many, or they are strong but few.
Secondary bonding is responsible for a number of critical properties, such as lack of a melting
temperature in polymers like cellulose, rayon, wool, and silk. One class of polymers, ionomers,
has charged groups built into the molecules. They are not present in high density, but they
impart interesting rheological and mechanical properties to the polymer. Golf ball covers are
made from ionomers.
When molecules are aligned in one direction in a fiber or film, then the product can be 100
times stronger in one direction than in the other. This is one reason that fiber producers strive
to align molecules along the fiber axis.
Solution:
Coments:
51.
Find:
Examples of materials with mixed bonding.
Assumptions: Mixed primary-primary bonding occurs when each bond displays characteristics of two of the
primary bond types. Mixed primary-secondary bonding occurs when some of the bonds are
primary bonds while other bonds in the compound are secondary bonds.
Solution:
Mixed bonding at the primary-primary level can occur to ceramics that are ionic/covalent. This
occurs when EN is in the range of 1.2-2.2. Examples include SiO2 (EN=1.54), Al2O3 (EN =
1.83, ZnO (EN 1.79), and many others. Mixed bonding at the primary-secondary level occurs
in graphite and in most TP polymers including all of the vinyls arid nylon.
Comments:
Mixed primary-primary bonding can also occur in metallic/covalent solids.
52.
Find:
Solution:
53.
Find:
Given:
Assumptions:
Solution:
Comments:
54
Find:
Data:
Solution:
55.
Find:
Given:
Solution:
56.
Find:
Given
Solution:
Comments:
57.
Find:
Given:
55.
Find:
Solution:
Imagine what might occur when a polymerization reactor goes out of control.
The reduction of a double bond to a single bond, such as for ethylene, H3C = CH3, liberates a
vast amount of heat.
Assumptions: The heat cannot be removed fast enough, so the temperature builds.
Solutions:
Kaboom!
Comments:
Many precautions are taken to prevent the temperature from running away. For example, in
one type of reactor, the mer (say ethylene} is in the form of tiny droplets suspended in water.
Each droplet is a reaction vessel. If the rate were to become very high in one droplet, then the
surrounding water would absorb the liberated heat and the kaboom is avoided. Thus, in
todays modern reactors, runaway polymerization is no longer a significant problem.
Comments:
59.
Find:
Solution:
60.
Find:
Solution:
How does the stiffness of a rubber change with oxygen or sulfur additions?
Both C and S act as crossiinking agents in rubber. Since increasing the crosslink density
restricts molecular motion, we should expect the stiffness of the rubber to increase as the
amount of 0 or S increases.