CHE3330
HW1
2.1. Silicon has three naturally-occurring isotopes: 92.23% of 28Si, with an atomic weight of 27.9769 amu,
4.68% of 29Si, with an atomic weight of 28.9765 amu, and 3.09% of 30Si, with an atomic weight of 29.9738
amu. On the basis of these data, confirm that the average atomic weight of Si is 28.0854 amu.
Solution
The average atomic weight of silicon (ASi ) is computed by adding fraction-of-occurrence/atomic
weight products for the three isotopes. Thus
€
ASi = f 28 A28 + f 29 A29 + f 30 A30
Si Si Si Si Si Si
= (0.9223)(27.9769) + (0.0468)(28.9765) + (0.0309)(29.9738) = 28.0854
€
2. 3 €
Allowed values for the quantum numbers of electrons are as follows:
n = 1, 2, 3, . . .
l = 0, 1, 2, 3, . . . , n –1
ml = 0, ±1, ±2, ±3, . . . , ±l
1
ms = ±
2
The relationships between n and the shell designations are noted in Table 2.1. Relative to the subshells,
€ l = 0 corresponds to an s subshell
l = 1 corresponds to a p subshell
l = 2 corresponds to a d subshell
l = 3 corresponds to an f subshell
For the K shell, the four quantum numbers for each of the two electrons in the 1s state, in the order of
1 1
nlmlms, are 100( ) and 100( − ). Write the four quantum numbers for all of the electrons in the L and M
2 2
shells, and note which correspond to the s, p, and d subshells.
Solution
€ €
For the L state, n = 2, and eight electron states are possible. Possible l values are 0 and 1, while
1
possible ml values are 0 and ±1; and possible ms values are ± . Therefore, for the s states, the
2
€
1 1 1
quantum numbers are 200 ( ) and 200 (− ) . For the p states, the quantum numbers are 210 ( ) ,
2 2 2
1 1 1 1 1
210 (− ) , 211 ( ) , 211 (− ) , 21 (−1)( ) , and 21 (−1)(− ).
2 2 2 2 2
For the M€state, n = 3,€and 18 states are possible. Possible l values are 0, 1, and
€ 2; possible ml
1
values are 0, ±1, and ±2; and possible ms values are ± . Therefore, for the s states, the quantum numbers
€ € € € € 2
1 1 1 1 1 1 1
are 300 ( ) , 300 (− ) , for the p states they are 310 ( ) , 310 (− ) , 311 ( ) , 311 (− ) , 31 (−1)( ) , and
2 2 2 2 2 2 2
1 1 1 1 1 1 1
31 (−1)(− ) ; for the d states they are 320 ( ) , 320 (− ) , 321 ( ) , 321 (− ) , 32 (−1)( ) , 32 (−1) (− ) ,
2 2 2 2 2 2 2
1 1 1 1
€ 322€( ) , 322 (− ) , 32 (−2)( ) , and 32 (€
−2) (− ) €
. € € €
2 2 2 2
€ € € € € € €
€ € € consulting Figure
2.6 Without € 2.6 or Table 2.2, determine whether each of the electron configurations
given below is an inert gas, a halogen, an alkali metal, an alkaline earth metal, or a transition metal.
Justify your choices.
(a) 1s22s22p63s23p5
(b) 1s22s22p63s23p63d104s24p6
(c) 1s22s22p63s23p63d104s24p64d55s2
Solution
(a) The 1s22s22p63s23p5 electron configuration is that of a halogen because it is one electron
deficient from having a filled p subshell.
(b) The 1s22s22p63s23p63d104s24p6 electron configuration is that of an inert gas because of
filled 4s and 4p subshells.
(c) The 1s22s22p63s23p63d104s24p64d55s2 electron configuration is that of a transition metal
because of an incomplete d subshell.
2.8 Calculate the force of attraction between a Ca2+ and an O2– ion the centers of which are separated by
a distance of 1.25 nm.
Solution
The attractive force between two ions FA is just the derivative with respect to the interatomic
separation of the attractive energy expression, Equation 2.8, which is just
# A&
d%− (
dE A $ r' A
FA = = =
dr dr r2
€
The constant A in this expression is defined in footnote 3. Since the valences of the Ca2+ and O2- ions (Z1
and Z2) are both 2, then
(Z1e) (Z 2 e)
FA =
4πε0r 2
(2 )(2 )(1.6 × 10−19 C)2
= €
(4)(π) (8.85 × 10−12 F / m) (1.25 × 10−9 m)2
= 5.89 ´ 10-10 N
€
2.12 Compute the percentage ionic character of the interatomic bond for each of the following
compounds: MgO and CdS
.
Solution
The percent ionic character is a function of the electron negativities of the ions XA and XB
according to Equation 2.10. The electronegativities of the elements are found in Figure 2.7.
For MgO, XMg = 1.2 and XO = 3.5, and therefore,
# 2&
%IC = %1 − e (− 0.25) (3.5−1.2) ( × 100 = 73.4%
$ '
For CdS, XCd = 1.7 and XS = 2.5, and therefore,
€
# 2&
%IC = %1 − e (− 0.25) (2.5−1.7) ( × 100 = 14.8%
$ '
2.15 Explain why hydrogen fluoride (HF) has a higher boiling temperature than hydrogen chloride (HCl)
€
(19.4 vs. –85°C), even though HF has a lower molecular weight.
Solution
The intermolecular bonding for HF is hydrogen, whereas for HCl, the intermolecular bonding is
van der Waals. Since the hydrogen bond is stronger than van der Waals, HF will have a higher melting
temperature.
3.1 If the atomic radius of lead is 0.175 nm, calculate the volume of its unit cell in cubic meters.
Solution
Lead has an FCC crystal structure (Table 3.1). The FCC unit cell volume may be computed from
Equation 3.4 as
VC = 16R3 2 = (16) (0.175 × 10-9 m)3 ( 2 ) = 1.213 × 10-28 m3
3.2 Show that the atomic packing factor for BCC is 0.68.
€
Solution
The atomic packing factor is defined as the ratio of sphere volume to the total unit cell volume, or
VS
APF =
VC
Since there are two spheres associated with each unit cell for BCC
€
# 4πR3 & 8πR3
VS = 2 (sphere volume) = 2 %% (( =
$ 3 ' 3
Also, the unit cell has cubic symmetry, that is VC = a3. But a depends on R according to Equation 3.3, and
€
" 4R %3 64 R3
VC = $ ' =
# 3& 3 3
Thus,
€
VS 8π R3 /3
APF = = = 0.68
VC 64 R3 /3 3
3.3 Molybdenum has a BCC crystal structure, an atomic radius of 0.1363 nm, and an atomic weight of
€
95.94 g/mol. Compute its theoretical density and compare it with the experimental value found inside the
front cover.
Solution
This problem calls for a computation of the density of molybdenum. According to Equation 3.5
nAMo
ρ =
VC N A
€
For BCC, n = 2 atoms/unit cell, and realizing that VC = a3, and using Equation 3.3
" 4 R %3
VC = $ '
# 3&
Thus,
€
nAMo
ρ =
# 4 R &3
% ( N
$ 3' A
(2 atoms/unit cell)(95.94 g/mol)
= 3
€ -7
[ (4) (0.1363 × 10 cm) / 3 /(unit cell) (6.02 × 1023 atoms/mol)
]
= 10.22 g/cm3
€
The value given inside the front cover is 10.22 g/cm3.
3.4 Calculate the radius of a palladium atom, given that Pd has an FCC crystal structure, a density of
12.0 g/cm3, and an atomic weight of 106.4 g/mol.
Solution
For FCC, n = 4 atoms/unit cell, and VC = 16R 3 2 (Equation 3.4). Now,
€ nAPd
ρ =
VC N A
nAPd
=
€ (16R3 2 ) N A
And solving for R from the above expression yields
€
# nA &1/3
R = %% Pd ((
$ 16ρN A 2 '
# (4 atoms/unit cell) (106.4 g/mol) &1/3
= % € (
%$ (16)(12.0 g/cm3 )(6.02 × 1023 atoms/mol)( 2 ) ('
€
= 1.38 ´ 10-8 cm = 0.138 nm
3.9 Magnesium has an HCP crystal structure, a c/a ratio of 1.624, and a density of 1.74
g/cm3. Compute the atomic radius for Mg.
Solution
In order to compute the atomic radius for Mg we must use Equation 3.7, as well as the expression
which relates the atomic radius to the unit cell volume for HCP; It was shown that
VC = 6 R2 c 3
In this case c = 1.624a, but, for HCP, a = 2R, which means that
€
VC = 6 R2 (1.624)(2R) 3 = (1.624)(12 3)R3
And from Equation 3.5, the density is equal to
€
nAMg nAMg
ρ = =
VC N A (1.624)(12 3) R3 N A
And, solving for R from the above equation leads to the following:
€
# nAMg &1/3
R = % (
$ (1.624) (12 3) ρ N A '
# (6 atoms/unit cell) (24.31 g/mol) &1/3
= %€ (
%$ (1.624) (12 3)(1.74 g/cm3 )(6.02 × 1023 atoms/mol) ('
= 1.60 ´ 10-8 cm = 0.160 nm
€
