普化Ch07 Lecture
普化Ch07 Lecture
Periodic Properties
of the Elements
Zeff = Z − S
– where Z is the atomic number
and S is a screening constant,
usually close to the number of
inner electrons.
Solution
Analyze and Plan We are given three bonds and told to use Figure 7.7 for bonding atomic radii. We will assume
that each bond length is the sum of the bonding atomic radii of the two atoms involved.
Solve
Check The experimentally determined bond lengths are C—S = 133 pm, C—H = 110 pm, and S—H = 182 pm. (In
general, the lengths of bonds involving hydrogen show larger deviations from the values predicted from bonding
atomic radii than do bonds involving larger atoms.)
Comment Notice that our estimated bond lengths are close but not exact matches to the measured bond lengths.
Bonding atomic radii must be used with some caution in estimating bond lengths.
Practice Exercise
Using Figure 7.7, predict which is longer, the P—Br bond in PBr 3 or the As—Cl bond in AsCl3.
Solution
Analyze and Plan We are given the chemical symbols for four elements and told to use their relative positions in the
periodic table to predict the relative size of their atomic radii. We can use the two periodic trends described in the text
to help with this problem.
Solve
B and C are in the same period, with C to the right of B. Therefore,
we expect the radius of C to be smaller than that of B
because radii usually decrease as we move across a period. radius C < radius B
Al and Si are in the same period, with Si to the right of Al. radius Si < radius Al
The radius increases as we move down a group with radius B < radius Al
Al and B belonging to the same group, as do C and Si. radius C < radius Si
Check Referring back to Figure 7.7, we can obtain numerical values for each atomic radius that allow us to say that
the radius of Si is greater than that of B.
C(076 pm) < B (084 pm) < Si (111 pm) < Al (121 pm)
If you examine Figure 7.7 carefully, you will discover that for the sand p-block elements the increase in radius moving
one element down a column tends to be greater than the increase moving one element left across a row. There are
exceptions, however.
Comment Note that the trends we have just discussed are for the s- and p-block elements. As seen in Figure 7.7, the
transition elements do not show a regular decrease moving across a period.
Practice Exercise
Arrange Be, C, K, and Ca in order of increasing atomic radius.
Solution
Cations are smaller than their parent atoms, and so Ca 2+ < Ca. Because Ca is below Mg in group 2A, Ca 2+ is larger
than Mg2+. Consequently, Ca > Ca2+ > Mg2+.
Practice Exercise
Arrange the following atoms and ions in order of increasing ionic radius: F, S 2–, Cl, and Se2–.
Solution
This is an isoelectronic series, with all ions having 18 electrons. In such a series, size decreases as nuclear charge
(atomic number) increases. The atomic numbers of the ions are S 16, Cl 17, K 19, Ca 20. Thus, the ions decrease in
size in the order S2– > Cl– > K+ > Ca2+.
Practice Exercise
Arrange the following ions in order of increasing ionic radius: Br –, Rb+, Se2–, Sr2+, Te2–.
(a) Sr2+ < Rb+ < Br– < Se2– < Te2–
(b) Br– < Sr2+ < Se2– < Te2– < Rb+
(c) Rb+ < Sr2+ < Se2– < Te2– < Br–
(d) Rb+ < Br– < Sr2+ < Se2– < Te2–
(e) Sr2+ < Rb+ < Br– < Te2– < Se2–
Solution
Analyze and Plan The locations of the elements in the periodic table allow us to predict the electron configurations.
The greatest ionization energies involve removal of core electrons. Thus, we should look first for an element with only
one electron in the outermost occupied shell.
Solve The red box represents Na, which has one valence electron. The second ionization energy of this element is
associated, therefore, with the removal of a core electron. The other elements indicated, S (green) and Ca (blue), have
two or more valence electrons. Thus, Na should have the largest second ionization energy.
Check A chemistry handbook gives these I2 values: Ca, 1145 kJ/mol; S, 2252 kJ/mol; Na, 4562 kJ/mol.
Practice Exercise
The third ionization energy of bromine is the energy required for which of the following processes?
(a) Br(g) Br+(g) + e–
(b) Br+(g) Br2+(g) + e–
(c) Br(g) Br2+(g) + 2 e–
(d) Br(g) Br3+(g) + 3 e–
(e) Br2+(g) Br3+(g) + e–
Solution
Analyze and Plan We are given the chemical symbols for five elements. To rank them according to increasing first
ionization energy, we need to locate each element in the periodic table. We can then use their relative positions and
the trends in first ionization energies to predict their order.
Solve Ionization energy increases as we move left to right across a period and decreases as we move down a group.
Because Na, P, and Ar are in the same period, we expect I1 to vary in the order Na < P < Ar. Because Ne is above Ar
in group 18, we expect Ar < Ne. Similarly, K is directly below Na in group 1, and so we expect K < Na.
Practice Exercise
Solution
Analyze and Plan We are asked to write electron configurations for three ions. To do so, we first write the electron
configuration of each parent atom and then remove or add electrons to form the ions. Electrons are first removed
from the orbitals having the highest value of n. They are added to the empty or partially filled orbitals having the
lowest value of n.
Solve
(a) Calcium (atomic number 20) has the electron configuration [Ar]4s2. To form a 2+ ion, the two outer 4s electrons
must be removed, giving an ion that is isoelectronic with Ar:
Ca2+: [Ar]
(b) Cobalt (atomic number 27) has the electron configuration [Ar]4s23d7. To form a 3+ ion, three electrons must be
removed. As discussed in the text, the 4s electrons are removed before the 3d electrons. Consequently, we
remove the two 4s electrons and one of the 3d electrons, and the electron configuration for Co 3+ is
Co3+ : [Ar]3d6
(c) Sulfur (atomic number 16) has the electron configuration [Ne]3s23p4. To form a 2– ion, two electrons must be
added. There is room for two additional electrons in the 3p orbitals. Thus, the S2– electron configuration is
Comment Remember that many of the common ions of the s- and p-block elements, such as Ca2+ and S2–, have the
same number of electrons as the closest noble gas. (Section 2.7)
Practice Exercise
The ground-state electron configuration of a Tc atom is [Kr]5s24d5. What is the electron configuration of a Tc 3+ ion?
(a) [Kr]4d4 (b) [Kr]5s24d2 (c) [Kr]5s14d3 (d) [Kr]5s24d8 (e) [Kr]4d10
© 2022 Pearson Education Ltd. Figure 7.16 Metal oxides react with acids.
Sample Exercise 7.8 Properties of Metal Oxides
(a) Would you expect scandium oxide to be a solid, liquid, or gas at room temperature?
(b) Write the balanced chemical equation for the reaction of scandium oxide with nitric acid.
Solution
Analyze and Plan We are asked about one physical property of scandium oxide—its state at room temperature—
and one chemical property—how it reacts with nitric acid.
Solve
(a) Because scandium oxide is the oxide of a metal, we expect it to be an ionic solid. Indeed it is, with the very high
melting point of 2485 °C.
(b) In compounds, scandium has a 3+ charge, Sc 3+, and the oxide ion is O2–. Consequently, the formula of scandium
oxide is Sc2O3. Metal oxides tend to be basic and, therefore, to react with acids to form a salt plus water. In this
case, the salt is scandium nitrate, Sc(NO 3)3:
Practice Exercise
Suppose that a metal oxide of formula M 2O3 were soluble in water. What would be the major product or products of
dissolving the substance in water?
Solution
Analyze and Plan We note that selenium is a nonmetal. We therefore need to write chemical equations for the
reaction of a nonmetal oxide with water and with a base, NaOH. Nonmetal oxides are acidic, reacting with water to
form an acid and with bases to form a salt and water.
Solve
(a) The reaction between selenium dioxide and water is like that between carbon dioxide and water (Equation 7.13):
(It does not matter that SeO2 is a solid and CO2 is a gas under ambient conditions; the point is that both are
water-soluble nonmetal oxides.)
(b) The reaction with sodium hydroxide is like that in Equation 7.15:
Practice Exercise
Consider the following oxides: SO2, Y2O3, MgO, Cl2O, N2O5.
How many are expected to form acidic solutions in water?
(a) 1 (b) 2 (c) 3 (d) 4 (e) 5
K + O2 KO2
Figure 7.22 Placed in a flame, ions of each alkali metal emit light
of a characteristic wavelength.
© 2022 Pearson Education Ltd.
Flame Tests
Solution
Analyze and Plan Because cesium is an alkali metal, we expect its chemistry to be dominated by oxidation of the
metal to Cs+ ions. Further, we recognize that Cs is far down the periodic table, which means it is among the most
active of all metals and probably reacts with all three substances.
Solve The reaction between Cs and Cl 2 is a simple combination reaction between a metal and a nonmetal, forming
the ionic compound CsCl:
From Equations 7.18 and 7.16, we predict the reactions of cesium with water and hydrogen to proceed as follows:
All three reactions are redox reactions where cesium forms a Cs + ion. The Cl–, OH–, and H– are all 1– ions, which
means the products have 1:1 stoichiometry with Cs +.
Practice Exercise
Consider the following three statements about the reactivity of an alkali metal M with oxygen gas:
(i) Based on their positions in the periodic table, the expected product is the ionic oxide M 2O.
(ii) Some of the alkali metals produce metal peroxides or metal superoxides when they react with oxygen.
(iii)When dissolved in water, an alkali metal oxide produces a basic solution.
(a) Based on values presented in Figure 7.7 and Tables 7.5 and 7.6, what might you expect for the bonding atomic
radius of bismuth?
(b) What accounts for the general increase in atomic radius going down the group 15 elements?
(c) Another major use of bismuth has been as an ingredient in low-melting metal alloys, such as those used in fire
sprinkler systems and in typesetting. The element itself is a brittle white crystalline solid. How do these
characteristics fit with the fact that bismuth is in the same periodic group with such nonmetallic elements as
nitrogen and phosphorus?
(d) Bi2O3 is a basic oxide. Write a balanced chemical equation for its reaction with dilute nitric acid. If 6.77 g of Bi 2O3
is dissolved in dilute acidic solution to make 0.500 L of solution, what is the molarity of the solution of Bi 3+ ion?
(e) 209Bi is the heaviest stable isotope of any element. How many protons and neutrons are present in this nucleus?
(f) The density of Bi at 25 °C is 9.808 g ⁄ cm3. How many Bi atoms are present in a cube of the element that is 5.00
cm on each edge? How many moles of the element are present?
Solution
(a) Bismuth is directly below antimony, Sb, in group 15. Based on the observation that atomic radii increase as we
go down a column, we would expect the radius of Bi to be greater than that of Sb, which is 139 pm. We also
know that atomic radii generally decrease as we proceed from left to right in a period. Tables 7.5 and 7.6 each
give an element in the same period, namely Ba and Po. We would therefore expect that the radius of Bi is
smaller than that of Ba (215 pm) and larger than that of Po (140 pm). We also see that in other periods, the
difference in radius between the neighboring group 15 and group 16 elements is relatively small. We might
therefore expect that the radius of Bi is slightly larger than that of Po—much closer to the radius of Po than to
the radius of Ba. The tabulated value for the atomic radius on Bi is 148 pm, in accord with our expectations.
(b) The general increase in radius with increasing atomic number in the group 15 elements occurs because
additional shells of electrons are being added, with corresponding increases in nuclear charge. The core
electrons in each case largely screen the outermost electrons from the nucleus, so the effective nuclear charge
does not vary greatly as we go to higher atomic numbers. However, the principal quantum number, n, of the
outermost electrons steadily increases, with a corresponding increase in orbital radius.
(c) The contrast between the properties of bismuth and those of nitrogen and phosphorus illustrates the general rule
that there is a trend toward increased metallic character as we move down in a given group. Bismuth, in fact, is
a metal. The increased metallic character occurs because the outermost electrons are more readily lost in
bonding, a trend that is consistent with its lower ionization energy.
Molecular equation:
In the net ionic equation, nitric acid is a strong acid and Bi(NO 3)3 is a soluble salt, so we need to show only the
reaction of the solid with the hydrogen ion forming the Bi 3+(aq) ion and water. To calculate the concentration of
the solution, we proceed as follows (Section 4.5):
(e) Recall that the atomic number of any element is the number of protons and electrons in a neutral atom of the
element. (Section 2.3) Bismuth is element 83; there are therefore 83 protons in the nucleus. Because the
atomic mass number is 209, there are 209 – 83 = 126 neutrons in the nucleus.