Chemistry 2810

Answers to the 4th assignment

Topic: Brnsted A/B Theory and Hydrogen, Groups 1 & 2 and Solids. The sections in the textbooks are indicated on the
course outline. If between your text and the lecture notes you CANNOT find the information required for answering the
questions, please consult your instructor. Note that we use a simpler form of the Born-Meyer equation than that developed in
SAL (see the lecture notes). Use the table provided in the lecture notes for all ionic radii, not those in the text!
1.

Sketch an outline of the s and p blocks of the periodic table and indicate on it the elements that form (a) strongly acidic
oxides and (b) strongly basic oxides, and (c) show the regions for which amphoterism is common.
See the diagram at right. If you cannot write out the s-, p- and d blocks
from memory, you should spend some time learning that part of the
periodic table. This knowledge will permit you to integrate many chemical
facts into a logical pattern of trends. The elements that form basic oxides in
plain type, those forming acidic oxides in outline type, and those forming
amphoteric oxides in boldface type. Note the diagonal region from upper
left to lower right that includes the elements forming amphoteric oxides.
The elements Ge, Sn, Pb, As, Sb, and Bi form amphoteric oxides only in
their lower oxidation state (II for Ge, Sn, and Pb, III for As, Sb, and Bi).
They form acidic oxides in their higher oxidation state (IV for Ge, Sn, and
Pb, V for As, Sb, and Bi).

2.

Identify the conjugate bases corresponding to the following acids:,

(a) [Co(NH3)5(OH2)] +3: A conjugate base is a species with one fewer proton than the parent acid. Therefore, the
conjugate base in this case is [Co(NH3)5(OH)]2+, shown below right (L = NH3).
(b) HSO4: The conjugate base is SO42.
(c) CH3OH,: The conjugate base is CH3O.
(d) H2PO4: The conjugate base is HPO42.
(e) Si(OH)4,: The conjugate base is SiO(OH)3.
(f) HS: The conjugate base is S2.
(g) [Fe(OH2)6]2+: The conjugate base is [Fe(OH)(OH2)5]+
(similar to (a) with L = H2O and Fe in place of Co).

3.

Identify the conjugate acids of the bases:

(a) Sb(OH)3,: A conjugate acid is a species with one more proton than the parent
base. Therefore, the conjugate acid in this case is (H2O)Sb(OH)2+.
(b) C5H5N (pyridine): The conjugate acid is the pyridinium ion, C5H6N+, shown at
right.
(c) HPO42: The conjugate acid is H2PO4.
(d) O2: The conjugate acid is OH.
(e) CH3COOH (acetic acid): The conjugate acid is CH3C(OH)2+, shown above next to the
pyridinium ion.
(f) [Co(CO)4]: The conjugate acid is HCo(CO)4, shown at right.
(g) CN: The conjugate acid is HCN

4.

List the bases HS, F, I, and NH2 in order of increasing proton affinity.
You should make use of Table 5.2 (notes p.49) to answer this question. The species with the greatest proton affinity will
be the strongest base, and its conjugate acid will be the weakest acid. The weakest acid will have the smallest value of Ka
(or the most positive value of pKa). Since Table 5.2 shows that HI is a stronger acid than HF which is a stronger acid than
H2S, a partial order of proton affinity is I < F < HS. Since NH3 is a very weak acid, NH2 must be a very strong base.
Therefore, our final list, in order of increasing proton affinity, is I < F < HS < NH2.

5.

Using Pauling's rules (consult the table of examples given in the notes, and consider also their conjugates), and taking the
concept of solvent leveling into account, identify which bases from the following lists are (a) too strong to be studied
experimentally; (b) too weak to be studied experimentally; or (c) of directly measurable base strength under the conditions
specified
(i) In water solution: CO32, O2, ClO4, and NO3. You can interpret the term "studied experimentally" to mean that the
base in question exists in water (i.e. it is not completely protonated to its conjugate acid) and that the base in question can
be partially protonated (i.e. it is not so weak that the strongest acid possible in water, H3O+, will fail to produce a
measurable amount of the conjugate acid). The pKb of H2O is 14 (the weakest base in water), while pKb of OH is 0 (the
strongest base in water). Thus bases with pKb between these two values can be studied in water. Using these criteria:
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(a) CO32 has a pKa for its conjugate of 8 - 5 + 5 = 8, hence a pKb of 14 - 8 = 6. This fits the range of study in water.
(b) O2 is derived from water, for which Pauling's first rule doesn't work. But we know this species well. Since the base
OH is the strongest base in water is its conjugate acid, it stands to reason that oxide must be a more powerful base. We
can estimate its pKa using Pauling's second rule by subtracting 5 from the value for hydroxide, which gives about -7.
Oxide can definitely not be studied in aqueous solution. It is instantly solvent leveled to hydroxide.
(c) ClO4 has a pKa for its conjugate of 8 - 15 = -7. Hence its pKb of 14 - (-7) = 21. It is a weaker base than water and it
cannot be protonated in water, so cannot be studied in aqueous solution.
(d) NO3- has a pKa for its conjugate of 8 - 10 = -2. Hence its pKb of 14 - (-2) = 16. It is thus also a weaker base than water,
so cannot be studied in aqueous solution.
(ii) In liquid H2SO4 solution: HSO4, NO3, ClO4
(a) HSO4: The hydrogen sulfate ion, HSO4 is the strongest base possible in liquid sulfuric acid and it has a pKa for its
conjugate of 8 - 10 = -2. Hence its pKb of 14 - (-2) = 16. However, since acids can protonate it, it is not too strong to be
studied experimentally.
(b) NO3: It also has an (estimated) pKb of 14 - (-2) = 16 by Pauling's rules. We expect it to be quite comparable to
hydrogen sulfate ion, and hence it should be possible to study it experimentally.
(c) ClO4 has a pKa for its conjugate of 8 - 15 = -7. Hence its pKb of 14 - (-7) = 21. It is a weaker base than hydrogen
sulfate ion, so ClO4- cannot be protonated and studied in liquid sulfuric acid solution.
6.

The aqueous solution pKa values of HOCN, H2NCN, and CH3CN are approximately 4, 10.5, and 20 (estimated),
respectively. Explain the trend in these compounds in which a CN group has replaced a hydrogen in H2O, NH3 and
CH4 by comparison with the acidity of the parent hydrides. Is the cyano group electron donating or electron
withdrawing?
A comparison of the aqueous pKa values is necessary to answer this question. These are:
CH3CN, 20
HOCN, 4
H2NCN, 10.5
NH3, > 14
CH4, very large
H2O, 14
You know that the values of pKa are very large for ammonia and methane because these compounds are not normally
thought of as acids (this implies that they are extremely weak acids). Now, in all three cases, the cyanocontaining
compound has a lower pKa (a higher acidity) than the parent compound. In the case of H2O and HOCN, the latter
compound is 10 orders of magnitude more acidic than water. The deprotonation equilibrium involves the formation of an
anion, the conjugate base of the acid in question. For example:

Since a lower pKa means a larger Ka, this suggests that the anion OCN is better stabilized than OH. This occurs because
the -CN group is more electron withdrawing than the -H substituent.
7.

The pKa value of HAsO42 is 11.6. Is this value consistent with the two Pauling rules?
Pauling's first rule for predicting the pKa of a mononuclear oxoacid is pKa = 8 - 5p (where p represents the number of oxo
groups attached to the central element).
Since p = 1, the predicted value of pKa(l) for H3AsO4 is 8 - 5 x 1 = 3.
Pauling's second rule for predicting the pKa of a mononuclear oxoacid is that successive pKa
values for polyprotic acids increase by five units for each successive proton transfer. Since
pKa(l) for H3AsO4 was predicted to be 3, the predicted value of pKa for HAs04, which is pKa(3)
for H3AsO4, is 3 + (2)(5) = 13. The actual value, which differs by 1.5 pKa units, is 11.5. This
illustrates that Pauling's rules are only approximate.

8.

Draw the structures (VSEPR) and indicate the charges of the tetraoxoanions of Si, P, S and Cl. Summarize and account
for the trends in the pKa values of their conjugate acids.
The structures of these four anions, which can be determined to be tetrahedral using VSEPR, are shown below. As can be
seen, the charge on the anions decreases from -4 for the silicon-containing species to -1 for the chlorine-containing species.
The charge differences alone would make SiO44 the most basic species. Hence HSiO43 is the least acidic conjugate acid.
The acidity of the four conjugate acids increases in the order HSiO43 < HPO42 < HSO4 < HClO4.

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9.

Which of the following pairs is the stronger Brnsted acid? Give reasons for your choice. Where possible, calculate the
pKa values to confirm your answer.
(a) [Fe(OH2)6]3+ or [Fe(OH2)6]2+ (using radii from p.53 of notes and = 1.83 from p.30)

32

pKa = 1514
. 0.8816
+ 9.60(183
. 150
. ) = 2.2 The stronger acid.
0.78

2
2

For the Fe(II) complex: pKa = 1514

. 0.8816
+ 9.60(183
. 150
. ) = 8.5 The weaker acid.
0.92

For the Fe(III) complex:

(b) [Al(OH2)6]3+ or [Ga(OH2)6]3+

32

+ 9.60(161
. 150
. ) = 2.4 The slightly stronger acid.
0.67

. 0.8816
For the Al compound: pKa = 1514

32

. 0.8816
+ 9.60(181
. 150
. ) = 2.1 The slightly weaker acid. Note
For the Ga compound: pKa = 1514
0.76

that the difference is entirely due to the higher electronegativity of Ga, a consequence of the so-called Scandide (dblock) contraction, the fact that Ga is immediately proceeded by the 3d series, and that the filled 3d10 shell is poor at
shielding the valence electrons from the extra nuclear charge gained along with the 10 extra electrons. Thus gallium
chemistry is significantly out of line with that expected for a heavier analog of aluminum, and this is just one example
of this occurrence. (In the table on p.55, you can see experimental pKa data for the 3+ ions Al, Ga, In and Tl. They
oscillate in acid strength as follows: 5.0, 2.6, 4.0, 0.6. Thus Tl is the strongest acid (it follows the first 4f14 series,
known as the Lanthanide contraction), followed by Ga, then comes In and Al is the weakest. Note that all of these
values run counter to the trends in ionic radii, which normally are dominant for acid trends down a group in the
periodic table.
(c) Si(OH)4 or Ge(OH)4: Our equation for the hydrolysis of aquated cations is not directly applicable to these two
species. The equilibria that they undergo in aqueous solution result in the loss of two protons, so that they are
definitely still "acidic" compounds, even if they have formally already produced 4 hydronium ions in reaction with
water:
M(OH)4 + 2 H2O MO2(OH)22 + 2 H3O+
How will the differences between the two work out? We see that for Si and Ge are 1.90 and 2.01, while the radii are
0.40 and 0.53 . Again the two work in opposite directions. It would be very difficult to predict which of these
species were the more acidic given the structural changes from normal aqua cations.
(d) HClO3 or HClO4 These two acids are shown at right. According to
Pauling's rule 1 for mononuclear oxoacids, the species with more oxo
groups has the lower pKa and is the stronger acid. Thus, HClO4 is a
stronger acid (pKa = -7) than HClO3 (pKa = -2). Note that the oxidation
state of the central chlorine atom in the stronger acid (+7) is higher than in
the weaker acid (+5).
(e) H2CrO4 or HMnO4 As in part (d), above, the oxidation states of these two
acids are different, +6 for the chromium atom in H2CrO4 and +7 for the manganese atom in HMnO4. The species with
the higher central atom oxidation state, HMnO4, is the stronger acid (pKa = -7). Note that this acid has more oxo
groups, three, than H2CrO4 (pKa = -2), which has two.
(f) H3PO4 or H2SO4. The oxidation state of sulfur in H2SO4 (pKa = -2) is +6 while the oxidation state of phosphorus in
H3PO4 (pKa = +3) is only +5. Furthermore, sulfuric acid has two oxo groups attached to the central sulfur atom while
phosphoric acid has only one oxo group attached to the central phosphorus atom. Therefore, on both counts (which
by now you can see are really manifestations of the same underlying atomic properties) H2SO4 is a stronger acid than
H3PO4.
10. Arrange the oxides Al2O3, B2O3, BaO, CO2, Cl2O7, SO3 in order from the most acidic through amphoteric to the most
basic.
First you pick out the intrinsically acidic oxides, since these will be the least basic. The compounds B2O3, CO2, Cl2O7, and
SO3 are acidic, since the central element for each of them is found in the acidic region of the periodic table (see the s and p
block diagram in the answer to question #1). The most acidic compound, Cl2O7, has the highest central-atom oxidation
state, +7, while the least acidic, B2O3, has the lowest, +3. Of the remaining compounds, A12O3 is amphoteric, which puts
it on the borderline between acidic and basic oxides, and BaO is basic. Therefore, a list of these compounds in order of
increasing basicity is Cl2O7 < SO3 < CO2 < B2O3 < Al2O3 < BaO.
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11. Arrange the acids HSO4, H3O+, H4SiO4, CH3GeH3, NH3, HSO3F in order of increasing acid strength.
The weakest acids, CH3GeH3 and NH3, are easy to pick out of this group since they do not contain any -OH bonds.
Ammonia is the weaker acid of the two, since it has a lower central-atom oxidation state, +3, than that for the germanium
atom in CH3GeH3, which is +4. Of the remaining species, note that HSO3F is very similar to H2SO4 as far as structure and
sulfur oxidation state (+6) are concerned, so it is reasonable to suppose that HSO3F is a very strong acid, which it is. The
anion HSO4 is a considerably weaker acid than HSO3F, for the same reason that it is a considerably weaker acid than
H2SO4, namely Pauling's rule 2 for mononuclear oxoacids. Since HSO4 is not completely
deprotonated in water, it is a weaker acid than H3O+, which is the strongest possible acidic
species in water. Finally, it is difficult to place exactly Si(OH)4 in this group, for reasons
described in #9. It is certainly more acidic than NH3 and CH3GeH3, and it turns out to be
less acidic than HSO4, despite the negative charge of the latter species. Therefore, a list of
The structures of H2SO4
these species in order of increasing acidity is NH3 < CH3GeH3 < ??Si(OH)4 < HSO4 <
+
and HSO3F.
H3O < HSO3F.
12. The ions Na+ and Ag+ have similar radii. Which aqua ion is the stronger acid? Why? Confirm your answer by
calculating the pKa values of the aqua ions [M(OH2)6]+.
Even though these two ions have about the same ionic radius, Ag+OH2 bonds are much more covalent than Na+OH2
bonds, because of the much higher electronegativity of silver. The greater covalence of the Ag+OH2 bonds has the effect
of delocalizing the positive charge of the cation over the whole aqua complex. As a consequence, the departing proton is
repelled more by the positive charge of Ag+ (aq) than by the positive charge of Na+ (aq), and the former ion is the stronger
aqua cation acid. The reason that silver is more electronegative is due to the filled 3d10 level that is poor at shielding the
valence electrons from the high nuclear charge.

12
= 14.4
116
.
12

+
For Ag : pKa = 1514
. 0.8816
+ 9.60(193
. 150
. ) = 10.8
.
129

For Na+: pKa = 1514

. 0.8816

13. Which of the elements Al, As, Cu, Mo, Si, B, Ti form oxide polyanions and which form oxide polycations?
The aqua ions of metals that have amphoteric oxides generally undergo polymerization to polycations. The elements Al,
Cu, and Ti fall into this category. On the other hand, polyoxoanions (oxide polyanions) are important for some of the early
d-block metals, especially for V, Mo, and W. (See SAL sections 5.7 and 5.8 for more details.)
14. When a pair of aqua cations forms an MOM bridge with the elimination of water, what is the general rule for the
change in charge per M atom on the ion?
Consider the following example of the formation of a polymerized aqua cation:
The charge per aluminum atom is +3 for the mononuclear species on the left hand
side of the equation but only +2 for the dinuclear species on the right hand side.
Thus, polycation formation reduces the average positive charge per central M atom by
+1 per M. (The molecular structure of the dimerized aluminum ion is shown at right.)
15. (a) Write a balanced equation for the formation of P2O74 from PO43. (b) Write a balanced equation for the dimerization
of the complex [Fe(OH2)6]3+ to give [(H2O)4Fe(OH)2Fe(OH2)4]4+.
The two balanced equations are shown below. Note that the condensation reactions
involve a neutralization of charge, either by adding H+ to a highly charged anion or by
removing H+ from a highly charged cation. The structure of P4O124 , which is called
cyclotetrametaphosphate, is also shown at right. It is the dimer of the formula given in the
question, which is commonly used, but which species actually does not exist! (That is,
P2O74 is the empirical formula, and P4O124 is the correct molecular formula.)

The

structure

of

the

P4O124 ion in the salt

[NH4+][P4O12]
16. Consider the aqua ions resulting from the hydration of the following cations: U3+, Ag+, Pa5+, C4+, As3+, Tl+, Th4+
(a) Calculate the pKa and classify the acidity of each aqua ion.
NB: you need the radii provided in the table from the section on ionic solids to answer this question! Assume CN 6.
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(b) Write an equation for the reaction of their chlorides with water. Which of these would give cloudiness or
precipitation? The ones with a (s) in the product produce cloudiness or precipitate. CCl4 is immiscible with water.
UCl3 (s) + 6 H2O U(OH)3 (s) + 3 H3O+ (aq) + 3 Cl (aq)
AgCl (s) + H2O no reaction
2 PaCl5 (s) + 15 H2O Pa2O5 (s) + 10 H3O+ (aq) + 10 Cl (aq)
CCl4 (l) + H2O no reaction (but for kinetic reasons)
AsCl3 (s) + 6 H2O As(OH)3 (s) + 3 H3O+ (aq) + 3 Cl (aq)
In hot water: TlCl (s) + H2O Tl+ (aq) + Cl (aq)
ThCl4 (s) + 8 H2O ThO2 (s) + 4 H3O+ (aq) + 4 Cl (aq)
(c) If the solutions were adjusted to final pH's of 5.5 to 7, in what chemical form would each element be present? (See
page 55 in the lecture notes.)
U3+ (aq) (not UO22+ because of oxidation state); Ag+ (aq) (extremely low concentration since AgCl is rather insoluble);
Pa2O5 (s); CCl4 (l); As(OH)3 (not HAsO42 because of oxidation state); Tl+ (aq) (low concentration in cold water, TlCl
dissolves in hot water); ThO2 (s)
17. Extend Pauling's rules to predict the approximate basicity of the following polyoxo anions: (O3P-O-PO3)4, pyrophosphate
ion; (O3P-O-PO2-O-PO3)5, tripolyphosphate ion. (Hint: consider the acidity of the conjugate acids).
For the conjugate H2O3P-O-PO3H2, we apply Pauling's rule per phosphorus atom: pKa = 8 5 = 3. Now we deprotonate
on average twice per phosphorus, so 3 +10 = 13. The pKb = 1.
For the congjugate H2O3P-O-P(OH)O-O-PO3H2, we apply Pauling's rule for the terminal atoms to get 3 as above, while for
the central atom we get pKa = 8 5 = 3. Deprotonate an average of 1.67 per phosphorus, so 3+ 8.35 = 11.35. The pKb =
2.7. Hence pyrophosphate is more basic (smaller pKb) than tripolyphosphate.
18. Consider the chlorine oxoanions (Cl is the central atom in all): ClO, ClO2, ClO3 & ClO4.
(a) For each of these ions: (i) determine the Lewis structure, including resonance if applicable; (ii) determine the shape by
VSEPR theory, and sketch the molecule. Final answers should be as follows:

O C
v
Cl

O
Cl
O

C2v

O C
3v
Cl
O

O
Cl
O

Td
O

:
O
:
(b) Rank these anions in order of increasing Brnsted BASICITY in water, clearly indicating which is least and which is
most basic. Explain the origin of this series using your knowledge of acid-base theory in conjunction with the
structures of these anions which you have determined in part (a).
Consider their conjugates, which by Pauling's rules should be in the order of increasing acid strength in the order:
ClOH < OClOH < O2ClOH < O3ClOH
Hence the basicity of their conjugates will increase in the opposite order, with ClO4 (weakest base) < ClO3 (2nd
weakest base) < ClO2 (2nd strongest base) < ClO (strongest base)
19. Give formulas for the following common acids: nitric acid, sulfuric acid, hydrobromic acid, perchloric acid, carbonic
acid. What is the oxidation number of the central atom in each of these compounds? How are these related to the periodic
group number of the element?
N +5
Group 15 (Group number - 10)
HNO3
S +6
Group 16 (Group number - 10)
H2SO4
HBr
Br +1
Group 17 (18 -Group number). This example is not an oxoanion.)
Cl +7
Group 17 (Group number - 10)
HClO4
Group 14 (Group number - 10) - actually exists as the HCO3 ion in solution.
"H2CO3" C +4
20. Define the term amphoteric. Write chemical equations to illustrate the amphoteric character of Al(OH)3.
An amphoteric hydroxide will be neither basic nor acidic, and in the case of aluminum is a very insoluble solid. However,
aluminum hydroxide will react with either strong acid or strong base, and in the course of the reaction it will be dissolved.
See the following two equations:
Al(OH)3(s) + 3 H+(aq) Al3+(aq) + 3 H2O(l)
Al(OH)3(s) + OH(aq) Al(OH)4(aq)
21. Give examples of two basic oxides. Write equations illustrating the formation of each oxide from its component elements.
Write another chemical equation that illustrates the basic character of each oxide.
Li2O(s) + H2O(l) 2 LiOH(aq)
Group 1: 2 Li(s) + O2(g) Li2O(s)
BaO(s) + H2O(l) Ba(OH)2(aq)
Group 2: Ba(s) + O2(g) BaO(s)
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22. Give examples of two acidic oxides. Write equations illustrating the formation of each oxide from its component elements.
Write another chemical equation that illustrates the acidic character of each oxide.
P4O10(s) + 6 H2O(l) 4 H3PO4(aq)
Group 15: 4 P4(s) + 5 O2(g) P4O10(s)
Group 16: S8(s) + 8 O2(g) 8 SO2(s)
23. Write a balanced chemical equation for the reaction of an alkali metal with a halogen. Use M to represent the metal and X
to represent the halogen. Is the reaction likely to be exothermic or endothermic? Is the product ionic or covalent?
M (s) + X2 (l) MX (s) exothermic reaction, product is an ionic solid
24. Write a balanced chemical equation for the general reaction of an alkaline earth metal with oxygen. Use the symbol M to
represent the alkaline earth element. Is the reaction likely to be exothermic or endothermic? Is the product ionic or
covalent?
M (s) + O2 (l) MO (s) exothermic reaction, product is an ionic solid
25. Would you expect to find calcium naturally occurring in the earths crust as a free element? Why or why not?
Calcium is far too reactive (too easily oxidized) to survive in the environment in the metallic form. Remember the reaction
done in the lab where the element is placed in cold water, and produces the hydroxide and hydrogen gas spontaneously.
26. Place the following oxides in order of increasing basicity: CO2, SiO2, and SnO2.
See page 49 of the notes; the tin oxide is amphoteric, whereas carbon and silicon oxides are acidic. A reasonable guess
from their relative electronegativities is that SnO2 < SiO2 < CO2. Note that none are strong acid precursors.
27. Complete and balance equations for the following reactions.
(b) 2 Ca(s) + O2(g)
(a) 2 Li(s) + Cl2(g) 2 LiCl (s)

2 CaO (s)

28. Write balanced chemical equations for the reaction of hydrogen gas with oxygen, chlorine, nitrogen.
H2 (g) + N2 (g) 2 NH3 (g) (under catalysis)
H2 (g) + O2 (g) H2O (l) H2 (g) + Cl2 (g) 2 HCl (g)
29. Write an equation for the reaction of sodium and hydrogen. Name the product. Is it ionic or covalent? Predict one
physical property and one chemical property of this compound.
Na (s) + H2 NaH (s) sodium hydride is a salt-like hydride, so is ionic; it is a solid and reacts as a strong
reducing agent with most oxidizing agents (typically with the re-formation hydrogen gas)
30. One of the pieces of evidence for the hydride ion in metal hydrides comes from electrochemistry. Predict the reactions that
occur at each electrode when molten LiH is electrolyzed.
Anode: H H2 (g) + e
Cathode: Li+ (l) + e Li (l)
31. A method recently suggested for the preparation of hydrogen (and oxygen) proceeds as follows: (a) Sulfuric acid and
hydrogen iodide are formed from sulfur dioxide, water, and iodine.
(b) The sulfuric acid from the first step is decomposed by heat to water, sulfur dioxide, and oxygen.
(c) The hydrogen iodide from the first step is decomposed with heat to hydrogen and iodine.
Write a balanced equation for each of these steps and show that their sum is the decomposition of water to hydrogen and
oxygen.
SO2 (aq) + 2 H2O (l) + I2 (aq) H2SO4 (l) + 2 HI (g)
H2SO4 (l) H2O (g) + SO2 (g) + O2 (g)
.
2 HI (g) H2 (g) + I2 (g)
H2O (l) H2 (g) + O2 (g)
32. Calcium reacts with hydrogen gas at elevated temperatures to form a hydride. This compound reacts readily with water,
so it is an excellent drying agent for organic solvents.
(a) Write a balanced equation showing the formation of calcium hydride from Ca and H2.
Ca (s) + H2 (g) CaH2 (s)
(b) Write a balanced equation for the reaction of calcium hydride with water.
CaH2 (s) + 2 H2O (l) Ca(OH)2 (aq) + 2 H2 (g)
33. Write equations for the reaction of sodium with each of the halogens. Predict several physical properties that are common
to all of the alkali metal halides.
Na (s) + Cl2 (g) NaCl (s)
Na (s) + F2 (g) NaF (s)
Na (s) + I2 (g) NaI (s)
Na (s) + Br2 (g) NaBr(s)
All are colorless, brittle, ionic solids with intermediate melting points (several hundred, but less than a thousand degrees).
All are soluble in water to give solutions of the constituent ions. All conduct electricity in the molten state.
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34. Sodium peroxide is the primary product when sodium metal is burned in oxygen. Write a balanced equation for this
reaction.
2 Na (s) + O2 Na2O2 (s)
35. (a) Write balanced equations for the reaction of lithium, sodium, and potassium with O2. Specify which metal largely forms
oxides, which one forms peroxides, and which one forms superoxides.
a normal oxide
2 Li (s) + O2 (g) Li2O (s)
a peroxide
2 Na (s) + O2 Na2O2 (s)
a superoxide
K (s) + O2 KO2 (s)
(b) Write Lewis structures for the peroxide and superoxide ion.
2
.

:
:O
:O
O
O

peroxide

superoxide

36. A piece of sodium catches on fire in the laboratory! How do you extinguish the fire? What is the worst thing you could do?
Fire extinguishers for reactive metals act by smothering the flame. These so-called "class-D" extinguishers may contain
either graphite or sodium chloride. The graphite produces a solid coating of metal carbide over the surface of the burning
metal, thus smothering the fire. Sodium chloride melts at the temperatures involved, and the liquid forms an inert layer
over the surface of the metal, again smothering the combustion. Sand is also useful. Never use water!
37. When magnesium burns in air, it forms both an oxide and a nitride. Write balanced equations for the formation of both
3 Mg (s) + 2 N2 Mg3N2 (s)
compounds. Mg (s) + O2 MgO (s)
38. Name three uses of limestone. Write a balanced equation for the reaction of limestone with CO2 in water.
Agricultural: to furnish calcium ions to plants and to neutralize acidic soils
Bulding: lime (CaO) is used in mortar, and more importantly, in the manufacture of Portland cement
Steel-making: In the basic oxygen process, lime (formed in situ from the carbonate) reacts with gangue (silicon dioxide) to
form calcium silicate (slag)
CaCO3 (s) + H2O (l) + CO2 (aq) Ca(HCO3)2 (aq)
39. Explain what is meant by hard water. What causes hard water and what problems are associated with it?
Hard water contains metal ions such as Ca2+ and Mg2+. It is formed when ground water seeps through mineral beds of the
slightly soluble carbonates of these metals (e.g. the Dolomite in the Rocky Mountains). These ions react with soap
forming insoluble soap scum, thus reducing the efficiency of soaps. More problematically, they precipitate the carbonates
when the water is heated, causing the plugging of hot water pipes and boilers by "boiler scale".
40. Calcium hydroxide, Ca(OH)2, has a Ksp of 7.9 106, whereas that for Mg(OH)2 is 1.5 1011. Calculate the equilibrium
constant for the reaction
Ca(OH)2 (s) + Mg2+ (aq) Ca2+ (aq) + Mg(OH)2(s)
and explain why this reaction can be used in the commercial isolation of magnesium from sea water.
Ksp = 7.9 106
Ca(OH)2 (s) Ca2+ (aq) + 2 OH (aq)
2+

Mg (aq) + 2 OH (aq) Mg(OH)2(s)

1/Ksp = 1(1.5 1011)
2+
2+
Ca(OH)2 (s) + Mg (aq) Ca (aq) + Mg(OH)2(s)
Krxn = 5.3 105
Adding calcium hydroxide to sea water will displace magnesium ions by precipitation of magnesium hydroxide and
(partial) dissolving of the calcium ions. The magnesium hydroxide can be recovered and used to produce magnesium.
41. Why is hydrogen bonding important? Give some examples.
Hydrogen bonding is responsible for the lower density of the ice-I structure compared to liquid water. This ensures that
ice floats, keeping most lakes and oceans from freezing solid when exposed to very cold air masses. If the ice accumulated
at the bottom of the lake, in colder climates it would not completely thaw in a summer season, and then progressively more
of the lake would freeze until all were frozen, killing all living organisms in the lake.
Hydrogen bonding has many important functions in the regulation of biochemical processes. One famous example is the
H-bonds that link the two halves of the DNA double helix. pH control of solutions containing living cells is essential,
largely because big changes in the hydronium ion concentration would dramatically affect the hydrogen bonding
interactions in the cells, leading to cell death.
42. Describe the roles that the Group 1 metal play in living systems.
See your lecture notes.
43. Discuss the biological properties of the Group 2 elements.
See your lecture notes.

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