CHAPTER 22 THE ELEMENTS IN NATURE

AND INDUSTRY
END–OF–CHAPTER PROBLEMS

22.1 Hydrogen is abundant in the universe since its simple atoms were the first “created” after the “Big Bang.” H 2 has
the lowest density of any material, so it is only weakly held by the gravitational field of Earth.

22.2 Iron forms iron(III) oxide, Fe 2 O 3 (commonly known as hematite). Calcium forms calcium carbonate, CaCO 3 ,
(commonly known as limestone). Sodium is commonly found in sodium chloride (halite), NaCl. Zinc is
commonly found in zinc sulfide (sphalerite), ZnS.

22.3 a) Differentiation refers to the processes involved in the formation of Earth into regions (core, mantle, and crust)
of differing composition. Substances separated according to their densities, with the more dense material in the
core and less dense in the crust.
b) The four most abundant elements are oxygen, silicon, aluminum, and iron in order of decreasing abundance.
c) Oxygen is the most abundant element in the crust and mantle but is not found in the core. Silicon, aluminum,
calcium, sodium, potassium, and magnesium are also present in the crust and mantle but not in the core.

22.4 The left half of the transition metals are usually found as oxides, while the right half of the transition metals and
most of the p-block metals are found as sulfides. The more electronegative metals tend to form sulfides, the less
electronegative ones, oxides.

22.5 a) Bauxite (impure Al(OH) 3 ) b) Air (N 2 ) c) Seawater (NaCl) d) Limestone (CaCO 3 )

e) Seawater (NaCl)

22.6 Aluminosilicates are thermodynamically very stable. Great amounts of energy are needed for the production of a
metal from a silicate, making the process economically unfavorable.

22.7 Plants produced O 2 , slowly increasing the oxygen concentration in the atmosphere and creating an oxidative
environment for metals. Evidence of Fe(II) deposits pre-dating Fe(III) deposits suggests this hypothesis is true.
The decay of plant material and its incorporation into the crust increased the concentration of carbon in the crust
and created large fossil-fuel deposits.

22.8 Carbon atoms form a large number of bonds, which allows for the formation of a wide variety of complex
molecules necessary for life. Since C atoms are small, they form strong bonds with one another, giving organic
molecules stability, particularly with respect to reaction with O 2 and H 2 O.

22.9 Fixation refers to the process of converting a substance in the atmosphere into a form more readily usable by
organisms. Examples are the fixation of carbon by plants in the form of carbon dioxide and of nitrogen by
bacteria in the form of nitrogen gas. Fixation of carbon dioxide gas by plants converts the CO 2 into carbohydrates
during photosynthesis. Fixation of nitrogen gas by nitrogen-fixing bacteria involves the conversion of N 2 to
ammonia and ammonium ions.

22.10 If too much CO 2 enters the atmosphere from human activities (primarily forest clearing, decomposition of
limestone, and burning of carbon containing fuels), the possibility exists for an unnatural warming of Earth due to
trapping of heat by the “extra” CO 2 .

22.11 The labeled category in the figure is “Human activity and combustion.” Two other processes are the production of
compounds of Mg and Ca from dolomite, and the production of steel and aluminum.

22-1
22.12 Atmospheric nitrogen is utilized by three fixation pathways: atmospheric, industrial, and biological. Atmospheric
fixation requires high-temperature reactions (e.g., lightning) to convert N 2 into NO and other oxidized species.
Industrial fixation involves mainly the formation of ammonia, NH 3 , from N 2 and H 2 . Biological fixation occurs in
nitrogen-fixing bacteria that live in the roots of legumes. “Human activity” is referred to as “industrial fixation.”
Human activity is a significant factor, contributing about 17% of the nitrogen removed.

22.13 Because N–N single bonds are weak, cyclic and chain compounds containing these bonds are not very stable.

22.14 a) No gaseous phosphorus compounds are involved in the phosphorus cycle, so the atmosphere is not included in
the phosphorus cycle.
b) Two roles of organisms in phosphorus cycle: 1) Plants excrete acid from their roots to convert PO 4 3– ions into
more soluble H 2 PO 4 – ions, which the plant can absorb. 2) Through excretion and decay after death, organisms
return soluble phosphate compounds to the cycle.

22.15 a) Atmospheric fixation requires energy from lightning or fires; industrial fixation requires high temperature to
make the process proceed at a reasonable rate.
b) ∆H f for NO and NO 2 are both endothermic, so their formation requires energy. In contrast, ∆H f for NH 3 is
exothermic. The reaction is slow, however, and requires energy to increase its rate.
c) The energy comes from a widespread low-grade energy source: sunlight.
d) There would be less N 2 in the atmosphere and probably a greater biomass on Earth as a result of a low
activation energy for nitrogen fixation.

22.16 a) N 2 (g) + 2H 2 O(l) → 2NO(g) + 4H +(aq) + 4e– oxidation

b) 3H 2 O(l) + N 2 O(g) → 2NO 2 (g) + 6H +(aq) + 6e– oxidation
c) NH 3 (aq) + 2H 2 O(l) → NO 2 –(aq) + 7H +(aq) + 6e– oxidation
d) NO 3 –(aq) + 2H +(aq) + 2e– → NO 2 –(aq) + H 2 O(l) reduction
e) N 2 (g) + 6H 2 O(l) → 2NO 3 –(aq) + 12H +(aq) + 10e– oxidation

22.17 Plan: First determine the moles of F present in 100. kg of fluorapatite, using the molar mass of Ca 5 (PO 4 ) 3 F
(504.31 g/mol); take 15% of this amount. Convert mol F to mol SiF 4 , and use the ideal gas law to determine
the volume of the SiF 4 gas. For part b), convert moles of SiF 4 to moles of Na 2 SiF 6 using the mole ratio in the
given equation and convert moles of Na 2 SiF 6 to moles and then mass of F. The definition of ppm (“parts per
million”) states that 1 ppm F– = (1 g F–/(106 g H 2 O)). Find the volume of water that can be fluoridated with the
calculated mass of F.
Solution:
a) Moles of F =
 103 g Ca 5 (PO 4 )3 F   1 mol Ca 5 (PO 4 )3 F   1 mol F   15% 
(100. kg Ca 5 (PO4 )3 F )    504.31 g Ca (PO ) F   1 mol Ca (PO ) F   100% 
 1 kg Ca 5 (PO 4 3 
) F 5 4 3  5 4 3 
= 29.74361 mol F
 1 mol SiF4 
Moles of SiF 4 = ( 29.74361 mol F )   = 7.43590 mol SiF 4
 4 mol F 
PV = nRT

( 7.43590 mol SiF4 )  0.0821

L•atm 
 ( ( 273 + 1450. ) K )
V (L) =
nRT
=  mol•K  = 1051.86977 = 1.1x103 L
P (1.00 atm )
 1 mol Na 2SiF6 
b) Moles of Na 2 SiF 6 = ( 7.43590 mol SiF4 )   = 3.71795 mol Na 2 SiF 6
 2 mol SiF4 
 6 mol F−   19.00 g F− 
Mass (g) of F– = ( 3.71795 mol Na 2SiF6 )   
2
 = 423.8463 = 4.2x10 g F
–
 1 mol Na SiF −
 2 6   1 mol F 

22-2
 If 1 g F– will fluoridate 106 g H 2 O to a level of 1 ppm, how many grams (converted to mL using density, then
converted from mL to L to m3) of water can 423.8463 g F– fluoridate to the 1 ppm level? Necessary conversion
factors: 1 m3 = 1000 L, density of water = 1.00 g/mL .
3
 106 g H 2 O   mL H 2 O   1 cm3  10−2 m 
3
(
Volume (m ) = 423.8463 g F  −
)
 1 g F−   1.00 g H O   1 mL 
 1 cm 
= 423.8463 = 4.2x102 m3
  2   

22.18 Plan: Since the 50. t contains 2.0% Fe 2 O 3 by mass, 100 – 2.0 = 98% by mass of the 50. t contains
Ca 3 (PO 4 ) 2 . Find the moles of Ca 3 (PO 4 ) 2 in the sample and convert moles of Ca 3 (PO 4 ) 2 to moles and then mass
of P 4 , remembering that the production of P 4 has a 90% yield.
Solution:
a) The iron ions form an insoluble salt, Fe 3 (PO 4 ) 2 , that decreases the yield of phosphorus. This salt is of limited
value.
b) Use the conversion factor 1 metric ton (t) = 1x103 kg.
 98%   10 kg   10 g   1 mol Ca 3 (PO 4 ) 2 
3 3
Moles of Ca 3 (PO 4 ) 2 = ( 50. t )        = 157972.79 mol Ca 3 (PO 4 ) 2
 100%   1 t   1 kg   310.18 g Ca 3 (PO4 ) 2 
Mass (metric tons) of P 4 =
 1 mol P4   123.88 g P4   1 kg   1 t   90.% 
(157972.79 mol Ca 3 (PO4 )2 )    3  3  
 2 mol Ca 3 (PO 4 ) 2   1 mol P4   10 g   10 kg   100% 
= 8.80635 = 8.8 t P 4

22.19 a) An ore is a naturally occurring mixture of gangue and mineral from which an element can be profitably
extracted.
b) A mineral is a naturally occurring, homogeneous, crystalline solid, with a well-defined composition.
c) Gangue is the debris, such as sand rock and clay, associated with an ore.
d) Brine is a concentrated salt solution used as a source of Na, Cl, etc.

22.20 a) Roasting involves heating the mineral in air (O 2 ) at high temperatures to convert the mineral to the oxide.
b) Smelting is the reduction of the metal oxide to the free metal using heat and a reducing agent such as coke.
c) Flotation is a separation process in which the ore is removed from the gangue by exploiting the different
abilities of the two to interact with detergent. The gangue sinks to the bottom and the lighter ore-detergent mix is
skimmed off the top.
d) Refining is the final step in the purification process to yield the pure metal with no impurities.

22.21 Factors considered include cost, reducing strength needed, and by-products formed.

22.22 a) In general, the more active metal will be the one with the lower ionization energy and/or the greater enthalpy
of hydration. In this way, net energy will be given off when the more active element loses electrons and the less
active one gains them, with the formation of ions of the more active element and removal from solution of the
ions of the less active element. An example is:
Zn(s) + Cu2+(aq) → Cu(s) + Zn2+(aq)
b) This is similar to a) except that h ydration enthalpies are not involved. An example is:
Ca(l) + 2RbCl(l)  ∆ → CaCl (l) + 2Rb(g)
2

22.23 In general, nonmetals are obtained by oxidation and metals are obtained by reduction.

22.24 a) 6 b) 4 c) 2 d) 1

22.25 a) Slag is a waste product of iron metallurgy formed by the reaction:

CaO(s) + SiO 2 (s) → CaSiO 3 (l)
In other words, slag is a by-product of steelmaking and contains the impurity SiO 2 .
b) Pig iron, used to make cast iron products, is the impure product of iron metallurgy (containing 3–4% C) that is
purified to steel.

22-3
 c) Steel refers to the products of iron metallurgy, specifically alloys of iron containing small amounts of other
elements including 1–1.5% carbon.
d) Basic-oxygen process refers to the process used to purify pig iron to form steel. The pig iron is melted and
oxygen gas under high pressure is passed through the liquid metal. The oxygen oxidizes impurities to their oxides,
which then react with calcium oxide to form a liquid that is decanted. Molten steel is left after the basic-oxygen
process.

22.26 Pyrometallurgy uses heat to obtain the metal, electrometallurgy uses electrical energy, and hydrometallurgy uses
reactions in aqueous solution.
a) Fe is produced by a high-temperature process using C as the reductant.
b) Na is produced (with Cl 2 and H 2 ) electrochemically in a Downs cell.
c) Au is produced in a hydrometallurgical process using CN– as a complexing agent.
d) Al is produced electrochemically in the Hall-Heroult process after a hydrometallurgical step to dissolve the ore.

22.27 Iron and nickel are more easily oxidized than copper, so they are separated from the copper in the roasting step
and conversion to slag. In the electrorefining process, all three metals are oxidized into solution, but only Cu2+
ions are reduced at the cathode to form Cu(s).

22.28 Molten cryolite is a good solvent for Al 2 O 3 .

22.29 a) Molecules containing different isotopes of a given atom react at different rates (heavier atoms react more
slowly) if a bond is broken to the atom in question.
b) H compounds exhibit a relatively large effect, since the mass ratio of the isotopes is larger for H than for any
other atom.
c) It would be smaller for C, since the mass ratio of the isotopes is smaller.

22.30 The potassium in the molten potassium salt is reduced by molten sodium. Ordinarily, sodium would not be a
good reducing agent for the more active potassium. But the reduction is carried out above the boiling point of
potassium, producing gaseous potassium:
Na(l) + K+(l)  Na+(l) + K(g)
The potassium gas is removed as it is produced. Le Châtelier’s principle states that the system shifts toward
formation of more K as the gaseous metal leaves the cell.

22.31 a) Aqueous salt solutions are mixtures of ions and water. When two half-reactions are possible at an electrode,
the one with the more positive electrode potential occurs. In this case, the two half-reactions are:
M + + e– → M0 E° red = –3.05 V, –2.93 V, and –2.71 V
for Li+, K+, and Na+, respectively
2H 2 O + 2e → H 2 + 2OH
– –
E red = –0.42 V, with an overvoltage of about –1 V
In all of these cases, it is energetically more favorable to reduce H 2 O to H 2 than to reduce M+ to M.
b) The question asks if Ca could chemically reduce RbX, i.e., convert Rb+ to Rb0. In order for this to occur, Ca0
loses electrons (Ca0 → Ca2+ + 2e–) and each Rb+ gains an electron (2Rb+ + 2e– → 2Rb0). The reaction is written as
follows:
2RbX + Ca → CaX 2 + 2Rb
where ∆H = IE 1 (Ca) + IE 2 (Ca) – 2IE 1 (Rb) = 590 + 1145 – 2(403) = +929 kJ/mol.
Recall that Ca0 acts as a reducing agent for the Rb+ ion because it oxidizes. The energy required to remove an
electron is the ionization energy. It requires more energy to ionize calcium’s electrons, so it seems unlikely that
Ca0 could reduce Rb+. Based on values of IE and a positive ∆H for the forward reaction, it seems more reasonable
that Rb0 would reduce Ca2+.
c) If the reaction is carried out at a temperature greater than 688°C (the boiling point of rubidium), the product
mixture will contain gaseous Rb. This can be removed from the reaction vessel, causing a shift in equilibrium to
form more Rb product. If the reaction is carried out between 688°C and 1484°C (bp for Ca), then Ca remains in
the molten phase and remains separated from gaseous Rb.

22-4
 d) The reaction of calcium with molten CsX is written as follows:
2CsX + Ca → CaX 2 + 2Cs
where ∆H = IE 1 (Ca) + IE 2 (Ca) – 2IE 1 (Cs) = 590 + 1145 – 2(376) = +983 kJ/mol. This reaction is more
unfavorable than for Rb, but Cs has a lower boiling point of 671°C. If the reaction is carried out between 671°C
and 1484°C, then calcium can be used to separate gaseous Cs from molten CsX.

22.32 Plan: Write the balanced equation for the process. For every two moles of Na metal produced, one mole of Cl 2 is
produced. Calculate the amount of chlorine gas from the reaction stoichiometry, then use the ideal gas law to find
the volume of chlorine gas. For part b), write the balanced equation for the oxidation of Cl– to Cl 2 ; convert moles
of Cl 2 produced to moles of electrons required and then convert to coulombs with the conversion factor
96,485 C = 1 mole of e–. Convert coulombs to time with the conversion factor 1 C = 1 A•s.
Solution:
a) 2NaCl(l) → 2Na(l) + Cl 2 (g)
 103 g   1 mol Na   1 mol Cl2 
Moles of Cl 2 = ( 31.0 kg Na ) 
 1 kg   22.99 g Na   2 mol Na 
= 674.2062 mol Cl 2
   
PV = nRT

( 674.2062 mol Cl2 )  0.0821

L•atm 
 ( ( 273 + 540. ) K )
V (L) =
nRT
=  mol•K  = 4.50014x104 = 4.5x104 L
P (1.0 atm )
b) Two moles of electrons are passed through the cell for each mole of Cl 2 produced:
2Cl–(l) → Cl 2 (g) + 2e–
 2 mol e −   96, 485 C 
Coulombs = ( 674.2062 mol Cl 2 )  = 1.30101570x108 = 1.30x108 C
 1 mol Cl   1 mol e − 
 2 

(
c) Time (s) = 1.30101570x108 C 

)
A•s  1 

6
 = 1.689631x10 = 1.69x10 s
 1 C   77.0 A 
6

22.33 a) C (coke)
b) Fuel (increasing temperature)
c) CO
d) 3Fe 2 O 3 (s) + CO(g) → 2Fe 3 O 4 (s) + CO 2 (g)
Fe 3 O 4 (s) + CO(g) → 3FeO(s) + CO 2 (g)
FeO(s) + CO(g) → Fe(l) + CO 2 (g)

22.34 ∆ → CaO(s) + CO (g)

a) CaCO 3 (s)  2
b) The lime (CaO) reacts with SiO 2 present in the iron ore to produce CaSiO 3 slag. The word “flux” comes from
the Latin word meaning “to flow.” The liquid slag flows down to the bottom of the furnace and floats on the more
dense iron.
c) CaO(s) + SiO (s)  ∆ → CaSiO (l)
2 3

22.35 a) Mg2+ is more difficult to reduce than H 2 O, so H 2 (g) would be produced instead of Mg metal. Cl 2 (g) forms at
the anode due to overvoltage.
b) The ∆H f for MgCl 2 (s) is –641.6 kJ/mol: Mg(s) + Cl 2 (g) → MgCl 2 (s) + heat.
High temperature favors the reverse reaction (which is endothermic), so high temperatures favor the formation of
magnesium metal and chlorine gas.

22.36 a) Yes, iodine is near the bottom of the periodic table, thus it has a low electronegativity which allows it to adopt
positive oxidation states.
b) 2IO 3 –(aq) + 5HSO 3 –(aq) → 3HSO 4 –(aq) + 2SO 4 2–(aq) + H 2 O(l) + I 2 (s)
Oxidizing agent: IO 3 – Reducing agent: HSO 3 –

22-5
c) 0.78 mol% NaIO 3 leaves (100.00 – 0.78) mol% NaNO 3 = 99.22 mol% NaNO 3
Mass (g) of I 2 =
 1 kg   103 g   1 mol NaNO3   0.78 mol% NaIO3   1 mol I 2   253.8 g I 2 
( 2000. lb )           
 2.205 lb   1 kg   85.00 g NaNO3   ( 99.22 ) mol% NaNO3
 −
 2 mol IO3   1 mol I 2 
= 1.0645339x104 = 1.1x104 g I 2

22.37 a) Sulfur dioxide is the reducing agent and is oxidized to the +6 state (as sulfate ion, SO 4 2–).
b) The sulfate ion formed reacts as a base in the presence of acid to form the hydrogen sulfate ion.
SO 4 2–(aq) + H+(aq) → HSO 4 –(aq)
c) Skeleton redox equation: SO 2 (g) + H 2 SeO 3 (aq) → Se(s) + HSO 4 –(aq)
Reduction half-reaction: H 2 SeO 3 (aq) → Se(s)
balance O and H H 2 SeO 3 (aq) + 4H+(aq) → Se(s) + 3H 2 O(l)
balance charge H 2 SeO 3 (aq) + 4H+(aq) + 4e– → Se(s) + 3H 2 O(l)
Oxidation half-reaction: SO 2 (g) → HSO 4 –(aq)
balance O and H SO 2 (g) + 2H 2 O(l) → HSO 4 –(aq) + 3H+(aq)
balance charge SO 2 (g) + 2H 2 O(l) → HSO 4 –(aq) + 3H+(aq) + 2e–
Multiply oxidation half-reaction by 2 2SO 2 (g) + 4H 2 O(l) → 2HSO 4 –(aq) + 6H+(aq) + 4e–
Add the two half-reactions:
H 2 SeO 3 (aq) + 4H+(aq) + 4e– → Se(s) + 3H 2 O(l)
2SO 2 (g) + 4H 2 O(l) → 2HSO 4 –(aq) + 6H+(aq) + 4e–
H 2 SeO 3 (aq) + 2SO 2 (g) + H 2 O(l) → Se(s) + 2HSO 4 –(aq) + 2H+(aq)

22.38 The only halogen capable of oxidizing Cl– is F 2 , which is expensive and dangerous to handle. F 2 also reacts with
water, wasting the reagent.

22.39 3K 2 SiF 6 (s) + 4Al(s) → 6KF(s) + 3Si(s) + 4AlF 3 (s)

2 ( 55.85 g/mol )
22.40 Mass % Fe = (100% ) = 69.94364 = 69.94% Fe
159.70 g/mol
3 ( 55.85 g/mol )
Mass % Fe = (100% ) = 72.36018 = 72.36% Fe
231.55 g/mol
1( 55.85 g/mol )
mass % Fe = (100% ) = 46.545545 = 46.55% Fe
119.99 g/mol

22.41 4P(s) + 5O 2 (g) → P 4 O 10 (s)

P 4 O 10 (s) + 6CaO(s) → 2Ca 3 (PO 4 ) 2 (s)

22.42 a) The oxidation state of copper in Cu 2 S is +1 (sulfur is –2).

The oxidation state of copper in Cu 2 O is +1 (oxygen is –2).
The oxidation state of copper in Cu is 0 (oxidation state is always 0 in the elemental form).
b) The reducing agent is the species that is oxidized. Sulfur changes oxidation state from –2 in Cu 2 S to +4 in SO 2 .
Therefore, Cu 2 S is the reducing agent, leaving Cu 2 O as the oxidizing agent.

22.43 Al 2 O 3 is amphoteric and will dissolve in base:

Al 2 O 3 (s) + 2NaOH(aq) + 3H 2 O(l) → 2NaAl(OH) 4 (aq)
Fe 2 O 3 and TiO 2 have no acidic properties, so do not dissolve and can be removed.

22.44 a) Use the surface area and thickness of the film to calculate its volume. Multiply the volume by the density to
find the mass of the aluminum oxide. Convert mass to moles of aluminum oxide. The oxidation of aluminum
involves the loss of three electrons for each aluminum atom or six electrons for each Al 2 O 3 compound formed.
From this, find the number of electrons produced and multiply by Faraday’s constant to find coulombs.

22-6
 3
 1 cm   3.97 g Al 2O3   1 mol Al 2O3 
( 2
)(
Moles of Al 2 O 3 = 2.5 m 23x10 m  −2  −6
)   101.96 g Al O 
 10 m   cm3  2 3
= 2.2388682 mol Al 2 O 3
 6 mol e −   96, 485 C 
Coulombs = ( 2.2388682 mol Al 2O3 )  = 1.296103x106 = 1.3x106 C
 1 mol Al O   1 mol e − 
 2 3
b) Current in amps can be found by dividing charge in coulombs by the time in seconds.
[(1.296103x106 C)/[15 min (60 s/min)] x (1 A/(C/s)) = 1200 = 1.2x103 A

22.45 a) Work = ∆G° = –nFE°

Work = – (2 mol e–)(96,485 C/mol e–)(1.24 V)[(J/C)/V] = –2.392828x105 = –2.39x105 J
(The 2 in 2 mol e– is an exact number, and has no bearing on the significant figures.)
b) Efficiency = [(useful work done)/(energy input)] x 100%
Efficiency = [(2.392828x105 J)/(400 kJ(103 J/1 kJ) )] x 100% = 59.8207 = 59.8%
 400 kJ   1kW•s   1 h   $0.06 
c) Cost = ( 500. mol H 2 )      = 3.333333 = $3.33
 1 mol H 2   1 kJ   3600 s   kW•h 

22.46 a) H 2 and CO 2
b) The zeolite acts as a molecular filter to remove molecules larger than H 2 .

22.47 Plan: Free energy, ∆G  , is the measure of the ability of a reaction to proceed spontaneously. ∆G° can be
calculated with the relationship ∑m ∆Gf (products) – ∑n ∆Gf (reactants) .
Solution:
The direct reduction of ZnS follows the reaction:
2ZnS(s) + C(graphite) → 2Zn(s) + CS 2 (g)

∆Grxn = [(2 mol Zn)( ∆Gf of Zn) + (1 mol CS 2 )( ∆Gf of CS 2 )]
– [(2 mol ZnS)( ∆Gf of ZnS) + (1 mol C)( ∆Gf of C)]

∆Grxn = [(2 mol)(0 kJ/mol) + (1 mol)(66.9 kJ/mol)] – [(2 mol)(–198 kJ/mol) + (1 mol)(0 kJ/mol)]

∆Grxn = 462.9 = +463 kJ

Since ∆Grxn is positive, this reaction is not spontaneous at standard-state conditions. The stepwise reduction
involves the conversion of ZnS to ZnO, followed by the final reduction step:
2ZnO(s) + C(s) → 2Zn(s) + CO 2 (g)

∆Grxn = [(2 mol Zn)( ∆Gf of Zn) + (1 mol CO 2 )( ∆Gf of CO 2 )]
– [(2 mol ZnO)( ∆Gf of ZnO) + (1 mol C)( ∆Gf of C)]

∆Grxn = [(2 mol)(0 kJ/mol) + (1 mol)(–394.4 kJ/mol)] – [(2 mol)(–318.2 kJ/mol) + (1 mol)(0 kJ/mol)]

∆Grxn = +242.0 kJ
This reaction is also not spontaneous, but the oxide reaction is less unfavorable.

22.48 The formation of sulfur trioxide is very slow at ordinary temperatures. Increasing the temperature can speed up
the reaction, but the reaction is exothermic, so increasing the temperature decreases the yield. Recall that yield, or
the extent to which a reaction proceeds, is controlled by the thermodynamics of the reaction. Adding a catalyst
increases the rate of the formation reaction but does not impact the thermodynamics, so a lower temperature can be
used to enhance the yield. Catalysts are used in such a reaction to allow control of both rate and yield of the
reaction.

22.49 a) SO 3 (g) + H 2 SO 4 (l) → H 2 S 2 O 7 (l)

H 2 S 2 O 7 (l) + H 2 O(l) → 2H 2 SO 4 (l)

22-7
 b) At high temperature, H 2 O(g) catalyzes the polymerization of SO 3 to (SO 3 ) x , which forms a smoke which
makes poor contact with the H 2 O.

22.50 All the steps in its production are exothermic, and the excess heat (in the form of steam) can be sold profitably.

22.51 a) The chlor-alkali process yields Cl 2 , H 2 , and NaOH.

b) The mercury-cell process yields higher purity NaOH, but produces Hg-polluted waters that are discharged into
the environment.

22.52 Plan: ∆G° at 25°C can be calculated with the relationship ∑m ∆Gf (products) – ∑n ∆Gf (reactants) . Calculate ∆G°
    
at 500.°C with the relationship ∆Grxn = ∆H rxn – T ∆Srxn . ∆H rxn and ∆Srxn must be calculated first. The
equilibrium constant K is calculated by using ∆G° = –RT ln K. Finally, to find the temperature at which the
  
reaction becomes spontaneous, use ∆Grxn = 0 = ∆H rxn – T ∆Srxn and solve for temperature.
Solution:
a) The balanced equation for the oxidation of SO 2 to SO 3 is 2SO 2 (g) + O 2 (g) → 2SO 3 (g).

∆Grxn = ∑m ∆Gf (products) – ∑n ∆Gf (reactants)

∆Grxn = [(2 mol SO 3 )( ∆Gf of SO 3 )] – [(2 mol SO 2 )( ∆Gf of SO 2 ) + (1 mol O 2 )( ∆Gf of O 2 )]

∆Grxn = [(2 mol)(–371 kJ/mol)] – [(2 mol)(–300.2 kJ/mol) + (1 mol O 2 )(0 kJ/mol)]

∆Grxn = –141.6 = –142 kJ

Since ∆Grxn is negative, the reaction is spontaneous at 25°C.
b) The rate of the reaction is very slow at 25°C, so the reaction does not produce significant amounts of SO 3 at
room temperature.

c) ∆H rxn = ∑m ∆H f (products) – ∑n ∆H f (reactants)

∆H rxn = [(2 mol SO 3 )( ∆H f of SO 3 )] – [(2 mol SO 2 )( ∆H f of SO 2 ) + (1 mol O 2 )( ∆H f of O 2 )]

∆H rxn = [(2 mol)(–396 kJ/mol)] – [(2 mol)(–296.8 kJ/mol) + (1 mol)(0 kJ/mol)]

∆H rxn = –198.4 = –198 kJ
  
∆Srxn = ∑m Sproducts – ∑n Sreactants

∆Srxn = [(2 mol SO 3 )( S  of SO 3 )] – [(2 mol SO 2 )( S  of SO 2 ) + (1 mol O 2 )( S  of O 2 )]

∆Srxn = [(2 mol)(256.66 J/mol•K)] – [(2 mol)(248.1 J/mol•K) + (1 mol)(205.0 J/mol•K)]

∆Srxn = –187.88 = –187.9 J/K
  
∆G500 = ∆H rxn – T ∆Srxn = –198.4 kJ – ((273 + 500.) K)(–187.88 J/K)(1 kJ/103 J) = –53.16876 = –53 kJ
The reaction is spontaneous at 500°C since free energy is negative.
d) The equilibrium constant at 500°C is smaller than the equilibrium constant at 25°C because the free energy at
500°C indicates the reaction does not go as far to completion as it does at 25°C.
Equilibrium constants can be calculated from ∆G° = –RT ln K.
 103 J 
( − 142 kJ )  
∆G   1 kJ 
At 25°C: ln K = =– = 57.31417694
− RT (8.314 J/mol•K) ((273 + 25)K)
K 25 = e57.31417694 = 7.784501x1024 = 7.8x1024

22-8
  103 J 
 ( −53 kJ ) 
∆G   1 kJ 
At 500°C: ln K = =– = 8.246817
− RT (8.314 J/mol•K) ((273 + 500)K)

K 500 = e8.246817 = 3.815x103 = 3.8x103

e) Temperature below which the reaction is spontaneous at standard state can be calculated by setting ∆G° equal
to zero and using the enthalpy and entropy values at 25°C to calculate the temperature.
  
∆Grxn = 0 = ∆H rxn – T ∆Srxn
 
∆H rxn = T ∆Srxn
∆H  –198 kJ
T = = = 1.05375x103 = 1.05x103 K
  1 kJ 
∆S –187.9 J/K  3 
 10 J 

22.53 Plan: This problem deals with the stoichiometry of electrolysis. The balanced oxidation half-reaction for the
chlor-alkali process is given in the chapter:
2Cl–(aq) → Cl 2 (g) + 2e–
Use the Faraday constant, F, (1 F = 9.6485x104 C/mol e–) and the fact that one mol of Cl 2 produces two mol e– or
2 F, to convert coulombs to moles of Cl 2 .
Solution:
 C   3600 s   1 mol e −   1 mol Cl 2   70.90 g Cl 2   1 kg   2.205 lb 
(
Mass (lb) of Cl 2 = 3x104 A  s  
 A  1 h 
)
 ( 8 h )    −   3  
   96, 485 C   2 mol e   1 mol Cl 2   10 g   1 kg 
= 699.9689 = 7x102 lb Cl 2

22.54 a) The products are kept separate because Cl 2 reacts with NaOH(aq) to produce NaOCl(aq) and NaCl(aq).
b) The temperature at which the reaction is run determines the product formed.
c) Cl 2 (g) + 2OH –(aq) → Cl–(aq) + OCl–(aq) + H 2 O(l)
3Cl 2 (g) + 6OH –(aq) → 5Cl–(aq) + ClO 3 –(aq) + 3H 2 O(l)
Cl 2 / 2OH – is the mole ratio in both cases.

22.55 2SO 2 (g) + O 2 (g) → 2SO 3 (g)

(P )
2
SO3
a) K p = 3.18 = PSO2 = PSO3 (1:1 mole ratio)
(P ) (P )
2
SO2 O2

1
( PO )
3.18 =
2

PO2 = 0.3144654 = 0.314 atm O 2

(P )
2
SO3 ( 95)2
b) K p = 3.18 = =
(P ) (P )
SO2
2
O2
( 5)2 ( PO2 )
PO2 = 113.522 = 1x102 atm O 2

22.56 Plan: Write the balanced equation. Use the stoichiometry in the equation to find the moles of H 3 PO 4 produced by
the reaction of the given amount of P 4 O 10 . Divide moles of H 3 PO 4 by the volume to obtain its molarity. Since
H 3 PO 4 is a weak acid, use its equilibrium expression to find the [H 3 O+] and then pH.
Solution:
a) Because P 4 O 10 is a drying agent, water is incorporated in the formation of phosphoric acid, H 3 PO 4 .
P 4 O 10 (s) + 6H 2 O(l) → 4H 3 PO 4 (l)

22-9
  1 mol P4 O10   4 mol H3 PO 4 
b) Moles of H 3 PO 4 = ( 8.5 g P4 O10 )    = 0.11976892 mol H 3 PO 4
 283.88 g P4 O10   1 mol P4 O10 
 0.11976892 mol H3 PO 4 
Molarity of H 3 PO 4 =   = 0.1596919 M H 3 PO 4
 0.750 L 
Phosphoric acid is a weak acid and only partly dissociates to form H 3 O+ in water, based on its K a . Since
K a1 >> K a2 >> K a3 , assume that the H 3 O+ contributed by the second and third dissociation is negligible in
comparison to the H 3 O+ contributed by the first dissociation.
H 3 PO 4 (l) + H 2 O(l) → H 3 O+(aq) + H 2 PO 4 –(aq)

 H3O +   H 2 PO 4 − 
K a = 7.2x10 = –3  
H3 PO 4 

K a = 7.2x10–3 =
[ x ][ x ] Assume x is small compared to 0.1596919.
( 0.1596919 − x )
K a = 7.2x10–3 =
[ x ][ x ]
( 0.1596919 )
x = 0.0339084 M
Check assumption that x is small compared to to 0.1596919:
0.0339084
(100 ) = 21% error, so the assumption is not valid.
0.1596919
The problem will need to be solved as a quadratic.
x2 = (7.2x10–3)(0.1596919 – x) = 1.14978x10–3 – 7.2x10–3x
x2 + 7.2x10–3x – 1.14978x10–3 = 0
a=1 b = 7.2x10–3 c = –1.14978x10–3

x=
−7.2x10−3 ± ( 7.2x10 )
−3 2
(
− 4 (1) −1.14978x10−3 )
2 (1)
–2 +
x = 3.049897x10 M H 3 O
pH = –log [H 3 O+] = –log (3.049897x10–2) = 1.51571 = 1.52

22.57 a) D+(aq), OD–(aq) and traces of CH 3 O–(aq) and H +(aq). Eventually, HDO, H 2 O, and CH 3 OD would form.
b) D 2 O(l) → D+(aq) + OD–(aq)
CH 3 OH(aq) + OD–(aq) → CH 3 O–(aq) + HDO(l)
CH 3 O–(aq) + D 2 O(l) → CH 3 OD(l) + OD–(aq)
HDO(l) → D+(aq) + OH –(aq)
HDO(l) + OH –(aq) → H 2 O(l) + OD–(aq)

22.58 Plan: Write a balanced equation for the production of iron and use the reaction stoichiometry to calculate the
amount of CO 2 produced when the given amount of Fe is produced. Then write a balanced equation for the
combustion of gasoline (C 8 H 18 .) Find the total volume of gasoline, use the density to convert volume to mass
of gasoline, and use the reaction stoichiometry to calculate the amount of CO 2 produced.
Solution:
a)The reaction taking place in the blast furnace to produce iron is:
Fe 2 O 3 (s) + 3CO(g) → 2Fe(s) + 3CO 2 (g)
 2000 lb   1 kg   103 g   1 mol Fe   3 mol CO 2   44.01 g CO 2 
Mass (g) of CO 2 = ( 8400.t Fe )   
     
 1 t   2.205 lb   1 kg   55.85 g Fe   2 mol Fe   1 mol CO 2 
= 9.005755x109 = 9.006x109 g CO 2

22-10
 b) Combustion reaction for octane:
2C 8 H 18 (l) + 25O 2 (g) → 16CO 2 (g) + 18H 2 O(l)
Mass (g) of CO 2 =
 5.0 gal   4 qt   1 L   1 mL   0.74 g   1 mol C8 H18   16 mol CO2   44.01 g CO2 
( )
1.0x106 autos      −3      
 1 auto   1 gal   1.057 qt   10 L   mL   114.22 g C8 H18   2 mol C8 H18   1 mol CO 2 
= 4.31604x1010 = 4.3x1010 g CO 2
The CO 2 production by automobiles is much greater than that from steel production.

22.59 a) Step 1 Cl 2 (g) + CH 2 =CH 2 (g) → CH 2 ClCH 2 Cl(g)

Step 2 CH 2 ClCH 2 Cl(g) → CH 2 =CHCl(g) + HCl(g)
b) Cl 2 (g) + CH 2 =CH 2 (g) → CH 2 =CHCl(g) + HCl(g)
c) Addition reaction
d) Elimination reaction
 1 mol CH 2 =CHCl   62.49 g CH 2 =CHCl 
e) ( 0.45 mol Cl2 )    = 28.1205 = 28 g CH 2 =CHCl
 1 mol Cl2   1 mol CH 2 =CHCl 

22.60 Plan: Step 2 of “Isolation of Magnesium” describes this reaction. Sufficient OH– must be added to precipitate
Mg(OH) 2 . The necessary amount of OH– can be determined from the K sp of Mg(OH) 2 . For part b), use the K sp of
Ca(OH) 2 to determine the amount of OH– that a saturated solution of Ca(OH) 2 provides. Substitute this amount
into the K sp expression for Mg(OH) 2 to determine how much Mg2+ remains in solution with this amount of OH–.
Calculate the fraction of [Mg2+] remaining and subtract from 1 to obtain the fraction of [Mg2+] that precipitated.
Solution:
a) Mg(OH) 2 (s) → Mg2+(aq) + 2OH–(aq)
K sp = 6.3x10–10 = [Mg2+][OH –]2
6.3x10−10 6.3x10−10
[OH –] = = = 1.100699x10–4 = 1.1x10–4 M
[Mg 2+ ] 0.052
Thus, if [OH –] > 1.1x10–4 M (i.e., if pH > 10.04), Mg(OH) 2 will precipitate.
b) Ca(OH) 2 (s) → Ca2+(aq) + 2OH–(aq)
K sp = 6.5x10–6 = [Ca2+][OH –]2 = (x)(2x)2 = 4x3
x = 0.011756673; [OH –] = 2x = 0.023513347 M
K sp (Mg(OH) 2 ) = 6.3x10–10 = [Mg2+][OH –]2
6.3x10−10
[Mg2+] = = 1.1394930x10–6 M
( 0.023513347 ) 2

This concentration is the amount of the original 0.052 M Mg2+ that was not precipitated. The percent
precipitated is the difference between the remaining [Mg2+] and the initial [Mg2+] divided by the initial
concentration.
Fraction Mg2+ remaining = (1.1394930x10–6 M)/(0.052 M) = 2.19134x10–5
Mg2+ precipitated = 1 – 2.19134x10–5 = 0.9999781 = 1 (To the limit of the significant figures, all
the magnesium has precipitated.)

    
22.61 Plan: The equation ∆Grxn = ∆H rxn – T ∆Srxn will be used to calculate ∆Grxn at the two temperatures. ∆H rxn

and ∆Srxn will have to be calculated first. Then use ∆G° = –RT ln K to determine K. Subscripts indicate the
temperature, and (1) or (2) indicate the reaction.
Solution:
For the first reaction (1):

∆H rxn = ∑m ∆H f (products) – ∑n ∆H f (reactants)

∆H rxn = [(4 mol NO)( ∆H f of NO) + (6 mol H 2 O)( ∆H f of H 2 O)]
– [(4 mol NH 3 )( ∆H f of NH 3 ) + (5 mol O 2 )( ∆H f of O 2 )]

22-11
 
∆H rxn = [(4 mol)(90.29 kJ/mol) + (6 mol)(–241.826 kJ/mol)] – [(4 mol)(–45.9 kJ/mol) + (5 mol)(0 kJ/mol)]

∆H rxn = –906.196 kJ

∆Srxn = [(4 mol NO)( S  of NO) + (6 mol H 2 O)( S  of H 2 O)]
– [(4 mol NH 3 )( S  of NH 3 ) + (5 mol O 2 )( S  of O 2 )]

∆Srxn = [(4 mol)(210.65 J/K•mol) + (6 mol)(188.72 J/K•mol)]
– [(4 mol)(193 J/K•mol) + (5 mol O 2 )(205.0 J/K•mol)](1 kJ/103 J)

∆Srxn = 0.17792 kJ/K
  
∆Grxn = ∆H rxn – T ∆Srxn

∆G25 = –906.196 kJ – [(273 + 25)K]( 0.17792 kJ/K) = –959.216 kJ

∆G900 = –906.196 kJ – [(273 + 900.)K]( 0.17792 kJ/K) = –1114.896 kJ
For the second reaction (2):

∆H rxn = [(2 mol N 2 )( ∆H f of N 2 ) + (6 mol H 2 O)( ∆H f of H 2 O)]
– [(4 mol NH 3 )( ∆H f of NH 3 ) + (3 mol O 2 )( ∆H f of O 2 )]

∆H rxn = [(2 mol)(0 kJ/mol) + (6 mol)(–241.826 kJ/mol)] – [(4 mol)(–45.9 kJ/mol) + (3 mol)(0 kJ/mol)]

∆H rxn = –1267.356 kJ

∆Srxn = [(2 mol N 2 )( S  of N 2 ) + (6 mol H 2 O)( S  of H 2 O)]
– [(4 mol NH 3 )( S  of NH 3 ) + (3 mol O 2 )( S  of O 2 )]

∆Srxn = [(2 mol)(191.5 J/K•mol) + (6 mol)(188.72 J/K•mol)]
– [(4 mol)(193 J/K•mol) + (3 mol)(205.0 J/K•mol)](1 kJ/103 J)

∆Srxn = 0.12832 J/K
  
∆Grxn = ∆H rxn – T ∆Srxn

∆G25 = –1267.356 kJ – [(273 + 25)K](0.12832 kJ/K) = –1305.595 kJ

∆G900 = –1267.356 kJ – [(273 + 900.)K](0.12832 kJ/K) = –1417.875 kJ
∆G 
= −
( −959.216 kJ/mol )  103 J 
a) ln K 25 (1) =   = 387.15977
− RT (8.314 J/mol•K ) ( ( 273 + 25) K )  1 kJ 
K 25 (1) = 1.38x10168 = 1x10168
∆G 
= −
( −1305.595 kJ/mol )  103 J 
ln K 25 (2) =   = 526.9655
− RT (8.314 J/mol•K ) ( ( 273 + 25) K )  1 kJ 
K 25 (2) = 7.2146x10228 = 7x10228
∆G 
= −
( −1114.896 kJ/mol )  103 J 
b) ln K 900 (1) =   = 114.3210817
− RT (8.314 J/mol•K ) ( ( 273 + 900 ) K )  1 kJ 
K 900 (1) = 4.4567x1049 = 4.6x1049
∆G 
= −
( −1417.875 kJ/mol )  103 J 
ln K 900 (2) =   = 145.388
− RT (8.314 J/mol•K ) ( ( 273 + 900 ) K )  1 kJ 
K 900 (2) = 1.38422x1063 = 1.4x1063
 175 mg Pt   10−3 g   1 kg   32.15 Troy Oz   $1557 
(
c) Cost ($) Pt = 1.01x107 t HNO3  )     3  
 1 t HNO3   1 mg   10 g   1 kg
 
  1 troy oz 
= 8.847672x107 = $8.8x107

22-12
  175 mg Pt   72%   10−3 g   1 kg   32.15 troy oz   $1557 
(
d) Cost ($) Pt = 1.01x107 t HNO3  )      3  
 1 t HNO3   100%   1 mg   10 g   1 kg
 
  1 troy oz 
= 6.3703238x107 = $6.4x107

22.62 Balanced reactions: 2FeTiO 3 (s) + 7Cl 2 (g) + 6C(s) → 2TiCl 4 (g) + 2FeCl 3 (l) + 6CO(g)
TiCl 4 (g) + 2Mg(l) → Ti(s) + 2MgCl 2 (l)
 103 kg   103 g   1 mol FeTiO3   1 mol Ti   47.88 g Ti   84%   93% 
Mass Ti = ( 21.5 t FeTiO3 )          

 1 t   1 kg   151.73 g FeTiO3   1 mol FeTiO3   1 mol Ti   100%   100% 
= 5.300092x106 = 5.3x106 g Ti

22.63 a) Balance the two steps and then add them.

(1) 16H 2 S(g) + 16O 2 (g) → S 8 (g) + 8SO 2 (g) + 16H 2 O(g)
(2) 16H 2 S(g) + 8SO 2 (g) → 3S 8 (g) + 16H 2 O(g)
32H 2 S(g) + 16O 2 (g) → 4S 8 (g) + 32H 2 O(g)
The coefficients in the overall equation can be reduced since all are divisible by 4.
8H 2 S(g) + 4O 2 (g) → S 8 (g) + 8H 2 O(g)
b) Replace oxygen with chlorine:
8H 2 S(g) + 8Cl 2 (g) → S 8 (g) + 16HCl(g)
Calculate ∆G° to determine if this reaction is thermodynamically possible.

∆Grxn = ∑m ∆Gf (products) – ∑n ∆Gf (reactants)

∆Grxn = [(1 mol S 8 )( ∆Gf of S 8 ) + (16 mol HCl)( ∆Gf of HCl)]
– [(8 mol H 2 S)( ∆Gf of H 2 S) + (8 mol Cl 2 )( ∆Gf of Cl 2 )]

∆Grxn = [(1 mol)(49.1 kJ/mol) + (16 mol)(–95.30 kJ/mol)] – [(8 mol)(–33 kJ/mol) + (8 mol)(0 kJ/mol)]

∆Grxn = –1211.7 = –1212 kJ
The reaction is spontaneous.
c) Oxygen is readily available from the air, so chlorine is a more expensive reactant. In addition, water is less
corrosive than HCl as a product.

22.64 Plan: Balance each reaction. Acidity is a measure of the concentration of H 3 O+ (H+), so any reaction that
produces H+ will increase the acidity.
Solution:
a) 2H 2 O(l) + 2FeS 2 (s) + 7O 2 (g) → 2Fe2+(aq) + 4SO 4 2–(aq) + 4H+(aq) Increases acidity.
b) 4H+(aq) + 4Fe2+(aq) + O 2 (g) → 4Fe3+(aq) + 2H 2 O(l)
c) Fe3+(aq) + 3H 2 O(l) → Fe(OH) 3 (s) + 3H+(aq) Increases acidity.
d) 8H 2 O(l) + FeS 2 (s) + 14Fe3+(aq) → 15Fe2+(aq) + 2SO 4 2–(aq) + 16H+(aq) Increases acidity.

22.65 Plan: The carbon fits into interstitial positions. The cell size will increase slightly to accommodate the carbons
atoms. The increase in size is assumed to be negligible. The mass of the carbon added depends upon the carbon in
the unit cell.
Solution:
Ferrite:
 7.86 g   7.86 g  0.0218% 
+
3
   = 7.86171 = 7.86 g/cm
 cm3   cm3  100% 
Austenite:
 7.40 g   7.40 g  2.08% 
 3 
+ 3   = 7.55392 = 7.55 g/cm
3

 cm   cm  100% 

22-13
 
22.66 ∆Grxn = ∑m ∆Gf (products) – ∑n ∆Gf (reactants)
a) N 2 (g) + 2O 2 (g) → 2NO 2 (g)

∆Grxn = [(2 mol)(51 kJ/mol)] – [(1 mol)(0 kJ/mol) + (2 mol)(0 kJ/mol)] = 102 kJ (unfavorable)
b) 3NO 2 (g) + H 2 O(l) → 2HNO 3 (aq) + NO(g)

∆Grxn = [(2 mol)(–110.5 kJ/mol) + (1 mol)(86.60 kJ/mol)] – [(3 mol)(51 kJ/mol) + (1 mol)(–237.192 kJ/mol)]

∆Grxn = –50.208 = –50. kJ (favorable)
c) 2NO(g) + O 2 (g) → 2NO 2 (g)

∆Grxn = [(2 mol)(51 kJ/mol)] – [(2 mol)(86.60 kJ/mol) + (1 mol)(0 kJ/mol)] = –71.2 = –71 kJ (favorable)
(overall) 3N 2 (g) + 6O 2 (g) + 2H 2 O(l) → 4HNO 3 (aq) + 2NO(g)

∆Grxn = [(4 mol)(–110.5 kJ/mol) + (2 mol)(86.60 kJ/mol)]
– [(3 mol)(0 kJ/mol) + (6 mol)(0 kJ/mol) + (2 mol)(–237.192 kJ/mol)]

∆Grxn = 205.584 = 205.6 kJ
Overall, the reaction is thermodynamically unfavorable, due to the unfavorability of the first step.

22.67 Plan: Decide what is reduced and what is oxidized of the two ions present in molten NaOH. Then, write half-
reactions and balance them. Then write the overall equation for the electrolysis of NaOH and also for the
reaction of Na with water. Examine the molar ratios involving water and Na in these equations.
Solution:
a) At the cathode, sodium ions are reduced: Na+(l) + e– → Na(l)
At the anode, hydroxide ions are oxidized: 4OH–(l) → O 2 (g) + 2H 2 O(g) + 4e–
b) The overall cell reaction is 4Na+(l) + 4OH–(l) → 4Na(l) + O 2 (g) + 2H 2 O(g) and the reaction between sodium
metal and water is 2Na(l) + 2H 2 O(g) → 2NaOH(l) + H 2 (g).
For each mole of water produced, two moles of sodium are produced, but for each mole of water that reacts only
one mole of sodium reacts. So, the maximum amount of sodium that reacts with water is half of the sodium
produced. In the balanced cell reaction, four moles of electrons are transferred for four moles of sodium.
Since 1/2 of the Na reacts with H 2 O, the maximum efficiency is 1/2 mol Na/mol e–, or 50%.

22.68 a) 4Au(s) + O 2 (g) + 2H 2 O(l) → 4Au+(aq) + 4OH –(aq)

pH = 13.55, pOH = 14.00 – pH = 14.00 – 13.55 = 0.45
[OH–] = 10–0.45 = 0.3548 M
E° = E°O2 – E°Au = 0.40 V – 1.68 V = –1.28 V
  + 4  −
4 
0.0592 0.0592 V   Au  OH  
E = E° – log Q = E° – log  
n n  Poxygen 
 
0.0592 V  [ 0.50]4 [ 0.3548]4 
E = –1.28 V – log   = –1.245569 = –1.25 V
4  0.21 
 
This reaction is not spontaneous (the voltage is negative).
b) Qualitatively, the addition of CN– will lower the concentration of free Au+ by forming Au(CN) 2 –. This will
make [Au+] much lower than 1 M, making the second term in the Nernst equation larger in magnitude. If [Au+] is
lowered sufficiently, the second term offsets the first and E cell becomes favorable.

22.69 a) Nitric oxide destroys ozone by forming nitrogen dioxide and oxygen.
NO(g) + O 3 (g)  NO 2 (g) + O 2 (g)
NO 2 (g) + O 2 (g)  NO(g) + O 3 (g) (reverse)
b) The order translates to the exponent in the rate law, and the rate is dependent on the concentration of the
reactants.
Rate f = k f [NO][O 3 ]
Rate r = k r [NO 2 ][O 2 ]

22-14
   
c) ∆Grxn = ∆H rxn – T ∆Srxn because the reaction does not take place at 298 K.

∆H rxn = ∑m ∆H f (products) – ∑n ∆H f (reactants)

∆H rxn = [(1 mol NO 2 )(33.2 kJ/mol) + (1 mol O 2 )(0 kJ/mol)]
– [(1 mol NO)(90.29 kJ/mol) + (1 mol O 3 )(143 kJ/mol)]

∆H rxn = –200.09 kJ

∆Srxn = [(1 mol NO 2 )(239.9 J/mol•K) + (1 mol O 2 )(205.0 J/mol•K)]
– [(1 mol NO)(210.65 J/mol•K) + (1 mol O 3 )(238.82 J/mol•K)]

∆Srxn = –4.57 J/K
  
∆Grxn = ∆H rxn – T ∆Srxn = (–200.09 kJ) – (280. K)(–4.57 J/K)(1 kJ/103 J) = –198.810 = –199 kJ
d) Assume that the reaction reaches equilibrium at 280. K. At equilibrium, the forward rate equals the reverse rate
and their ratio equals the equilibrium constant: k f /k r = K eq . Both ∆G and K eq express the extent to which a
reaction proceeds and are related by the equation ∆G = –RT ln K eq .
∆G   −198.810 kJ/mol   103 J 
=    
ln K = = 85.402591
 − (8.314 J/mol•K )( 280. K )   1 kJ 
− RT 
K = 1.22991x1037 = 1.2x1037
Therefore, the ratio of rate constants, k f /k r , is 1.2x1037 and the forward rate is much faster than the reverse rate.

22.70 Plan: Convert mass of CO 2 to moles of O 2 using the reaction stoichiometry in the balanced equation.
PV = nRT is used to convert moles of O 2 to volume. Temperature must be in units of Kelvin.
Solution:
a) The reaction for the fixation of carbon dioxide includes CO 2 and H 2 O as reactants and (CH 2 O) n and O 2 as
products. The balanced equation is:
nCO 2 (g) + nH 2 O(l) → (CH 2 O) n (s) + nO 2 (g)
b) The moles of carbon dioxide fixed equal the moles of O 2 produced.
 48 g CO 2   1 mol CO 2   1 mol O 2 
Mole O 2 /day =     = 1.090661 mol O 2 /day
 day   44.01 g CO 2   1 mol CO 2 
To find the volume of oxygen, use the ideal gas equation. Temperature must be converted to K.
5 5
T (in K) = T ( °F ) − 32  + 273.15 = T ( 78.° ) − 32  + 273.15 = 298.7056 K
9 9
PV = nRT
nRT (1.090661 mol O2 )( 0.0821 L•atm/mol•K )( 298.7056 K )
V = = = 26.74708 = 27 L
P (1.0 atm )
c) The moles of air containing 1.090661 mol of CO 2 is:
48 g CO2 1 mol CO2 100 mol % air
Mole CO 2 /day = � �� �� � = 2.7266530x103 mol air/day
day 44.01 g CO2 0.040 mol % CO2
𝑛𝑅𝑇 �2.7266530x103 mol air�(0.0821 L•atm/mol•K)(298.7056 K)
𝑉= = (1.0 atm)
= 6.6867x104 = 6.7x104 L
𝑃

22.71 This problem requires a series of conversion steps:

Concentration =
 210. kg (NH 4 ) 2 SO 4   103 g   1 mol (NH 4 ) 2 SO 4   2 mol NO3−   37%   62.01 g NO3−   1 mg   10−3 m3 
           −
  −3   
 1000. m3   1 kg   132.15 g (NH 4 ) 2 SO 4   1 mol (NH 4 ) 2 SO 4   100%   1 mol NO3   10 g   1 L 
= 72.9198 = 73 mg/L
This assumes the plants in the field absorb none of the fertilizer.

22-15
22.72 Plan: Write a balanced equation. Determine which one of the three reactants is the limiting reactant by
determining the amount of cryolite produced by each reactant. The amount of Al(OH) 3 requires conversion of kg
to g; the amount of NaOH requires conversion from amount of solution to mass in grams by using the density; the
amount of HF requires conversion from volume to moles using the ideal gas law.
Solution:
The balanced chemical equation for this reaction is:
6HF(g) + Al(OH) 3 (s) + 3NaOH(aq) → Na 3 AlF 6 (aq) + 6H 2 O(l)
a) Assuming Al(OH) 3 is the limiting reactant:
 103 g   1 mol Al(OH)3   1 mol Na 3 AlF6 
Moles of Na 3 AlF 6 = ( 365 kg Al(OH)3 ) 
 1 kg   78.00 g Al(OH)   1 mol Al(OH) 
  3  3 
3
= 4.6795x10 mol Na 3 AlF 6
b) Assuming NaOH is the limiting reactant:
Moles of Na 3 AlF 6 =
 1 L   1 mL   1.53 g   50.0% NaOH   1 mol NaOH   1 mol Na 3 AlF6 
( )
1.20 m3  −3 3   −3  
 10 m   10 L   mL   100%   40.00 g NaOH   3 mol NaOH 
  
  
3
= 7.650x10 mol Na 3 AlF 6
c) Assuming HF is the limiting reactant:
PV = nRT
PV (
( 305 kPa ) 265 m 3
)  103 Pa  
  
1 atm  1 L 
Moles of HF = =  
RT ( 0.0821 L•atm/mol•K ) ( ( 273.2 + 91.5) K )  1 kPa   1.01325 x10 Pa   10−3 m3 
5

= 26,640.979 mol HF
 1 mol Na 3AlF6 
Moles of Na 3 AlF 6 = ( 26, 640.979 mol HF )  3
 = 4.4402x10 mol Na 3 AlF 6
 6 mol HF 
Because the 265 m3 of HF produces the smallest amount of Na 3 AlF 6 , it is the limiting reactant. Convert moles
Na 3 AlF 6 to g Na 3 AlF 6 , using the molar mass, convert to kg, and multiply by 95.6% to determine the final yield.
 209.95 g Na 3AlF6   1 kg   95.6% 
(
Mass (g) of cryolite = 4.4402x103 mol Na 3AlF6  )  3 
 1 mol Na 3AlF6   10 g   100% 


= 891.195 = 891 kg Na 3 AlF 6

22.73 Plan: The rate of effusion is inversely proportional to the square root of the molar mass of the molecule
(Graham’s law).
Solution:
Rate H molar mass D 4.00 g/mol
a) = = = 1.40859
Rate D molar mass H 2.016 g/mol
The time for D 2 to effuse is 1.41 times greater than that for H 2 .
Time D2 = (1.40859)(16.5 min) = 23.2417 = 23.2 min
b) Set x equal to the number of effusion steps. The ratio of mol H 2 to mol D 2 is 99:1.
Set up the equation to solve for x: 99/1 = (1.40859)x.
When solving for an exponent, take the log of both sides.
log (99) = log (1.40859)x
Remember that log (ab) = b log (a)
log (99) = x log (1.40859)
x = 13.4129
To separate H 2 and D 2 to 99% purity requires 14 effusion steps.

22.74 a) The equilibrium constant is large, the rate constant is small, and E a is large.
b) 2CO(g)  C(graphite) + CO 2 (g)

22-16
 
c) ∆Grxn = ∑m ∆Gf (products) – ∑n ∆Gf (reactants)

∆Grxn = [(1 mol C)(0 kJ/mol) + (1 mol CO 2 )(–394.4 kJ/mol)] – [(2 mol CO)(–137.2 kJ/mol]) = –120.0 kJ

∆Grxn = – RT ln K c
∆G 
= −
( −120.0 kJ )  103 J 
ln K c =   = 48.4345
− RT (8.314 K/mol•K )( 298 K )  1 kJ 
K c = 1.0835x1021 = 1.1x1021
d) K p = K c (RT)∆ngas
K p = 1.0835x1021 [(0.0821 L•atm/mol•K)(298)]–1 = 4.428631x1019 = 4.4x1019

22.75 Plan: Use the stoichiometric relationships found in the balanced chemical equation to find the mass of Al 2 O 3 ,
mass of graphite, and moles of CO 2 . Use the ideal gas law to convert moles of CO 2 into volume.
Solution:
a) 2Al 2 O 3 (in Na 3 AlF 6 ) + 3C(gr) → 4Al(l) + 3CO 2 (g)
 103 kg   10 3g   1 mol Al   2 mol Al2 O3   101.96 g Al2 O3   1 kg   1 t 
Mass (t) of Al 2 O 3 = (1 t Al ) 
 1 t   1 kg   26.98 g Al   4 mol Al   1 mol Al O   103 g   103 kg 
     2 3   
= 1.8895478 = 1.890 t Al 2 O 3
Therefore, 1.890 t of Al 2 O 3 are consumed in the production of 1 t of pure Al.
 103 kg   10 3g   1 mol Al   3 mol C   12.01 g C   1 kg   1 t 
b) Mass (t) of C = (1 t Al ) 
 1 t   1 kg   26.98 g Al   4 mol Al   1 mol C   103 g   103 kg 
       
= 0.3338584 = 0.3339 t C
Therefore, 0.3339 t of C is consumed in the production of 1 t of pure Al, assuming 100% efficiency.
c) The percent yield with respect to Al 2 O 3 is 100% because the actual plant requirement of 1.89 t Al 2 O 3 equals
the theoretical amount calculated in part a).
d) The amount of graphite used in reality to produce 1 t of Al is greater than the amount calculated in part b). In
other words, a 100% efficient reaction takes only 0.3339 t of graphite to produce a ton of Al, whereas real
production requires more graphite and is less than 100% efficient. Calculate the efficiency using a simple ratio:
(0.45 t)(x) = (0.3338584 t)(100%)
x = 74.19076 = 74%
e) For every four moles of Al produced, three moles of CO 2 are produced.
 103 kg   103 g   1 mol Al   3 mol CO 2 
Moles of C = (1 t Al )  = 2.7798x104 mol CO 2
 1 t   1 kg   26.98 g Al   4 mol Al 
    
The problem states that 1 atm is exact. Use the ideal gas law to calculate volume, given moles, temperature, and
pressure.
PV = nRT

V = =
( 4
)
nRT  2.7798x10 mol CO2 ( 0.08206 L•atm/mol•K ) ( ( 273 + 960. ) K )   10−3 m3 
 
 
P  1 atm   1 L 
 
= 2.812601x103 = 2.813x103 m3

22.76 a) The reactions are:

4FeCr 2 O 4 (s) + 8Na 2 CO 3 (aq) + 7O 2 (g) → 8Na 2 CrO 4 (aq) + 2Fe 2 O 3 (s) + 8CO 2 (g)
2Na 2 CrO 4 (aq) + 2H 3 O+(aq) → Na 2 Cr 2 O 7 (s) + 3H 2 O(l) + 2Na+(aq)
Na 2 Cr 2 O 7 (s) + 2C(s) → Cr 2 O 3 (s) + Na 2 CO 3 (s) + CO(g)
Cr 2 O 3 (s) + 2Al(s) → 2Cr(s) + Al 2 O 3 (s)
b) Mass (kg) of Cr =
 103 kg   103 g   1 mol FeCr2O 4   2 mol Cr   52.00 g Cr   1 kg 
(1.97x107 t FeCr2O4  )  1 t   1 kg   223.85 g FeCr O   1 mol FeCr O   1 mol Cr   103 g 
2 4  
   2 4  
= 9.152558x109 = 9.2x109 kg Cr

22-17
22.77 a) HDO + H 2  HD + H 2 O
b) At equilibrium, there are more reactants than products. This is a reactant-favored reaction so
the equilibrium constant K must be less than 1.

c) K =
[ H 2 O][ HD] = [0.20][0.20] = 0.44
[ HDO][ H 2 ] [0.30][0.30]
22.78 K sp (NiS) = 1.1x10–18 = [Ni2+][HS–][OH –] = (0.10)[HS–][OH –],
so if [HS–][OH –] < 1.1x10–17, K sp will not be exceeded and NiS will not precipitate.
K sp (CuS) = 8x10–34 = [Cu2+][HS–][OH –] = (0.10)[HS–][OH –],
so if [HS–][OH –] > 8x10–33, K sp will be exceeded and CuS will precipitate.
 HS−   H3O +   HS−   H3O + 
–8
K a1 = 9x10 =     =
  
[ H 2S] 0.10
[HS–][H 3 O+] = 9x10–9 , or [HS–] = 9x10–9 M/[H 3 O+]
K w = [H 3 O+][OH –] or [OH –] = K w /[H 3 O+]
so [HS–][OH –] = (9x10–9 )(1.0x10–14)/[H 3 O+]2 = (9x10–23)/[H 3 O+]2
[HS–][OH –] < 1.1x10–17
[H 3 O+] > 3x10–3 M and pH < 2.5
[HS ][OH –] > 8x10–33
–

[H 3 O+] < 1x105 M and pH > –5.0

So, maintaining the pH between –5.0 and 2.5 would allow CuS to precipitate but prevent precipitation of NiS.

 1 kg   100% 
22.79 (
a) Mass (kg) of ore = 2.0x105 lb Cu  )  
 2.205 lb   0.25% 
= 3.6281x107 = 3.6x107 kg ore

 0.25% Cu   183.54 g FeCuS2 

b) Mass % chalcopyrite =    (100% ) = 0.7220 = 0.72% chalcopyrite
 100%   63.55 g Cu 

22.80 Plan: Solubility of a salt can be calculated from its K sp . K sp for Ca 3 (PO 4 ) 2 is 1.2x10–29. Phosphate is derived
from a weak acid, so the pH of the solution impacts exactly where the acid-base equilibrium lies. Phosphate can
gain one H+ to form HPO 4 2-. Gaining another H+ gives H 2 PO 4 – and a last H+ added gives H 3 PO 4 . The K a values
for phosphoric acid are K a1 = 7.2x10–3, K a2 = 6.3x10–8, K a3 = 4.2x10–13. To find the ratios of the various forms of
phosphate, use the equilibrium expressions and the concentration of H+.
Solution:
a) Ca 3 (PO 4 ) 2 (s)  Ca2+(aq) + 2PO 4 3–(aq)
___
Initial 0 0
Change –x +3x +2x
__
Equilibrium 3x 2x
K sp = 1.2x10 = [Ca2+]3[PO 4 3–]2 = (3x)3(2x)2 = 108x5
–29

x = 6.4439x10–7 = 6.4x10–7 M Ca 3 (PO 4 ) 2

b) [H 3 O+] = 10–4.5 = 3.162x10–5 M
H 3 PO 4 (aq) + H 2 O(l)  H 2 PO 4 –(aq) + H 3 O+(aq)
 H 2 PO 4 −   H3O + 
K a1 =   
H3 PO 4 
 H 2 PO 4 − 
  = K a1 7.2x10−3
= = 227.70
H3 PO 4   H3O +  3.162x10−5
 
H 2 PO 4 –(aq) + H 2 O(l)  HPO 4 2–(aq) + H 3 O+(aq)
 HPO 4 2 −   H3O + 
K a2 =   
 H 2 PO 4 
−
 

22-18
  HPO 4 2 − 
  = Ka 2 6.3x10−8
= = 1.9924x10–3
 H 2 PO 4 −   H3O +  3.162x10−5
   
HPO 4 2–(aq) + H 2 O(l)  PO 4 3–(aq) + H 3 O+(aq)
 PO 43−   H3O + 
K a3 =   
 HPO 4 2 − 
 
 PO 4 
3 −
  = K a3 4.2x10−13
= −5
= 1.32827x10–8
 HPO 4  2 −  H3O  + 3.162x10
   
From the ratios, the concentration of H 2 PO 4 – is at least 100 times more than the concentration of any other
species, so assume that dihydrogen phosphate is the dominant species and find the value for [PO 4 3–].
 PO 43 −   HPO 4 2 − 
  = 1.32827x10–8 and   = 1.9924x10–3
 HPO 4 2 −   H 2 PO 4 − 
   
[PO 4 3–] = (1.32827x10–8)[HPO 4 2–] and [HPO 4 2–] = (1.9924x10–3)[H 2 PO 4 –]
[PO 4 3–] = (1.32827x10–8)[HPO 4 2–] = (1.32827x10–8)(1.9924x10–3)[H 2 PO 4 –]
[PO 4 3–] = (2.6464x10–11)[H 2 PO 4 –]
Substituting this into the K sp expression gives
K sp = [Ca2+]3[PO 4 3–]2 = 1.2x10–29
K sp = [Ca2+]3{(2.6464x10–11)[H 2 PO 4 –]}2
Rearranging gives
K sp /(2.6464x10–11)2 = [Ca2+]3[H 2 PO 4 –]2
The concentration of calcium ions is still represented as 3x and the concentration of dihydrogen phosphate ion as
2x, since each H 2 PO 4 – comes from one PO 4 3–.
K sp /(2.6464x10–11)2 = (3x)3(2x)2
(1.2x10–29)/(2.6464x10–11)2 = 108x5
x = 1.0967x10–2 = 1.1x10–2 M
Acid rain increases the leaching of PO 4 3– into the groundwater, due to the protonation of PO 4 3– to form HPO 4 2–
and H 2 PO 4 –. As shown in calculations a) and b), solubility increases from 6.4x10–7 M (in pure water) to
1.1x10–2 M (in acidic rainwater).

22.81 a) The mole % of oxygen missing may be estimated from the discrepancy between the actual and ideal formula.
 ( 2.000 − 1.98 ) mol O 
Mol % O missing =   x 100% = 1.00%
 2.000 mol O
 
b) The molar mass is determined like a normal molar mass except that the quantity of oxygen is not an integer
value.
Molar mass = 1 mol Pb (207.2 g/mol) + 1.98 mol O (16.00 g/mol) = 238.88 = 238.9 g/mol

22.82 Using ∆G values:

H 2 O(l) → H 2 (g) + 1/2O 2 (g) ∆G = +237.192 kJ/mol
H 2 S(g) → H 2 (g) + 1/8S 8 (s) ∆G = +33 kJ/mol
Both these processes require energy to proceed, but the second requires less energy and would be more
favorable (or less unfavorable) based on this criterion.

22.83 Plan: Convert the unit cell edge length to cm and cube that length to obtain the volume of the cell. A face-
centered cubic structure contains four atoms of silver. Divide that number by Avogadro’s number to find the
moles of silver in the cell and multiply by the molar mass to obtain the mass of silver in the cell. Density is
obtained by dividing the mass of silver by the volume of the cell. The calculation will now be repeated replacing
the atomic mass of silver with the “atomic mass” of sterling silver. The “atomic mass” of sterling silver is simply
a weighted average of the masses of the atoms present (Ag and Cu).

22-19
 Solution:
 10−12 m   1 cm 
Edge length (cm) = ( 408.6 pm )  = 4.086x10–8 cm
 1 pm   10−2 m 
 
Volume (cm3) of cell = (4.086x10–8 cm)3 = 6.82174x10–23 cm3
 4 Ag atoms   1 mol Ag   107.9 g Ag  –22
Mass (g) of silver =   23   = 7.1671x10 g
 unit cell   6.022x10 Ag atoms   1 mol Ag 
7.1671x10−22 g
Density of silver = = 10.506264 = 10.51 g/cm3
6.82174x10−23 cm3
 107.9 g   (100.0 − 7.5 ) %   63.55 g   7.5% 
Atomic mass of sterling silver =    +    = 104.57375 g/mol
 mol   100%   mol   100% 
 4 Ag atoms   1 mol Ag   104.57375 g Ag  –22
Mass (g) of sterling silver =   23   = 6.946x10 g
 unit cell   6.022x10 Ag atoms   1 mol Ag 

6.9461 x 10−22 g
Density of sterling silver = = 10.1823 = 10.2 g/cm3
6.82174x10−23 cm3

 10 3 g   0.05%   1 mol Ti 
22.84 (
a) Moles of Ti = 5.98x1024 kg  )  1 kg   100%   47.88 g Ti 
 
= 6.24x1022 = 6x1022 mol Ti
 
b) Mass (g) of ilmenite =
 103 g   0.05%   1 mol Ti   50%   1 mol FeTiO3   151.73 g FeTiO3 
(5.98x1024 kg  )
 1 kg   100%   47.88 g Ti   100%   1 mol Ti   1 mol FeTiO 
    3 
 
= 4.73760x1024 = 5x1024 g FeTiO 3
 0.05%   2.205 lbs   1 ton   
(
c) Yr = 5.98 x1024 kg  )  100% 


1 kg

 2000 lb


yr
5
13 13
 = 3.296x10 = 3x10 yr
1.00 x 10 tons 

22.85 a) 2NaCl(s) + H 2 SO 4 (aq) → Na 2 SO 4 (aq) + 2HCl(g)

Na 2 SO 4 (s) + 2C(s) → Na 2 S(s) + 2CO 2 (g)
Na 2 S(s) + CaCO 3 (s) → Na 2 CO 3 (s) + CaS(s)
Total: CaCO 3 (s) + Na 2 SO 4 (s) + 2C(s) + 2NaCl(s) + H 2 SO 4 (aq)
→ Na 2 SO 4 (aq) + 2HCl(g) + 2CO 2 (g) + Na 2 CO 3 (s) + CaS(s)
b) Notice that Na 2 SO 4 (aq) and Na 2 SO 4 (s) are different substances, and, as such, will not cancel in this Hess’s law
calculation. The values for Na 2 SO 4 (aq) and Na 2 SO 4 (s) are not in the Appendix so they must be found from
another source. The other enthalpies of formation are either given in the problem or are given in the Appendix.

∆H rxn = ∑m ∆H f (products) – ∑n ∆H f (reactants)

∆H rxn = [(1 mol Na 2 SO 4 (aq))( ∆H f of Na 2 SO 4 (aq)) + (2 mol HCl)( ∆H f of HCl) + (2 mol CO 2 )( ∆H f of CO 2 )
+ (1 mol Na 2 CO 3 )( ∆H f of Na 2 CO 3 ) + (1 mol CaS)( ∆H f of CaS)] – [(1 mol CaCO 3 )( ∆H f of CaCO 3 )
+ (1 mol Na 2 SO 4 (s))( ∆H f of Na 2 SO 4 (s)) + (2 mol C)( ∆H f of C) + (2 mol NaCl)( ∆H f of NaCl)
+ (1 mol H 2 SO 4 )( ∆H f of H 2 SO 4 )]
351.8 kJ/mol = [(1 mol)(–1389.5 kJ/mol) + (2 mol)(–92.31 kJ/mol) + (2 mol)(–393.5 kJ/mol)
+ (1 mol)(–1130.8 kJ/mol) + (1 mol)( ∆H f of CaS)] – [(1 mol)(–1206.9 kJ/mol)
+ (1 mol)(–1387.1 kJ/mol) + (2 mo)(0 kJ/mol) + (2 mol)(–411.1 kJ/mol) + (1 mol)(–907.51 kJ/mol)]
∆H f of CaS(s) = –479.99 = –480.0 kJ

22-20
 c) The reaction is very endothermic, therefore it is probably not spontaneous even though the entropy change may
be expected to be positive. It will take a ∆G determination to know for sure.
 1 mol NaCl   1 mol Na 2 CO3   105.99 g Na 2 CO3   73% 
d) Mass (g) of Na 2 CO 3 = ( 250. g NaCl )     
 58.44 g NaCl   2 mol NaCl   1 mol Na 2 CO3   100% 
= 165.4960 = 165 g Na 2 CO 3

22.86 a) For CaCO 3 :

CaCO 3 (s) → CaO(s) + CO 2 (g)

∆H rxn = ∑m ∆H f (products) – ∑n ∆H f (reactants)

∆H rxn = [(1 mol)( ∆H f of CaO) + (1 mol)( ∆H f of CO 2 )] – [(1 mol)( ∆H f of CaCO 3 )]

∆H rxn = [(1 mol)(–635.1 kJ/mol) + (1 mol)(–393.5 kJ/mol)] – [(1 mol)(–1206.9 kJ/mol)]

∆H rxn = 178.3 kJ
  
∆Srxn = ∑m Sproducts – ∑n Sreactants

∆Srxn = [(1 mol)( S  of CaO) + (1 mol)( S  of CO 2 )] – [( 1 mol)( S  of CaCO 3 )]

∆Srxn = [(1 mol)(38.2 J/mol•K) + (1 mol)(213.7 J/mol•K)] – [(1 mol)(92.9 J/mol•K)]

∆Srxn = 159.0 J/K
  
∆Grxn = 0 = ∆H rxn – T ∆Srxn
 
∆H rxn = T ∆Srxn
∆H   178.3 kJ   103 J 
T =

=     = 1121.3836 = 1121 K for CaCO 3
∆S  159.0 J/K   1 kJ 
For MgCO 3 :
MgCO 3 (s) → MgO(s) + CO 2 (g)

∆H rxn = ∑m ∆H f (products) – ∑n ∆H f (reactants)

∆H rxn = [(1 mol)( ∆H f of (MgO) + (1 mol)( ∆H f of (CO 2 )] – [(1 mol)( ∆H f of (MgCO 3 )]

∆H rxn = [(1 mol)(–601.2 kJ/mol) + (1 mol)(–393.5 kJ/mol)] – [(1 mol)(–1112 kJ/mol)]

∆H rxn = 117.3 kJ
  
∆Srxn = ∑m Sproducts – ∑n Sreactants

∆Srxn = [(1 mol)( S  of MgO)) + (1 mol)( S  of CO 2 )] – [(1 mol)( S  of MgCO 3 )]

∆Srxn = [(1 mol)(26.9 J/mol•K) + (1 mol)(213.7 J/mol•K)] – [(1 mol)(65.86 J/mol•K)]

∆Srxn = 174.74 J/K
  
∆Grxn = 0 = ∆H rxn – T ∆Srxn
 
∆H rxn = T ∆Srxn
∆H   117.3 kJ   103 J 
T = =     = 671.283 = 671 K for CaCO 3
∆S   174.74 J/K   1 kJ 
b) CaO(s) + SiO 2 (s) → CaSiO 3 (s)
Mass (kg) of CaCO 3 =
 2.236x106 tons   84%   52 weeks   50 kg slag   103 g   1 mol slag   1 mol CaCO3   100.09 g CaCO3   1 kg 
       1 kg   116.17 g slag   1 mol slag   1 mol CaCO   3 
 week   100%   yr  ton     3   10 g 
= 4.2075x109 = 4.2x109 kg CaCO 3

22-21
22-22