SOLUTIONS TO SELECTED PROBLEMS IN CHAP. 9 & 10 The Arrhenius Theory (Section 9.1) 9.

1 Write the dissociation equations for the following that emphasize their behavior as Arrhenius acids: a) HI b) HBrO c) HCN d) HClO2 Solution a) HI(aq) H+(aq) + I -(aq) c) HCN(aq) H+(aq) + CN-(aq) 9.3 b) HBrO(aq) H+(aq) + BrO -(aq) d) HClO2 (aq) H+(aq) + ClO- (aq) 2

Each of the following produces a basic solution when dissolved in water. Identify those that behave as Arrhenius bases and write dissociation equations to illustrate that behavior. a) CsOH b) CH3 NH2 c) NH 3 d) Ca(OH)2 Solution a) CsOH(aq) Cs+(aq) + OH-(aq) c) not an Arrhenius base b) not an Arrhenius base d) Ca(OH)2 (aq) Ca2+(aq) + 2OH-(aq)

The Brnsted Theory (Section 9.2) 9.5 Identify each Br nsted acid and base in the following equations. Note that the reactions are assumed to be reversible. + 2a) HBr (aq) + -H2 O (l) H3 O (aq) + Br (aq) d) SO3 (aq)+H2O(l) HSO3(aq)+OH (aq) b) H2 O (l) + N3 (aq) NH3 (aq) + OH (aq) e) HC N ( aq ) + H 2O ( l) H3 O +( aq ) + CN - (a q) + c) H2 S(aq) +H2 O(l) H3 O (aq) +HS (aq) Solution a) HBr (aq) + H 2 O (l) H3 O +(aq) + Br- (aq) acid base acid base b) H2 O (l) + N- (aq) NH3 (aq) + OH- (aq) 3 acid base acid base c) H2 S (aq) + H2 O (l) H3 O +(aq) + HS- (aq) acid base acid base 2 HSO - (aq) + OH- (aq) d) SO 3 (aq) + H2 O (l) 3 base acid acid base + e) HCN (aq) + H2 O (l) H3 O (aq) + CN- (aq) acid base acid base 9.7 Identify each conjugate acid-base pair in the equations for Exercise 9.5 Solution a) b) c) d) e) Acid HBr H2O H2S H2O HCN Conjugate Base BrOHHSOHCNBase H2O N3 H2O
SO3
2-

H2O

Conjugate Acid H3O + HN3 H3O + HSO3 H3O +

9.11

Write a formula for the conjugate base formed when each of the following behaves as a Brnsted acid: a) HSOb) HPO2 c) HClO 3 d) CH3 NH+ e) H2C2O 4 3 4 3 Solution a) SO23 b) PO2 4 c) ClO3 d) CH3 NH2 e) HC2 O4

9.13

Write a formula for the conjugate acid formed when each of the following behaves as a Brnsted base: a) NHb) CO2 c) OHd) (CH3 )2NH e) NO-2 2 3 Solution a) NH3 b) HCO3 c) H2O d) (CH3 )2 NH+ 3 e) HNO2

Naming Acids (Section 9.3) 9.21 Name the following acids. Refer to Table 4.7 as needed. a) H2Se(aq) b) HClO3 c) H2SO 4 Solution a) hydroselenic acid 9.25 b) chloric acid c) sulfuric acid d) HNO3 d) nitric acid

Refer to Table 4.7 and write the formula for chromic acid. Solution H2CrO4

The Self-Ionization of Water (Section 9.4) 9.27 Calculate the molar concentration of OH - in water solutions with the following H3O + molar concentrations: a) 1.0 x 10-7 b) 3.2 x 10-3 c) 4.7 x 10-11 d) 1.2 e) 0.043 Solution
1.0 x10 - 14 - 7 - 7 =1.0 x10 M a) 1.0 x10 1.0 x10- 14 - 12 [OH ] = M - 3 = 3.1x10 b) 3.2 x10 1.0 x10 - 14 - 4 [OH- ]= - 11 = 2.1x10 M c) 4.7 x10 [OH ]=
-

d) e)

[OH ]=

1.0 x10 - 14 - 15 = 8.3 x10 M 1.2

[OH ]=

1.0 x10- 14 - 13 = 2.3 x10 M 0.043

9.29

Calculate the molar concentration of H3 O+ in water solutions with the following OH- molar concentrations: a) 1.0 x 10-7 b) 5.2 x 10-4 c) 9.9 x 10-10 d) 0.092 e) 3.7 Solution a)
[H3 O ]=
+

1.0 x10 - 14 - 7 - 7 =1.0 x10 M 1.0 x10

[H3O+ ]= 1.0 x10 - 2 = 1.1x10- 13 M 9.2 x10 d)

- 14

- 14 + 1.0 x10- 14 - 11 [H3 O ] = M [H3O+ ] = 1.0 x10 = 2.7 x10- 15 M - 4 = 1.9 x10 b) 5.2 x10 3.7 e) - 14 + 1.0 x10 -5 c) [H3O ] = 9.9 x10- 10 =1.0 x10 M

9.31

Classify the solutions represented in Exercises 9.27 and 9.29 as acidic, basic, or neutral. Solution #9.27 a) neutral #9.29 a) neutral b) acidic b) basic c) basic c) acidic d) acidic d) basic e) acidic e) basic

The pH Concept (Section 9.5) 9.33 Classify solutions with the following characteristics as acidic, basic, or neutral. a) pH=10 b) pH=4 c) pH=7.3 d) pH=6 Solution a) basic 9.35 b) acidic c) basic d) acidic

Determine the pH of water solutions with the following characteristics. Classify each solution as acidic, basic, or neutral. a) [H+] = 1.0 x10-5 M b) [OH -] = 6.0 x10 -3 M c) [H+] = [OH-] + -4 -9 d) [H ] = 9.0 x10 M e) [OH ] = 3.0 x10 M Solution Use the calculator to get pH. pH = -log[H+] a) pH = 5.0; acidic c) pH = 7.0; neutral d) pH = 3.1; acidic - 14 [H+ ] = 1.0 x10 - 9 = 3.3 x10- 6 M ; pH= 5.5 ; acidic 3.0 x10 e) Determine the pH of water solutions with the following characteristics. Classify each solution as acidic, basic, or neutral. a) [H+] = 3.7 x10-4 M b) [H+] = 7.4 x10-8 M c) [H+] = 1.9 x10 -10 M d) [OH-] = 1.3 x10 -1 M e) [OH-] = 6.8 x10 -7 M Solution Use the calculator to get pH. pH = -log[H+] a) pH = 3.4; acidic b) pH = 7.1; basic c) pH = 9.7; basic - 14 [H+ ]= 1.0 x10 - 1 = 7.7 x10 - 14 M ; pH =13 ; basic d) 1.3 x10 + 1.0 x10 - 14 -8 [H ]= - 7 = 1.5 x10 M ; pH = 7.8 ; basic e) 6, 8 x10
+ 1.0 x10 - 12 b) [H ] = 6.0 x10 - 3 =1.7 x10 M ; pH =12 ; basic - 14

9.37

9.39

Determine the [H+] value for solutions with the following characteristics: a) pH = 4.45 b) pH = 13.12 c) pH = 7.73

Solution a) [H+] = 3.55 x 10-5 M b) [H+] = 7.586 x 10-14 M 9.41

c) [H+] = 1.86 x 10 -8 M

Convert the following pH values into both [H +] and [OH -] values: a) pH = 8.00 b) pH = 6.15 c) pH = 1.30 Solution
1.00 x10- 14 -6 - 8 =1.00 x10 M a) 1.00 x10 + - 7 1.00 x10 - 14 = 1.41x10- 8 M b) [H ]= 7.08 x10 M [OH ] = 7.08 x10- 7 + -2 1.00 x10- 14 - 13 [H ]= 5.01x10 M [OH ]= M - 2 = 2.00 x10 c) 5.01x10 [H ]= 1.00 x10 M
+ -8

[OH ]=

9.45

The pH values of specific samples of food items are listed below. Convert each value to [H +] and classify the sample as acidic, basic, or neutral. a) milk, pH = 6.39 b) coffee, pH = 5.10 c) orange juice, pH = 4.07 d) vinegar, pH = 2.65 Solution a) [H+] = 4.07 x10-7 M; acidic c) [H+] = 8.51 x10-5 M; acidic b) [H+] = 7.94 x10-6 M; acidic d) [H+] = 2.24 x10-3 M; acidic

Properties of Acids (Section 9.6) 9.47 Use the information in Table 9.4 and describe how you would prepare each of the following solutions. a) about 750 mL of 0.500 M H 2SO4 from dilute sulfuric acid b) about 200 mL of 0.1 M NaOH from stock sodium hydroxide solution c) about 1.0 L of 1.0 M acetic acid from glacial acetic acid Solution Solve equation 7.9 for Vc . a) 750 mlx 0.500 M
Vd x Cd Cc 2 or 1 x 10 using question values Vc = = 125 mL Measure 125 mL of the dilute (3 M) H2SO 4 and 3.00 M put it in enough water (about 625 mL) to make 750 mL solution. Vc =
Vc = 200 ml x 0.1M Take 3 mL of stock NaOH and put it in enough = 3 mL 6M water (about 197 mL) to make 200 mL solution.

b) c)

Vc =

1.0 L x 1.0 M 1000 mL or 6 rounded for question value x = 56 mL 18 M 1L Measure 56 mL glacial acetic acid and

put it in enough water (about 944 mL) to make 1.0 L solution. 9.53 Write balanced molecular equations to illustrate five different reactions that could be used to prepare BaCl2 from hydrochloric acid (HCl) and other appropriate substances:

Solution a) BaO(s) + 2HCl(aq) BaCl2 (aq) + H2 O(l) b) Ba(OH)2(s) + 2HCl(aq) BaCl2(aq) + 2H2 O(l) c) BaCO3(s) + 2HCl(aq) BaCl 2(aq) + 2H2 O(l) + CO2 (g) d) Ba(HCO3 )2(s) + 2HCl(aq) BaCl 2(aq) + 2H2 O(l) + 2CO2(g) e) Ba(s) + 2HCl(aq) BaCl2(aq) + H 2(g) Salts (Section 9.8) 9.61 Identify with ionic formulas the cations and anions of the following salts: a) LiCI b) Cu(NO3 )2 c) SrSO4 d) K3 PO4 e) K2 HPO4 f) CaCO3 Solution a) Li+, Cld) 3K+, PO3 4 9.65 b) Cu2+ , 2NO-3 e) 2K+, HPO2 4 c) Sr2+, SO2 4 f) Ca 2+, CO2 3

Calculate the mass of water that would be released if the water of hydration were completely driven off 1.0 mol of: (a) plaster of Paris and (b) gypsum (see Table 9.6). How would the products of these reactions compare? Solution From Table 9.6, plaster of Paris is CaSO4 H2 O and gypsum is CaSO42H 2O. 1mol H2 O 18 g H2 O 1mol CaSO 4 : H2 O x x = 18 g H2 O 1mol CaSO4 : H2 O 1molH2 O a) 2 mol H2 O 18 g H2 O 1mol CaSO 4 : H2 O x x = 36 g H2 O 1mol CaSO4 : H2 O 1molH2 O b) The products are water (H2 O) and CaSO4 in both cases. The amount of water is greater from gypsum.

9.67

Write formulas for the acid and indicated a solid that could be used to prepare each of the following salts: a) CuCl2 (solid is an oxide); b) MgSO4 (solid is a carbonate); c) LiBr (solid is a hydroxide) Solution a) HCI and CuO b) H2SO 4 and MgCO3 c) HBr and LiOH

9.69

Write balanced full equations to illustrate each salt preparation described in Exercise 9.67. Solution a) CuO + 2HCl CuCl2 + H2O b) MgCO 3 + H2 SO4 MgSO4 + H2O + CO2 c) LiOH + HBr LiBr + H 2O

9.73

Determine the number of equivalents and milliequivalents in each of the following: a) 0.10 mol KI b) 0.25 mol MgCl2 c) 4.73 x 10-2 mol AgNO 3

Solution
a) 0.10 molKI x 0.10 eq x 1eq = 0.10eg 1molKI
b) 0.25 molMgCl2 x 0.50 eq x 1eq = 0.50 eg 1molMgCl2

1000 meq =1.0 x102 meq eq

1000 meq = 5.0 x102 meq eq

c) 4.73 x10- 2 mol AgNO 3 x 4.73 x10- 2 eq x

1eq = 4.73 x10- 2 eg 1mol AgNO 3

1000 meq = 47.3 meq eq

9.75

Determine the number of equivalents and milliequivalents in 5.00 g of each of the following salts. Include any waters of hydration given in the salt formula when you calculate salt formula weights. a) NaCl b) NaNO3 c) Na 3PO 4 d) MgSO4 7H2O Solution a) b) c)
5.00 g NaCl x 1mol NaCl 1eq x = 8.55 x10- 2 eq = 85.8 meq 58.5 gNaCl 1mol NaCl 1mol NaNO 3 1eq x = 5.88 x10- 2 eq = 58.8 meq 85.0 g NaNO3 1molNaNO3 1mol Na 3PO4 1eq x = 9.15 x10- 2 eq = 91.5 meq 164 gNa3 PO4 1molNa3 PO4

5.00 g NaNO3 x 5.00 g Na3 PO4 x

d) 5.00 g MgSO4 2 O (MW = 24.3 + 32.1 + 64.0 + 7(18) = 246.4) H 1molMgSO4 :H2O 2eq 5.00gMgSO4 :H Ox x =4.06x10 2 eq=40.6meq 2 246.4 gMgSO4 :H O 1molMgSO4 :H2O 2 9.77 A sample of intracellular fluid contains 45.1 meq/L of Mg2+ ion. Assume the Mg2+ comes from dissolved MgCl2 and calculate the number of moles and number of grams of MgCl2 that would be found in 250 mL of the intracellular fluid. Solution 45.1meq 1eq 1mol MgCl2 -3 x 0.250 L soln x x = 5.64 x10 mol MgCl2 L soln 1000 meq 2 eq 95.2 gMgCl2 5.64 x10- 3 mol MgCl2 x = 0.537 g MgCl2 1mol MgCl2

Strengths of Acids and Bases (Section 9.9) 9.79 Illustrate the difference between weak, moderately strong, and strong acids by writing dissociation reactions for the hypothetical acid HB using arrows of various lengths. Solution

9.81

Arrange the four acids classified as weak in Table 9.7 in order of increasing strength (weakest first, strongest last). Solution Use the % dissociation (smallest = weakest) or Ka (smallest = weakest). H3BO 3, H2 CO3, HC2 H3 O2 , and HNO2

9.83

Write dissociation reactions and K a expressions for the following weak acids: a) hypobromous acid, HBrO b) sulfurous acid, H 2SO3 (1st H only) c) hydrogen sulfite ion, HSO3 d) hydroselenic acid; H2 Se (1st H only) e) arsenic acid, H 3AsO4 (1st H only) Solution
+ a) HBrO H + BrO + b) H2 SO3 H +HSO3

c)

HSO- H+ + SO2 3 3

+ d) H2 Se H + HSe + e) H3 AsO 4 H +H2 AsO4

[H+ ][BrO- ] Ka = [HBrO] [H+ ] [HSO- ] 3 Ka = [H2 SO3 ] [H+ ][SO2 - ] 3 Ka = [HSO- ] 3 [H+ ][HSe- ] Ka = [H Se] 2 [H+ ][H2 AsO- ] Ka = [H AsO ] 4 3 4

9.85

Equal molar solutions are made of three monoprotic acids: HA, HB, and HC. The pHs of the solution are respectively 4.82, 3.16, and 5.47. Rank the acids in order of increasing acid strength and explain your reasoning. Solution The strongest acid will have the highest [H3O+] and lowest pH. HC, HA, HB

9.87

Arsenic acid (H3 AsO4 ) is a moderately weak, triprotic acid. Write equations showing its stepwise dissociation. Which of the three anions formed in these reactions will be the strongest Brnsted base? Which will be the weakest Brnsted base? Explain your answers. Solution

2+ 3+ + 21) H3 AsO4 H +H2 AsO4 2) H2 AsO4 H + HAsO4 3) HAsO 4 H + AsO4 H3AsO 4 is the strongest acid; H2 AsO- is the weakest base. 4

HAsO4 is the weakest acid;

2-

AsO4 , is the strongest base.

3-

Analysis of Acids and Bases (Section 9.10) 9.89 Describe the difference between the information obtained by measuring the pH of an acid solution and by titrating the solution, using and indicator, with base. Solution The pH of a solution measures the [H+] actually present in the solution at that instant. The titration determines the total amount of [H+] ultimately available from the acid for reaction with the base. 9.91 Determine the number of moles of NaOH that could be neutralized by each of the following: a) 1.00 L of 0.200 M HCl b) 500 mL of 0.150 M HNO3 Solution
0.200 mol HCl 1mol NaOH x = 0.200 mol NaOH a) 1L soln 1mol HCl 0.150 mol HNO3 1mol NaOH 0.500 L soln x x = 0.0750 mol NaOH 1L soln 1molHNO3 b) 1.00 L soln x

Titration Calculations (Section 9.11) 9.95 Write a balanced molecular equation to represent the neutralization reaction between HCl and each of the following bases: a) Cd(OH)2 b) Cr(OH) 3 c) Fe(OH)2 Solution a) Cd(OH)2 + 2HCl CdCl2 + 2H2O c) Fe(OH)2 + 2HCl FeCl2 + 2H2O 9.97 b) Cr(OH) 3 + 3HCl CrCl3 + 3H2 O

A 25.00 mL sample of gastric juice is titrated with 0.0210 M NaOH solution. The titration to the equivalence point requires 29.8 mL of NaOH solution. If the equation for the reaction is HCl(aq) + NaOH(aq) NaCl(aq) + H 2O(l) what is the molarity of HCl in the gastric juice? Solution
moles HCl =29.8mL x 1L 0.0210molNaOH 1molHCl x x =6.26 x10- 4 molHCl 1000 ml 1L 1molNaOH

-4 1000 mL MofHCl = 6.26X10 molHCl x =0.0250MHCl 1L 25.00 mL

9.99

A 20.00 mL sample of each of the following acid solution is to be titrated to the equivalence point using 0.120 M NaOH solution. Determine the milliliters of NaOH solution that will be needed for each acid sample. a) 0.180 M HCl b) 0.180 M H 2SO4

c) 0.100 M HCl d) 10.00 g of H 3PO4 in 250 mL solution e) 0.150 mol H2MoO4 in 500 mL solution f) 0.215 mol H2 MoO4 in 700 mL solution Solution At the equivalence point, the mol H+ = mol OH- or meq acid = meq base. Va Ma = V bMb , where the molarity of the acid and base must be the molarity of H+ or OH-. For the 0.120 M NaOH, the solution is 0.120 M in OH-. a) For 0.180 M HCI, the solution is 0.180 M in H+. 0.180 M M Vb = Va x a = 20.00 mL x = 30.0 mL NaOH Mb 0.120 M b) For 0.180 M H2SO 4, there are 2 H+ per H2 SO4; so it is 0.360 M in H +. 0.360 M M Vb = Va x a = 20.00 mL x = 60.0 mL NaOH Mb 0.120 M c) For 0.100 M HCI, the solution is 0.100 M in H+. 0.100 M M Vb = Va x a = 20.00 mL x = 16.7 mL NaOH Mb 0.120 M 1molH3 PO4 molH 3PO4 = 10.00 gH3 PO4 x = 0.1021mol H3PO 4 97.99 g H3 PO4 d) 0.1021molH3 PO4 M= = 0.408 MH3PO4 0.250 L soln For 0.408 M H3 PO4, there are 3 H+ per H3 PO4 ; so it is 1.23 M H+ . 1.23 M M Vb = Va x a = 20.00 mL x = 205 mL NaOH Mb 0.120 M 0.150 molH2 MoO4 = 0.300 M H2MoO 4 e) M ofH 2MoO 4 = 0.500 L + Since there are 2H per H2 MoO4, the solution is 0.600 M H+
Vb = Va x 0.600 M Ma = 20.00 mL x = 100 mL NaOH Mb 0.120 M

0.215 mol H2MoO4 = 0.307 MH2 MoO 4 f) M of H2 MoO 4 = 0.700 L + Since there are 2H per H 2MoO4 , the solution is 0.614 M H+ 0.614 M M Vb = Va x a = 20.00 mL x = 102 mL NaOH Mb 0.120 M 9.101 The following acid solutions were titrated to the equivalence point with the base listed. Use the titration data to calculate the molarity of each acid solution. a) 25.00 mL of HI solution required 27.15 mL of 0.250 M NaOH solution b) 20.00 mL of H 2SO4 solution required 11.12 mL of 0.109 M KOH solution c) 25.00 mL of gastric juice (HCl) required 18.40 mL of 0.0250 M NaOH solution

Solution

a) molesHI= 27.15 mL x MHI= 6.79 x10 molHI x 25mL

1L 0.250molNaOH x x 1molHI = 6.79 x10- 3 molHI 1000 mL 1L 1molNaOH

1000 mL =0.272 MHI 1L 1L 0.109molKOH 1molH2SO4 b) molesH2 SO4 =11.12mL x x x =6.06x10- 4 molH2 SO4 1000mL 1L 2molKOH
MH2SO4 = 6.06x10- 4 molH2SO4 1000mL x =0.303MH2SO4 20mL 1L

c) molesHCl=18.40mL x
-3

1L 0.250 molNaOH 1molHCl x x = 4.60 x10- 3 molHCl 1000 mL 1L 1molNaOH 1000 mL =0.184MHCl 1L

MHCl= 4.60 x10 molHCl x 25mL

9.103 A 20.00 mL sample of diprotic oxalic acid (H2 C2 O4 ) solution is titrated with 0.250 M NaOH solution. A total of 27.86 mL of NaOH is required. Calculate: a) the number of moles of oxalic acid in the 20.00 mL sample b) the molarity of the oxalic acid solution c) the number of grams of oxalic acid in the 20.00 mL sample Solution
1L 0.250molNaOH 1molH2C2O4 x x =3.48x10- 3 molH2C2O4 a) 1000mL 1L 2molNaOH 3.48 x10- 3 molH2 C2O4 1000 mL M= x = 0.174 MH2C2O 4 1L b) 20 mL 90.0 g H2 C2 O4 3.48 x10- 3 mol H2 C2 O4 x = 0.313 g H2 C2 O 4 1mol H2 C 2 O4 c) molH C2O4 =27.86mL 2

Hydrolysis Reactions of Salts (9.12) 9.105 A solution of solid NH4Cl in pure water is acidic (the pH is less than 7). Explain. Solution The NH+ is a Brnsted acid, establishing an equilibrium with H 2O: 4
NH+ + H2 O H3 O + + NH3 4

The H3O + formed makes the solution acidic (pH is less than 7). 9.107 Predict the relative pH (greater than 7, less than 7, etc) for water solutions of the following salts. Table 9.9 may be useful. For each solution in which the pH is greater or less than 7, explain why and write a net ionic equation to justify your answer. a) potassium sulfite, K2 SO3 b) lithium nitrite, LiNO2 c) sodium carbonate, Na 2CO3; d) methylammonium chloride, CH 3NH3 Cl (CH3NH2 is a weak base) Solution a) Basic. SO 2 - is a weak base. SO 2 - + H2 O HSO - + O H3 3 3 b) Basic. NO -2 is a weak base. NO - + H2 O HNO 2 + OH2

c) Basic. CO 2 - is a weak base. CO 2 - + H2 O HCO - + OH3 3 3 d) Acidic. CH3 NH+ is a weak acid. CH3 NH+ + H2 O H3 O + + CH3 NH2 3 3 9.109 A chemist has 20.00 mL samples of 0.100 M acid A and 0.100 M acid B in separate flasks. Both acids are monoprotic. Unfortunately, the flasks are not labeled, so the scientist does not know which sample is in which flask. But fortunately, it is known that acid A is strong and acid B is weak. Before thinking about the problem, the chemist adds 20.00 mL of 0.100 M NaOH to each flask. Explain how the chemist could use a pH meter (or pH paper) to determine which flask originally contained which acid. Solution The 20.00 mL of NaOH would react with all of the acid in both cases, giving essentially a solution of the sodium salt of the acid. The salt of the strong acid would not hydrolyze and would have a pH = 7. The salt of the weak acid would hydrolyze, giving a basic solution (pH greater than 7). 9.111 How would the pH of equal molar solutions of the following salts compare (highest, lowest, etc)? NaH2 PO4, Na2 HPO4, and Na 3PO4 Solution The Na 3PO4 would have the highest pH, definitely basic, because the PO3 4 is the strongest base of the three anions. The NaH2 PO4 would be the lowest pH, definitely acidic, because H2PO- is the strongest acid of the three 4 anions. The pH of the Na 2HPO4 would be higher than NaH2PO4 and lower than Na3 PO4. Buffers (Section 9.13) 9.113 Could a mixture of ammonia (NH 3), a weak base, and ammonium chloride (NH4 Cl) behave as a buffer when dissolved in water? Use equations to justify your answer. Solution Yes. The NH3 could react with added acid, and the NH+ could react with 4 added base. The equations are: NH3 + H+ " NH+ and NH+ + OH- " NH3 + H2 O 4 4 9.115 Calculate the pH of a buffer made by dissolving 1 mol formic acid (HCOOH) and 1 mol sodium formate (HCOONa) in 1 L of solution (see Table 9.9). Solution From Table 9.9, pKa = 3.74 [B-] = [HB] = 1.0 Using Equation 9.54, pH = 3.74 + log 1 = 3.74
pH = pKa + log [B- ] [HB]

9.117 Which of the following weak acids and its conjugate base would you use to make a buffer with a pH of 5.00? Explain your reasons. Acetic acid, nitrous acid, or formic acid. Solution The best buffer capacity is when the pH equals the pK a. The closer the pH Is to pKa , the higher the buffer capacity. Since pKa for acetic acid is the closest to 5.00, a mixture of acetic acid and acetic ion would be best. 9.119 Calculate the pH of the buffers with the acid and conjugate base concentrations listed below. 23a) [HPO 4 ]= 0.33 M, [PO4 ] = 0.52 M b) [HNO2 ]= 0.029M, [NO2 ]= 0.065 M 2c) [HCO3 ] = 0.50 M, [CO3 ]= 0.15 M Solution 2a) pKa forHPO4 = 12.66 pH = 12.66 + log 0.52 = 12.86 0.33
c) pKa for HCO- = 10.25 3 pH = 10.25 + log 0.15 = 9.73 0.50

b) pKa forHNO2 = 3.33 pH = 3.33 + log 0.065 = 3.68 0.029

9.121 A citric acid-citrate buffer has pH = 3.20. You want to increase the pH to a value of 3.35. Would you add citric acid or sodium citrate to the solution? Explain. Solution Add sodium citrate. There are at least two viable explanations: (1) to increase pH, add the Brnsted base, citrate; or (2) in Equation 9.54, if the [B-] increases, the value of the log term increases, which increases pH.

ADDITIONAL EXERCISES 9.123 Consider the following dissociation reaction of a weak acid, HA: It was determined that 2.63% of the acid in a 0.150 M solution of HA in water was dissociated. Calculate the pH of the 0.150 M solution. Solution

9.125 When sodium metal, Na, reacts with water, hydrogen gas, H 2, and sodium hydroxide, in solution are produced. Write a balanced equation for the reaction, and explain how a basic solution is produced.

Solution In this single replacement reaction, sodium and hydrogen exchange places. The resulting sodium hydroxide is a strong base. SOLUTIONS TO CHEMISTRY FOR THOUGHT 9.132 In an early industrial method, H2 SO4 was manufactured in lead-lined chambers. Propose an explanation for this. Solution Pb reacts with H2 SO4 to make PbSO4 and H2. The PbSO4 is not soluble and coats the surface of the lead, preventing further reaction between the acid and the metal. 9.133 A saturated solution of solid Ca(OH)2 in water has a [OH-] of only 2.50 x 10 -2 M, and yet Ca(OH)2 is a strong base. Explain this apparent contradiction. Solution Ca(OH)2 is only slightly soluble in water, but the limited amount of Ca(OH) 2 which dissolves is completely ionized (completely dissociated). Hence, it is a strong base because it ionizes completely, but the concentration of [OH-] is limited by the solubility. 9.134 Imagine a solution of weak acid is being titrated with a strong base. Describe the substances present in the solution being titrated when it has been titrated halfway to the equivalence point. How is the pH of this half-titrated solution related to pKa for the weak acid? Solution At that point in the titration of HB, one half of the original HB has reacted to form B -. Thus, the remaining concentration of HB equals the concentration of [B- ] log =0 B . Using Equation 9.54, the pH = pKa because [HB] 9.135 Calculate K a for the following weak acids based on the equilibrium concentrations and pH values given. a) Benzoic acid, represented by HBz: pH = 2.61, [Bz-] = 2.48 x 10 -3 , [HBz] = 0.0975 b) Abietic acid, represented by HAb: pH = 4.16, [Ab-] = 6.93 x 10-5, [HAb] = 0.200 c) Cacodylic acid, represented by HCc: pH = 3.55, [Cc-] = 0.000284, [HCc] = 0.150 Solution Rearranging Equation 9.54 gives -3 [2.48 x10 ] pKa = 2.61- log = 4.20 a) [0.0975]
pK a = pH- log [B- ] [HB]
-5

Ka = 6.93 x10

[6.93 x10- 5 ] b) pKa = 4.16 - log [0.200] = 7.62 [0.000284] pKa = 3.55 - log = 6.27 c) [0.150]

Ka = 2.40 x10- 8
Ka = 5.37 x10 - 7

9.136 Bottles of ketchup are routinely left on the counters of cafes, yet the ketchup does not spoil. Why not? Solution The vinegar in the ketchup makes the pH low enough (acidity high) that the ketchup is like pickles (see Chemistry Around Us 9.2). The microorganisms that makes many foods spoil cannot survive in the high acidity. 9.137 Refer to Figure 9.2 and answer the question. What implications does this reaction have for the long-term durability of marble structures when exposed to acid rain? Solution The CaCO 3 in the marble reacts with the acid to produce CO2 gas. The acid rain will react with marble, eroding the surface. Marble structures will ultimately erode away under long-term exposure to acid rain. 9.138 Refer to Figure 9.3 and answer the question. Do you think the results would be the same if sulfuric acid (H2 SO4 ) were substituted for the HCl? Explain. Solution Yes. The most active metal reacts most vigorously. The reaction would be the same using H 2SO4 , instead of HCI, for the three metals tested. If either the chloride salt or the sulfate salt of the metal were insoluble, there would then be a detectable difference in the reactions using HCI or H 2SO4 . (See 9.1) 9.140 Refer to Figure 9.6 and explain why the pH reading of the meter might not be 7.00 at the equivalence point in a titration. Would the pH at the equivalence point be greater or less than 7 if hydrochloric acid was titrated with aqueous ammonia? Solution A titration of a strong acid with a strong base would have pH = 7.00 at the equivalence point. If a weak acid is titrated with a strong base, hydrolysis of the B- makes the pH greater than 7 at the equivalence point. If a weak base (NH3 ) is titrated with a strong acid (HCI), the pH will be less than 7 at the equivalence point.

Radioactive Nuclei (Section 10.1) 10.3 Group the common nuclear radiations (Table 10.1) into the following categories: a) those with a negative charge b) those with a mass number greater than 0 c) those that consist of particles Solution a) The beta particle has a negative charge. b) The alpha and neutron have mass numbers greater than 0. c) The alpha, beta, neutron, and positron radiations consist of particles. 10.5 Discuss how the charge and mass of particles that radiation comprises influence the range or ability of the radiation to penetrate matter. Solution Particles having a high mass do not penetrate very far. The alpha particles with a high charge and high mass are extremely limited in penetration. Equations for Nuclear Reactions (Section 10.2) 10.7 Write appropriate symbols for the following particles using the, ZX symbolism. a) a tin-117 nucleus b) a nucleus of the chromium (Cr) isotope containing 26 neutrons c) a nucleus of element number 20 that contains 24 neutrons Solution a) 117 Sn 50 10.9
b)
50 24 Cr

c)

44 20Ca

Complete the following equations, using appropriate notations and formulas:

Solution a) 10Be - 0 10B 4 1 + 5

b)

210 4 206 Ti 83Bi 2 + 81

c)

15 0 15N 8O 1 + 7

d) 44 Ti + - 0e 44 Sc e) 8Be 4+ 4He f) 46 V 0 46 Ti 22 1 21 4 2 2 23 1 + 22 10.11 Write balanced equations to represent decay reactions of the following isotopes. The decay process or daughter isotope is given in parentheses.

Solution:
a) c) e)
66 0 + 66 29Cu - 1 30Zn 19 0 + 19 8O - 1 9F 108 0 108 50 Sn + - 1e 49In

b) d) f)

22 Na 0 22Ne 11 1 + 10 192 4 188 78Pt 2+ 76Os 67 0 67 28Ni - 1 + 29Cu

Isotope Half-Life (Section 10.3)

10.13 What is meant by a half-life? Solution A half-life is the time required for one half of the radioactive isotopes present at any time to undergo radioactive decay. 10.15 An isotope of lead, 194Pb , has a half-life of 11 minutes. What fraction of the lead82 194 atoms in a sample would remain after 44 minutes had elapsed? Solution The time period, 44 minutes, is four half-life periods. The fraction remaining is
1 x 1 x 1 x 1 x = ( 1)4 = 1 2 2 2 2 2 16

10.17 An archaeologist sometime in the future analyzes the iron used in an old building. The iron contains tiny amounts of nickel-63, with a half-life of 92 years. On the basis of the amount of nickel-63 and its decay products found, it is estimated that about 0.78% (1/128) of the original nickel-63 remains. If the building was constructed in 1980, in what year did the archeologist make the discovery? Solution
Since1/128 of the original is left,( 1 )n = 1 . n= 7 half - lives 2 128 7 half - lives x 92 yrs/half - life =644 yrs after 1980.The year is about 2624

Health Effects of Radiation (Section 10.4) 10.23 A radiologist found that in a 30 minute period the dose from a radioactive source was 75 units at a distance of 12.0 m from the source. What would the dose be in the same amount of time at a distance of 2.00 m from the source? Solution
2 Ix dy = 2; where Ix =?; Iy = 75units; dx = 2.00m; dy =12.0 m Iy dx

Ix =Iy x

d2 y

(12.0 m)2 = 75 units x = 2.7 x 103 units d2 (2.00 m)2 x

Measurement Units for Radiation (Section 10.5) 10.25 Explain why the rem is the best unit to use when evaluating the radiation received by a person working in an area where exposure to several types of radiation is possible. Solution The rem measures both the intensity of the radiation and the extent of damage by the different types of radiation. 10.27 Describe how scintillation counters and Geiger-Muller counters detect radiation.

Solution A scintillation counter counts the flashes of light as radiation strikes a phosphor. A Geiger counter measures the pulses of electrical current as the radiation creates a path for electricity to flow through the gas in the detector. Medical Uses of Radioisotopes (Section 10.6) 10.29 Explain what a diagnostic tracer is and list the ideal characteristics one should have. Solution A diagnostic tracer is a radioactive isotope that concentrates in a specific organ. It should have a short, but reasonable, half-life, have a stable daughter isotope, be non-toxic, and give off radiation that can penetrate out of the tissue and be detected. 10.31 List the ideal characteristics of a radioisotope that is to be administered internally for therapeutic use. Solution A therapeutic radioisotope administered internally should be an alpha or beta emitter; have a half-life long enough to do the desired radiation; be non-toxic (and have non-toxic, non-radioactive daughter isotopes); and be concentrated by the target tissue. 10.33 Gold-198 is a emitter used to treat leukemia. It has a half-life of 2.7 days. The dosage is 1.0 mCi/kg body weight. How long would it take for a 70 mCi dose to decay to an activity of 2.2 mCi? Solution The fraction left is 2.2 mCi = about 1 or( 1 )5. n = 5 half - lives 32 2 70 mCi 2.7 days x 5 = 13.5 days or about 14 days Nonmedical Uses of Radioisotope (Section 10.7) 10.35 Suppose you are planning a TV commercial for motor oil. Describe how you would set it up to show your oil prevents engine wear better than a competing brand. Solution Use a radioisotope to make the metal surfaces on two identical engines. Use a Geiger counter to measure the radioactivity present in the oil after running the engines for the same length of time. The one with the higher radioactivity in the oil had more wear on the metal parts.

10.37 Explain why carbon-14 with a half-life of about 5600 years would not be a good radioisotope to use if you want to determine the age of a coal bed thought to be several million years old. Solution After 10 half-lives, the amount of the radioisotope left is less than 1/1000 of the original amount. This would almost be undetectable. Ten half-lives for 14C = 56,000 years. The amount of 14C left after several million years would be essentially zero. Induced Nuclear Reactions (Section 10.8) 10.43 To make indium-111 for diagnostic work, silver-109 is bombarded with particles. What isotope forms when a silver-109 captures an particle? Write a balanced equation to represent the process. What two particles must be emitted by the isotope to form indium-111? Solution
1 09 47 Ag 1 + 4 111In + 2 0n 49 2

Two neutrons are emitted as a result of the bombardment. Nuclear Energy (Section 10.9) 10.45 Write one balanced equation that illustrates nuclear fission. Solution 235 1 1 139 Xe + 95 Sr + 2 0n 92U + 0n 54 38 10.47 Explain why critical mass is an important concept in neutron-induced fission chain reactions. Solution A critical mass is when there is enough fissionable material present to support a self-sustained fission reaction. This process is used for commercial power generation. 10.49 Complete the following equations, which represent two additional ways uranium235 can undergo nuclear fission. Solution

ADDITIONAL EXERCISES 10.51 Polonium-210 decays by alpha emission and has a half-life of 138 days. Suppose a sample of Po-210 contains 6.02x1020 Po-210 atoms and undergoes

decay for 138 days. What was the mass in grams of the original sample? Assume all alpha particles formed by the decay escape, and the daughter nuclei remains in the sample as nonradioactive isotopes, then calculate the mass of the sample in grams after 138 days. Solution Original mass is 6.02x10 20 atoms/6.02x1023 atoms/mol*210g/mol = 0.210 g. At 138 days, 50% of the Po-210 has decayed to daughter product by alpha emission. 50% of the Po-210 remains (0.105g) and the daughter has lost 4 out of 210 amu per decay (1.90%). The mass of the daughter would be 0.103 g. Total final mass at 138 days would be 0.208 grams. 10.55 At one time, nuclear bombs were tested by exploding them above ground. The fallout from such tests contained some Sr-90, a radioactive isotope of strontium. If Sr-90 gets into the food supply, it can be incorporated into the bones of humans and other animals. Explain how this can happen though strontium is not a normal component of bones. Solution Strontium is not normally available in the food chain but, if introduced in any manner, can behave as described. This is because it is chemically similar to calcium. ALLIED HEALTH EXAM CONNECTION 10.57 Rank the following from highest penetrating power to lowest penetrating power. a) alpha particles; b) beta particles; c) gamma rays; d) X rays Solution Gamma rays = X rays > beta particles > alpha particles 10.59 If a sample of a radioactive element with a half-life of 100 years has a mass of 31.5 kg remaining after 400 years, what was the mass in kg of the original sample. Solution After each half-life, 50% of the material remains. After 4 half-lives have passed, only 6.25% would remain. The original amount would be found by: 31.5 kg / 0.0625 = 504 kg. 10.61 Which of the following statements best expresses the fundamental principle of the mass-energy equivalency represented by the Einstein equation, E=mC2 ? a) small mass = much energy b) small mass = little energy c) little energy = great mass Solution Item a comes closest. Any mass will equate to a large amount of energy.

SOLUTIONS TO CHEMISTRY FOR THOUGHT 10.62 One (unrealized) goal of ancient alchemists was to change one element into another. Do such changes occur naturally? Explain your reasoning. Solution Yes. In naturally occurring and decay, the radioisotope changes from one kind of atom into a different kind of atom. 10.63 Refer to Figure 10.2. Some isotopes used as positron emitters in PET scans are fluorine-18, oxygen-15, and nitrogen-13. What element results in each case when a positron is emitted? Solution

10.64 Consider the concept of half-life and decide if, in principle, a radioactive isotope ever completely disappears by radioactive decay. Explain your reasoning. Solution In principle, no. Half of the remaining radioisotope decays each half-life. Eventually, a condition will be reached where there is only a single atom left, which would finally decay. 10.66 Nuclear wastes typically have to be stored for at least 20 half-lives before they are considered safe. This can be a time of hundreds of years for some isotopes. With that in mind, would you consider sending such wastes into outer space a responsible solution to the nuclear waste disposal problems? Explain your answer. Solution Sending nuclear wastes into space, ultimately to reach the sun, is a possible solution. But the risk of launch failure has to be small enough to be an acceptable risk. A launch failure would spread the radioactivity into the environment of the Earth. 10.68 Uranium-238 is the most abundant naturally occurring isotope of uranium. It undergoes radioactive decay to form other isotopes. In the first three steps of this decay, uranium-238 is converted to thorium-234, which is converted to protactinium-234, which is converted to uranium-234. Assume only one particle in addition to the daughter is produced in each step, and use equations for the decay processes to determine the type of radiation emitted during each step. Solution Step 1. U-238 Th-234 + Step 2. Th-234 Pa-234 +
Step 3. Pa-234 U-234 +