Fundamentals of Analytical Chemistry: 8th ed.

Chapter 4

Chapter 4

4-1 (a) The millimole is an amount of a chemical species, such as an atom, an ion, a molecule

or an electron. A millimole contains

particles mole particles

6.02 × 10 23 ∗ 10 −3 = 6.02 × 10 20
mole millimole millimole

(b) The molar mass is the mass in grams of one mole of a chemical species.

(c) The millimolar mass is the mass in grams of one millimole of a chemical species.

(d) Parts per million, cppm, is a term expressing the concentration of very dilute solutions.

Thus,

cppm = mass of solute × 10 6 ppm

mass of solution

The units of mass in the numerator and the denominator must be the same.

4-2 The species molarity of a solution expresses the equilibrium concentration of a chemical

species in terms of moles per liter. The analytical molarity of a solution gives the total

number of moles of a solute in one liter. The species molarity takes into account

chemical reactions that occur in solution. The analytical molarity specifies how the

solution was prepared, but does not account for any subsequent reactions.

3
1000 mL 1 cm 3  m 
4-3 1L = ×  = 10 −3 m 3
mL  100 cm 
×
1L

1 mole L 1 mole
1M = × =
L 10 m 3
−3
10 −3 m 3
Fundamentals of Analytical Chemistry: 8th ed. Chapter 4

kHz
4-4 (a) 3.2 × 105 Hz × = 320 kHz
1000 Hz

10 9 ng
(b) 4.56 × 10 −8 g × = 45.6 ng
g

mmol
(c) 8.43 × 10 5 µmol × = 843 mmol
10 3 µmol

Ms
(d) 6.5 × 10 6 s × = 6.5 Ms
10 6 s

µm
(e) 8.96 × 10 4 nm × = 89.6 µm
10 3 nm

kg
(f) 72,000g × = 72 kg
1000g

1 mol Na 3 PO 4 3 mol Na + 6.02 × 10 23 Na +

4-5 5.43 g Na 3 PO 4 × × × = 5.98 × 10 22 Na +
163.94g mol Na 3 PO 4 mol Na +

3 mol K + 6.02 × 10 23 K +
4-6 6.76 mol K 3 PO 4 × × +
= 1.22 × 10 25 K +
mol K 3 PO 4 mol K

mol B2 O 3
4-7 (a) 4.96 g B2 O 3 × = 0.0712 mol B2 O 3
69.62 g B2 O 3

(b)

g mol Na 2 B4 O 7 ⋅ 10H 2 O
333 mg Na 2 B4 O 7 • 10 H 2 O × ×
1000 mg 381.37g
= 8.73 × 10 − 4 mol Na 2 B4 O 7 ⋅ 10H 2 O

mol Mn 3O 4
(c) 8.75 g Mn 3O 4 × = 0.0382 mol Mn 3O 4
228.81 g Mn 3O 4

g mol CaC 2 O 4
(d) 167.2 mg CaC 2 O 4 × × = 1.31 × 10 −3 mol CaC 2 O 4
1000 mg 128.10 g CaC 2 O 4
Fundamentals of Analytical Chemistry: 8th ed. Chapter 4

g mol P2 O 5 1000 mmol

4-8 (a) 57 mg P2 O 5 × × × = 0.40 mmol P2 O 5
1000 mg 141.94 g P2 O 5 mol

mol CO 2 1000 mmol

(b) 12.92 g CO 2 × × = 293.6 mmol CO 2
44.01 g CO 2 mol

mol NaHCO 3 1000 mmol

(c) 40.0 g NaHCO 3 × × = 476 mmol NaHCO 3
84.01 g NaHCO 3 mol

(d)

g mol MgNH 4 PO 4 1000 mmol

850 mg MgNH 4 PO 4 × × ×
1000 mg 137.32 g MgNH 4 PO 4 mol
= 6.2 mmol MgNH 4 PO 4

4-9 (a)

−3 3.25 × 10 −3 mol KMnO 4 1000 mmol

3.25 × 10 M KMnO 4 ≡ × × 2.00 L
L mol
= 6.50 mmol KMnO 4

(b)

0.0555 mol KSCN 1000 mmol L

0.0555 M KSCN ≡ × × × 750 mL
L mol 1000 mL
= 41.6 mmol KSCN

(c)

5.41 mg CuSO 4 g mol CuSO 4 1000 mmol

5.41 ppm CuSO 4 ≡ × × ×
L 1000 mg 159.61 g CuSO 4 mol
L
× × 250 mL = 8.47 × 10 −3 mmol CuSO 4
1000 mL

0.333 mol KCl 1000 mmol

(d) 0.333 M KCl ≡ × × 3.50 L = 1165.6 mmol KCl
L mol
Fundamentals of Analytical Chemistry: 8th ed. Chapter 4

4-10 (a)

0.320 mol HClO 4 1000 mmol L

0.320 M HClO 4 ≡ × × × 175 mL
L mol 1000 mL
= 56.0 mmol HClO 4

(b)

8.05 × 10 −3 mol K 2 CrO 4 1000 mmol

8.05 × 10 −3 M K 2 CrO 4 ≡ × × 15.0 L
L mol
= 121 mmol K 2 CrO 4

(c)

6.75 mg AgNO 3 g mol AgNO 3 1000 mmol

6.75 ppm AgNO 3 ≡ × × × ×
L 1000 mg 169.87 g AgNO 3 mol
5.00 L = 0.199 mmol AgNO 3

(d)

0.0200 mol KOH 1000 mmol L

0.0200 M KOH ≡ × × × 851 mL
L mol 1000 mL
= 17.0 mmol KOH

63.01 g HNO 3 1000 mg

4-11 (a) 0.777 mol HNO 3 × × = 4.90 × 10 4 mg HNO 3
mol HNO 3 g

mol 40.30 g MgO 1000 mg

(b) 500 mmol MgO × × × = 2.015 × 10 4 mg MgO
1000 mmol mol MgO g

80.04 g NH 4 NO 3 1000 mg
(c) 22.5 mol NH 4 NO 3 × × = 1.80 × 10 6 mg NH 4 NO 3
mol NH 4 NO 3 g

(d)

548.23 g ( NH 4 ) 2 Ce( NO 3 ) 6 1000 mg

4.32 mol ( NH 4 ) 2 Ce( NO 3 ) 6 × ×
mol ( NH 4 ) 2 Ce( NO 3 ) 6 g
= 2.37 × 10 6 mg ( NH 4 ) 2 Ce( NO 3 ) 6
Fundamentals of Analytical Chemistry: 8th ed. Chapter 4

119.0 g KBr
4-12 (a) 7.1 mol KBr × = 840 g KBr
mol KBr

mol 223.20 g PbO

(b) 20.1 mmol PbO × × = 4.49 g PbO
1000 mmol mol PbO

120.37 g MgSO 4
(c) 3.76 mol MgSO 4 × = 452 g MgSO 4
mol MgSO 4

(d)

mol 392.23 g Fe( NH 4 ) 2 (SO 4 ) 2 ⋅ 6 H 2 O

9.6 mmol Fe( NH 4 ) 2 (SO 4 ) 2 ⋅ 6H 2 O × ×
1000 mmol mol Fe( NH 4 ) 2 (SO 4 ) 2 ⋅ 6 H 2 O
= 3.8 g Fe( NH 4 ) 2 (SO 4 ) 2 ⋅ 6H 2 O

4-13 (a)

0.250 mol sucrose L 342 g sucrose 1000 mg

0.250 M sucrose ≡ × × × × 26.0 mL
L 1000 mL mol sucrose g
= 2.22 × 10 3 mg sucrose

(b)

−3 4.76 × 10 −3 mol H 2 O 2 34.02 g H 2 O 2 1000 mg

4.76 × 10 M H 2 O 2 ≡ × × × 2.92 L
L mol H 2 O 2 g
= 472.8 mg H 2 O 2

(c)

4.96 mg Pb( NO 3 ) 2 L
4.96 ppm Pb( NO 3 ) 2 ≡ × × 656 mL = 3.25 mg Pb( NO 3 ) 2
L 1000 mL

(d)

0.0619 mol KNO 3 101.10 g KNO 3 1000 mg L

0.0619 M KNO 3 ≡ × × × × 6.75 mL
L mol g 1000 mL
= 42.2 mg KNO 3
Fundamentals of Analytical Chemistry: 8th ed. Chapter 4

4-14 (a)

0.164 mol H 2 O 2 L 34.02 g H 2 O 2

0.164 M H 2 O 2 ≡ × × × 450 mL
L 1000 mL mol H 2 O 2
= 2.51 g H 2 O 2

(b)

8.75 × 10 −4 mol benzoic acid L 122 g benzoic acid

8.75 × 10 − 4 M benzoic acid ≡ × × ×
L 1000 mL mol benzoic acid
27.0 mL = 2.88 × 10 −3 g benzoic acid

21.7 mg SnCl 2 g
(c) 21.7 ppm SnCl 2 ≡ × × 3.50 L = 0.0760 g SnCl 2
L 1000 mg

(d)

0.0125 mol KBrO 3 L 167 g KBrO 3

0.0125 M KBrO 3 ≡ × × × 21.7 mL
L 1000 mL mol KBrO 3
= 0.0453 g KBrO 3

4-15 (a)

pNa = − log(0.0335M + 0.0503M ) = − log(0.0838M ) = − log(8.38 × 10 −2 M )

= − log(8.38) − log(10 −2 )
= −0.923 − ( −2) = 1.077

pCl = − log(0.0335M ) = − log(3.35 × 10 −2 M )

= − log(3.35) − log(10 − 2 )
= −0.525 − ( −2) = 1.475

pOH = − log(0.0503M ) = − log(5.03 × 10 −2 M )

= − log(5.03) − log(10 −2 )
= −0.702 − ( −2) = 1.298
Fundamentals of Analytical Chemistry: 8th ed. Chapter 4

(b)

pBa = − log(7.65 × 10 −3 M )
= − log(7.65) − log(10 −3 )
= −0.884 − ( −3) = 2.116

pMn = − log(1.54 M ) = − 0.188

pCl = − log(7.65 × 10 −3 M + ( 2 × 1.54 M )) = − log(3.08M ) = − 0.490

(c)

pH = − log(0.600 M ) = − log(6.00 × 10 −1 M )
= − log(6.00) − log(10 −1 )
= −0.778 − ( −1) = 0.222

pCl = − log(0.600 M + ( 2 × 0.101M )) = − log(0.802 M ) = − log(8.02 × 10 −1 M )

= − log(8.02) − log(10 −1 )
= 0.904 − ( −1) = 0.096

pZn = − log(0.101M ) = − log(1.01 × 10 −1 M )

= − log(1.01) − log(10 −1 )
= −0.00432 − ( −1) = 0.996

(d)

pCu = − log(4.78 × 10 −2 M )
= − log(4.78) − log(10 −2 )
= −0.679 − ( −2) = 1.320

pZn = − log(0.104 M ) = − log(1.04 × 10 −1 M )

= − log(1.04) − log(10 −1 )
= −0.0170 − ( −1) = 0.983

pNO 3 = − log((2 × 0.0478M ) + ( 2 × 0.104 M )) = − log(0.304 M ) = − log(3.04 × 10 −1 M )

= − log(3.04) − log(10 −1 )
= −0.483 − ( −1) = 0.517
Fundamentals of Analytical Chemistry: 8th ed. Chapter 4

(e)

pK = − log((4 × (2.62 × 10 −7 M )) + 4.12 × 10 −7 M ) = − log(1.46 × 10 −6 M )

= − log(1.46) − log(10 −6 )
= −0.164 − ( −6) = 5.836

pOH = − log(4.12 × 10 −7 M )
= − log(4.12) − log(10 −7 )
= −0.615 − ( −7) = 6.385

pFe(CN ) 6 = − log(2.62 × 10 −7 M )
= − log(2.62) − log(10 −7 )
= −0.418 − ( −7) = 6.582

(f)

pH + = − log(6.75 × 10 −4 M )
= − log(6.75) − log(10 −4 )
= −0.829 − ( −4) = 3.171

pBa = − log(3.35 × 10 −4 M )
= − log(3.35) − log(10 −4 )
= −0.525 − ( −4) = 3.475

pClO 4 = − log(2 × (3.35 × 10 −4 M ) + 6.75 × 10 −4 M ) = − log(1.34 × 10 −3 M )

= − log(1.34) − log(10 −3 )
= −0.127 − ( −3) = 2.873

4-16 (a) [ H 3O + ] = antilog(0.240) × antilog( −5) = 1.7 × 10 −5 M

as in part (a)

(b) [ H 3O + ] = 2.6 × 10 −5 M

(c) [ H 3O + ] = 0.30 M
Fundamentals of Analytical Chemistry: 8th ed. Chapter 4

(d) [ H 3O + ] = 2.4 × 10 −14 M

(e) [ H 3O + ] = 4.8 × 10 −8 M

(f) [ H 3O + ] = 1.7 × 10−6 M

(g) [ H 3O + ] = 2.04 M

(h) [ H 3O + ] = 3.3M

4-17 (a)

pNa = pBr − = − log(0.0200 M ) = − log(2.00) − log(10 −2 )

= −0.301 − ( −2) = 1.699

pH = pOH = - log(1.0×10-7M) = 7.00

(b)

pBa = − log(0.0100 M ) = − log(1.00) − log(10 −2 )

= 0.000 − ( −2) = 2.000

pBr = − log(2 × 0.0100M ) = − log(2.00) − log(10 −2 )

= −0.301 − ( −2) = 1.699

pH = pOH = - log(1.0×10-7M) = 7.00

(c)

pBa = − log(3.5 × 10 −3 M ) = − log(3.5) − log(10 −3 )

= −0.54 − ( −3) = 2.46

pOH = − log(2 × (3.5 × 10 −3 M ) = − log(7.0 × 10 −3 M ) = − log(7.0) − log(10 −3 )

= −0.84 − ( −3) = 2.15

pH = 14.00 – pOH = (14.00 – 2.15) = 11.85

Fundamentals of Analytical Chemistry: 8th ed. Chapter 4

(d)

pH = − log(0.040M ) = − log(4.0 × 10 −2 M ) = − log(4.0) − log(10 −2 )

= −0.60 − ( −2) = 1.40

pNa = − log(0.020 M ) = − log(2.0 × 10 −2 M ) = − log(2.0) − log(10 −2 )

= −0.30 − ( −2) = 1.70

pCl = − log(0.040 M + 0.020 M ) = − log(0.060 M ) = − log(6.0 × 10 −2 M )

= − log(6.0) − log(10 −2 )
= −0.78 − ( −2) = 1.22

pOH = 14.00 – 1.40 = 12.60

(e)

pCa = log(6.7 × 10 −3 M ) = − log(6.7) − log(10 −3 )

= −0.83 − ( −3) = 2.17

pBa = − log(7.6 × 10 −3 M ) = − log(7.6) − log(10 −3 )

= −0.88 − ( −3) = 2.12

pCl = − log((2 × (6.7 × 10 −3 M )) + ( 2 × (7.6 × 10 −3 M ))) = − log(2.9 × 10 −2 M )

= − log(2.9) − log(10 −2 )
= −0.46 − ( −2) = 1.54

pH = pOH = - log(1.0×10-7M) = 7.00

(f)

pZn = − log(4.8 × 10 −8 M ) = − log(4.8) − log(10 −8 )

= −0.68 − ( −8) = 7.32

pCd = − log(5.6 × 10 −7 M ) = − log(5.6) − log(10 −7 )

= −0.75 − ( −7) = 6.25
Fundamentals of Analytical Chemistry: 8th ed. Chapter 4

pNO 3 = − log((2 × ( 4.8 × 10 −8 M )) + (2 × (5.6 × 10 −7 M ))) = − log(1.2 × 10 −6 M )

= − log(1.2) − log(10 −6 )
= −0.79 − ( −6) = 5.92

pH = pOH = - log(1.0×10-7M) = 7.00

4-18 (a) [ H 3O + ] = antilog(0.33) × antilog( −10) = 2.14 × 10 −10 M

as in part (a),

(b) [OH − ] = 0.733 M

(c) [ Br − ] = 0.92 M

(d) [Ca 2+ ] = 4.5 × 10 −13 M

(e) [Li+] = 1.66 M

(f) [ NO 3 ] = 1.7 × 10 −8 M
−

(g) [ Mn 2+ ] = 0.99 M

(h) [Cl-] = 0.0955 M

4-19 (a)

1 1.02 g 1000 mL mol Na +

1.08 × 10 3 ppm Na + × × × × = 0.0479 M Na +
10 6 ppm mL L 22.99 g

3−
2− 1 1.02 g 1000 mL mol SO 4 2−
270 ppm SO 4 × 6 × × × = 2.87 × 10 −3 M SO 4
10 ppm mL L 96.06 g

(b)

pNa = − log(4.79 × 10 −2 M ) = − log(4.79) − log(10 −2 )

= −0.680 − ( −2) = 1.320
Fundamentals of Analytical Chemistry: 8th ed. Chapter 4

pSO 4 = − log(2.87 × 10 −3 M ) = − log(2.87) − log(10 −3 )

= −0.458 − ( −3) = 2.543

4-20 (a)

18 mg K + 1000 mL g mol K +
× × × = 4.6 × 10 −3 M K +
100 mL L 1000 mg 39.10 g

365 mg Cl − 1000 mL g mol Cl −

× × × = 0.103 M Cl −
100 mL L 1000 mg 35.45 g

(b)

pK = − log(4.6 × 10 −3 M ) = − log(4.6) − log(10 −3 )

= −0.66 − ( −3) = 2.34

pCl = –log(1.03×10-1M) = –log(1.03)–log(10-1)

= –0.0133–(–1) = 0.987

4-21 (a)

5.76 g KCl ⋅ MgCl 2 ⋅ 6 H 2 O mol KCl ⋅ MgCl 2 ⋅ 6 H 2 O

× = 0.01037 M KCl ⋅ MgCl 2 ⋅ 6 H 2 O
2.00 L 277.85 g
(b)

mol Mg 2+
0.01037 M KCl ⋅ MgCl 2 ⋅ 6 H 2 O × = 0.01037 M Mg 2+
mol KCl ⋅ MgCl 2 ⋅ 6 H 2 O

3 mol Cl −
(c) 0.01037 M KCl ⋅ MgCl 2 ⋅ 6 H 2 O × = 0.0311 M Cl −
mol KCl ⋅ MgCl 2 ⋅ 6 H 2 O

5.76 g KCl ⋅ MgCl 2 ⋅ 6 H 2 O L

(d) × × 100% = 0.288% (w/v)
2.00 L 1000 mL
Fundamentals of Analytical Chemistry: 8th ed. Chapter 4

(e)

0.0311 mol Cl −
− L 1000 mmol
0.0311 M Cl ≡ × × × 25.0 mL = 0.777 mmol Cl −
L 1000 mL mol

(f)

1 mol K + 39.10 g K + 1000 mg

0.01037 M KCl ⋅ MgCl 2 ⋅ 6H 2 O × × ×
1 mol KCl ⋅ MgCl 2 ⋅ 6 H 2 O mol K + g
405 mg
= ≡ 405 ppm K +
L

(g) pMg = − log(1.04 × 10 −2 M ) = − log(1.04) − log(10 −2 ) = −0.0170 − ( −2) = 1.984

(h) pCl = − log(3.12 × 10 −2 M ) = − log(3.12) − log(10 −2 ) = −0.494 − ( −2) = 1.507

4-22 (a)

1210 mg K 3 Fe(CN ) 6 1210 g K 3 Fe(CN ) 6 mol K 3 Fe(CN ) 6

≡ × = 4.74 × 10 −3 M K 3 Fe(CN ) 6
775 mL 775 L 329.2 g

−3 3 mol K +
(b) 4.74 × 10 M K 3 Fe(CN ) 6 × = 0.0142 M K +
mol K 3 Fe(CN ) 6

3−
mol Fe(CN ) 6 3−
(c) 4.74 × 10 −3 M K 3 Fe(CN ) 6 × = 4.74 × 10 −3 M Fe(CN ) 6
mol K 3 Fe(CN ) 6

1210mgK 3 Fe(CN ) 6 g
(d) × × 100% = 0.156% (w/v)
775mL 1000mg

(e)

1.42 × 10 −2 mol K + L 1000 mmolK +

1.42 × 10 − 2 M K + ≡ × × × 50.0 mL
L 1000 mL mol K +
= 0.710 mmol K +
Fundamentals of Analytical Chemistry: 8th ed. Chapter 4

(f)
3−
−3 4.74 × 10 −3 mol K 3 Fe(CN) 6 mol Fe(CN) 6
4.74 × 10 M K 3 Fe(CN) 6 ≡ ×
L mol K 3 Fe(CN) 6
3−
211.95 g Fe(CN) 6 1000 mg 1000 mg 3− 3−
× 3−
× = Fe(CN) 6 ≡ 1.00 × 10 3 ppm Fe(CN) 6
mol Fe(CN) 6 g L

(g) pK = − log(1.42 × 10 −2 M ) = − log(1.42) − log(10 −2 ) = −0.152 − ( −2) = 1.848

3−
(h) pFe(CN ) 6 = − log(4.74 × 10 −3 M ) = − log(4.74) − log(10 −3 ) = −0.676 − ( −3) = 2.324

4-23 (a)

6.42 g Fe( NO 3 ) 3 1 1.059 g 1000 mL mol Fe( NO 3 ) 3

6.42% Fe( NO 3 ) 3 ≡ × × × ×
g solution 100 mL L 241.86 g
= 0.281 M Fe( NO 3 ) 3

(b)

−
0.281 mol Fe( NO 3 ) 3 3 mol NO 3 −
0.281 M Fe( NO 3 ) 3 ≡ × = 0.844 M NO 3
L mol Fe( NO 3 ) 3

(c)

0.281 mol Fe( NO 3 ) 3 241.86 g Fe( NO 3 ) 3 68.0 g Fe( NO 3 ) 3

0.281 M Fe( NO 3 ) 3 ≡ × =
L mol L

4-24 (a)

12.5 g NiCl 2 1 1.149 g 1000 mL mol NiCl 2

12.5% NiCl 2 ≡ × × × × = 1.11 M NiCl 2
g solution 100 mL L 129.61 g

1.11 mol NiCl 2 2 mol Cl −

(b) 1.11 M NiCl 2 ≡ × = 2.22 M Cl −
L mol NiCl 2

1.11 mol NiCl 2 129.61 g NiCl 2

(c) 1.11 NiCl 3 ≡ × × L = 144 g NiCl 2
L mol
Fundamentals of Analytical Chemistry: 8th ed. Chapter 4

4-25 (a)

4.75 g C 2 H 5OH 1
4.75% ( w / v ) C 2 H 5OH ≡ × × 500 mL soln = 23.8 g C 2 H 5OH
mL soln 100

Weigh 23.8 g ethanol and add enough water to give a final volume of 500 mL.

(b)

4.75 g C 2 H 5OH 1
4.75% ( w / w ) C 2 H 5OH ≡ × × 500 g soln = 23.8 g C 2 H 5OH
g soln 100
500 g soln = 23.8 g C 2 H 5OH + x g water
x g water = 500 g soln − 23.8 g C 2 H 5OH = 476.2 g water

Mix 23.8 g ethanol with 476.2 g water.

(c)

4.75 mL C 2 H 5OH 1
4.75% ( v / v ) C 2 H 5OH ≡ × × 500 mL soln = 23.8 mL C 2 H 5OH
mL soln 100

Dilute 23.8 mL ethanol with enough water to give a final volume of 500 mL.

4-26 (a)

21.0 g C 3 H 8 O 3 1 1000 mL
21.0% ( w / v ) C 3 H 8O 3 ≡ × × × 2.50 L soln = 525 g C 3 H 8 O 3
mL soln 100 L
Weigh 525 g glycerol and add enough water to give a final volume of 2.50 L.

(b)

21.0 g C 3 H 8 O 3 1 1000 g
21.0% ( w / w ) C 3 H 8O 3 ≡ × × × 2.50 kg soln = 525 g C 3 H 8 O 3
g soln 100 kg
2.50 kg soln = 0.525 kg C 3 H 8O 3 + x kg water
x kg water = 2.50 kg soln − 0.525 kg C 3 H 8O 3 = 1.98 kg water

Mix 525 g glycerol with 1.98 kg water.

Fundamentals of Analytical Chemistry: 8th ed. Chapter 4

(c)

21.0 mL C 3 H 8O 3 1 1000 mL
21.0% ( v / v ) C 3 H 8O 3 ≡ × × × 2.50 L soln = 525 mL C 3 H 8O 3
mL soln 100 L
Dilute 525 mL glycerol with enough water to give a final volume of 2.50 L.

4-27

6.00 mol H 3 PO 4 L
6.00 M H 3 PO 4 ≡ × × 750 mL = 4.50 mol H 3 PO 4
L 1000 mL
86 g H 3 PO 4 1 1.71 g reagent g water 1000 mL mol H 3 PO 4
86% ( w / w ) H 3 PO 4 ≡ × × × × ×
g reagent 100 g water mL L 98.0 g
15.0 mol H 3 PO 4
=
L
L
volume 86% ( w / w ) H 3 PO 4 required = 4.50 mol H 3 PO 4 × = 0.300 L
15.0 mol H 3 PO 4
Dilute 300 mL of the concentrated reagent to 750 mL using water.

4-28

3.00 mol HNO 3 L

3.00 M HNO 3 ≡ × × 900 mL = 2.70 mol HNO 3
L 1000 mL
70.5 g HNO 3 1 1.42 g reagent g water 1000 mL mol HNO 3
70.5% ( w / w ) HNO 3 ≡ × × × × ×
g reagent 100 g water mL L 63.0 g
15.9 mol HNO 3
=
L
L
volume 70.5% HNO 3 required = 2.70 mol HNO 3 × = 0.170 L
15.9 mol HNO 3
Dilute 170 mL of the concentrated reagent to 900 mL using water.

4-29 (a)

0.0750 mol AgNO 3 169.87 g AgNO 3 L

0.0750 M AgNO 3 ≡ × × × 500 mL
L mol 1000 mL
= 6.37 g AgNO 3

Dissolve 6.37 g AgNO3 in enough water to give a final volume of 500 mL.
Fundamentals of Analytical Chemistry: 8th ed. Chapter 4

(b)

0.285 mol HCl

0.285 M HCl ≡ × 1 L = 0.285 mol HCl
L
L
0.285 mol HCl × = 0.0475 L HCl
6.00 mol HCl

Take 47.5 mL of the 6.00 M HCl and dilute to 1.00 L using water.

(c)

0.0810 mol K + L
0.0810 M K + ≡ × × 400 mL = 3.24 × 10 − 2 mol K +
L 1000 mL
mol K 4 Fe(CN ) 6 368.43 g K 4 Fe(CN ) 6
3.24 × 10 −2 mol K + × × = 2.98 g K 4 Fe(CN ) 6
4 mol K + mol

Dissolve 2.98 g K4Fe(CN)6 in enough water to give a final volume of 400 mL.

(d)

3.00 g BaCl 2 1
3.00% ( w / v ) BaCl 2 ≡ × × 600 mL = 18.0 g BaCl 2
mL soln 100
mol BaCl 2 L
18.0 g BaCl 2 × × = 0.216 L
208.23 g 0.400 mol BaCl 2

Take 216 mL of the 0.400 M BaCl2 solution and dilute to 600 mL using water.

(e)

0.120 mol HClO 4

0.120 M HClO 4 ≡ × 2.00 L = 0.240 mol HClO 4
L
71 g HClO 4 1 1.67 g reagent g water 1000 mL mol HClO 4
71% ( w / w ) HClO 4 ≡ × × × × ×
g reagent 100 g water mL L 100.46 g
11.8 mol HClO 4
=
L
L
volume 71% ( w / w ) HClO 4 required = 0.240 mol HClO 4 × = 0.0203 L
11.8 mol HClO 4
Take 20.3 mL of the concentrated reagent and dilute to a final volume of 2.00 L using

water.
Fundamentals of Analytical Chemistry: 8th ed. Chapter 4

(f)

60 mg Na +
60 ppm Na + ≡ × 9.00 L = 540 mg Na +
L soln
+ g mol Na +
540 mg Na × × = 0.02348 mol Na +
1000 mg 22.99 g
mol Na 2SO 4 142.04 g Na 2SO 4
0.02348 mol Na + × × = 1.67 g Na 2SO 4
2 mol Na + mol

Dissolve 1.67 g Na2SO4 in enough water to give a final volume of 9.00 L.

4-30 (a)

0.0500 mol KMnO 4 158.03 g KMnO 4

0.0500 M KMnO 4 ≡ × 5.00 L × = 39.5 g KMnO 4
L mol
Dissolve 39.5 g KMnO4 in enough water to give a final volume of 5.00 L.

(b)

0.250 mol HClO 4

0.250 M HClO 4 ≡ × 4.00 L = 1.00 mol HClO 4
L
L
1.00 mol HClO 4 × = 0.125 L reagent
8.00 mol reagent

Take 125 mL of the 8.00 M reagent and dilute a final of volume of 4.00 L using water.

(c)

0.0250 mol I − L
0.0250 M I − ≡ × × 400 mL = 0.0100 mol I −
L 1000 mL
mol MgI 2 278.11 g MgI 2
1.00 × 10 − 2 mol I − × × = 1.39 g MgI 2
2 mol I − mol

Dissolve 1.39 g MgI2 in enough water to give a final volume of 400 mL.

(d)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 4

1.00 g CuSO 4 1
1.00% ( w / v ) CuSO4 ≡ × × 200 mL = 2.00 g CuSO 4
mL soln 100
mol CuSO 4 L
2.00 g CuSO 4 × × = 0.0343 L
159.60 g 0.365 mol CuSO 4

Take 34.3 mL of the 0.365 M CuSO4 and dilute to a final volume of 200 mL using water.

(e)

0.215 mol NaOH

0.215 M NaOH ≡ × 1.50 L = 0.3225 mol NaOH
L
50 g NaOH 1 1.525 g reagent g water 1000 mL mol NaOH
50% ( w / w ) NaOH ≡ × × × × ×
g reagent 100 g water mL L 40.00 g
19.062 mol NaOH
=
L
L
volume 50% ( w / w ) NaOH required = 0.3225 mol NaOH × = 0.0169 L
19.062 mol NaOH
Take 16.9 mL of the concentrated reagent and dilute to a final volume of 1.50 L using

water.

(f)

12 mg K +
12.0 ppm K + ≡ × 1.50 L = 1.8 × 101 mg K +
L soln
g mol K +
1.8 × 101 mg K + × × = 4.60 × 10 −4 mol K +
1000 mg 39.10 g
mol K 4 Fe(CN ) 6 368.35 g K 4 Fe(CN ) 6
4.60 × 10 −4 mol K + × × = 0.0424 g K 4 Fe(CN ) 6
4 mol K + mol

Dissolve 42.4 mg K4Fe(CN)6 in enough water to give a final volume of 1.50 L.

4-31

0.250 mol La 3+ L
0.250 M La 3+ ≡ × × 50.0 mL = 1.25 × 10 −2 mol La 3+
L 1000 mL
−
0.302 mol IO 3 L
× 75.0 mL = 2.27 × 10 −2 mol IO 3
− −
0.302 M IO 3 ≡ ×
L 1000 mL

Because each mole of La(IO3)3 requires three moles IO3-, IO3- becomes the limiting
Fundamentals of Analytical Chemistry: 8th ed. Chapter 4

reagent. Thus,

mol La ( IO 3 ) 3 663.6 g La ( IO 3 ) 3
2.27 × 10 −2 mol IO 3 ×
−
−
× = 5.01 g La ( IO 3 ) 3 formed
3 mol IO 3 mol

4-32

2+ 0.125 mol Pb 2+ L
0.125 M Pb ≡ × × 200 mL = 2.50 × 10 −2 mol Pb 2+
L 1000 mL
0.175 mol Cl − L
0.175 M Cl − ≡ × × 400 mL = 7.00 × 10 −2 mol Cl −
L 1000 mL

Because each mole of PbCl2 requires two moles Cl-, Pb2+ becomes the limiting reagent.

Thus,

mol PbCl 2 278.10 g PbCl 2

2.50 × 10 −2 mol Pb 2+ × × = 6.95 g PbCl 2 formed
mol Pb 2+ mol

4-33 A balanced chemical equation can be written as shown below.

Na 2 CO 3 + 2 HCl → 2 NaCl + H 2 O + CO 2 ( g )

(a)

mol Na 2 CO 3
0.2220 g Na 2 CO 3 × = 2.094 × 10 −3 mol Na 2 CO 3
105.99 g
0.0731 mol HCl L
0.0731 M HCl ≡ × × 100.0 mL = 7.31 × 10 −3 mol HCl
L 1000 mL

Because one mole of CO2 is evolved for every mole Na2CO3 reacted, Na2CO3 is the

limiting reagent. Thus,

mol CO 2 44.01 g CO 2
2.094 × 10 −3 mol Na 2 CO 3 × × = 0.09218 g CO 2 evolved
mol Na 2 CO 3 mol
Fundamentals of Analytical Chemistry: 8th ed. Chapter 4

(b)

mol HCl left = 7.31 × 10 −3 mol − ( 2 × ( 2.094 × 10 −3 mol)) = 3.12 × 10 −3 mol

3.12 × 10 −3 mol HCl 1000 mL
× = 0.0312 M HCl
100.0 mL L

4-34 A balanced chemical equation can be written as shown below.

Na 3 PO 4 + 3HgNO 3 → 3NaNO 3 + Hg 3 PO 4

(a)

0.3757 mol Na 3 PO 4 L
0.3757 M Na 3 PO 4 ≡ × × 25.0 mL = 9.39 × 10 −3 mol Na 2 PO 4
L 1000 mL
0.5151 mol HgNO 3 L
0.5151 M HgNO 3 ≡ × × 100.0 mL = 0.05151 mol HgNO 3
L 1000 mL
The limiting reagent is Na2PO4. Thus,

mol Hg 3 PO 4 696.74 g Hg 3 PO 4
9.39 × 10 −3 mol Na 2 PO 4 × × = 6.54 g Hg 3 PO 4 formed
mol Na 3 PO 4 mol

(b)

mol HgNO 3 unreacted = 5.151 × 10 −2 mol − (3 × (9.39 × 10 −3 mol)) = 0.0233 mol HgNO 3
0.0233 mol HgNO 3 1000 mL
× = 0.187 M HgNO 3
125.0 mL L

4-35 A balanced chemical equation can be written as shown below.

Na 2SO 3 + 2 HClO 4 → 2 NaClO 4 + H 2 O + SO 2 ( g )

(a)

0.3132 mol Na 2SO 3 L

0.3132 M Na 2SO 3 ≡ × × 75.00 mL = 0.02349 mol Na 2SO 3
L 1000 mL
0.4025 mol HClO 4 L
0.4025 M HClO 4 ≡ × × 150.0 mL = 0.06038 mol HClO 4
L 1000 mL

Because one mole SO2 is evolved per mole Na2SO3, Na2SO3 is the limiting reagent.
Fundamentals of Analytical Chemistry: 8th ed. Chapter 4

Thus,

mol SO 2 64.06 g SO 2
0.02349 mol Na 2SO 3 × × = 1.505 g SO 2 evolved
mol Na 2SO 3 moL

(b)

mol HClO 4 unreacted = (0.06038 mol - 2 × (0.02349 mol)) = 0.01340 mol HClO 4
0.01340 mol HClO 4 1000 mL
× = 0.0595 M HClO 4
225.0 mL L

4-36 A balanced chemical equation can be written as shown below.

+
MgCl 2 + Na 2 PO 4 + NH 4 → MgNH 4 PO 4 ( s ) + 2 Na + + 2Cl −

1.000 g MgCl 2 1 mol MgCl 2

1.000% ( w / v ) MgCl 2 ≡ × × 200.0 mL ×
mL 100 95.21 g
= 0.02101 mol MgCl 2

0.1753 mol Na 2 PO 4 L
0.1753 M Na 2 PO 4 ≡ × × 40.0 mL = 7.01 × 10 −3 mol Na 2 PO 4
L 1000 mL
The Na2PO4 is the limiting reagent. Thus,

137.35 g MgNH 4 PO 4
mass MgNH 4 PO 4 ppt = 7.01 × 10 −3 × = 0.9628 g MgNH 4 PO 4
mol
mol MgCl 2 unreacted = (0.02101 − 7.01 × 10 −3 ) = 0.0140 mol MgCl 2
0.0140 mol MgCl 2 1000 mL
× = 0.0583 M MgCl 2
240.0 mL L

4-37 A balanced chemical equation can be written as shown below.

−
AgNO 3 + KI → AgI( s ) + K + + NO 3

1 g mol KI
24.31 ppt KI × 3
× × 200.0 mL × = 0.02930 mol KI
10 ppt mL 166.0 g
mol AgNO 3 L 1000 mL
0.02930 mol KI × × × = 2930 mL AgNO 3
mol KI 0.0100 mol AgNO 3 L

2930 mL of 0.0100 M AgNO3 would be required to precipitate all I- as AgI.

Fundamentals of Analytical Chemistry: 8th ed. Chapter 4

4-38 A balanced chemical equation can be written as shown below.

3Ba ( NO 3 ) 2 + Al 2 (SO 4 ) 3 → 3BaSO 4 + 2Al +3 + 6 NO 3

−

(a)

1 g mol Ba ( NO 3 ) 2
480.4 ppm Ba ( NO 3 ) 2 × 6
× × 750.0 mL ×
10 ppm mL 261.34 g
= 1.38 × 10 −3 mol Ba ( NO 3 ) 2
0.03090 mol Al 2 (SO 4 ) 3 L
0.03090 M Al 2 (SO 4 ) 3 ≡ × × 200.0 mL
L 1000 mL
= 6.18 × 10 −3 mol Al 2 (SO 4 ) 3

The Ba(NO3)2 is the limiting reagent. Thus,

3 mol BaSO 4 233.39 g BaSO 4

1.38 × 10 −3 mol Ba ( NO 3 ) 2 × × = 0.322 g BaSO 4 formed
3 mol Ba ( NO 3 ) 2 mol
(b)

mol Al 2 (SO 4 ) 3 unreacted = (6.18 × 10 −3 − ( 1 × (1.38 × 10 −3 )) = 5.72 × 10 −3 mol Al 2 (SO 4 ) 3

3
−3
5.72 × 10 mol Al 2 (SO 4 ) 3 1000 mL
× = 6.02 × 10 −3 M Al 2 (SO 4 ) 3
950.0 mL L