SS 50 CHAPTER 15: SUPPLEMENTARY SOLUTIONS

ELECTRODES AND POTENTIOMETRY

S15-1. (a) -0.419 V (b) 0.720 V (c) -0.479 V (d) -0.009 V (e) 0.009 V

S15-2. Br2(aq) + 2e- = 2Br- E+̊ = 1.098 V

0.059 16 [Br-]2 0.059 16 [0.234]2
E+ = E+̊ - log = 1.098 - log
2 [Br2(aq)] 2 [0.002 17] = 1.057 V
E = E+ - E- = 1.057 - 0.241 = 0.816 V
1
S15-3. Ve = 25.0 mL. Ag + + e- = Ag(s) ⇒ E+ = 0.799 - 0.059 16 log
[Ag+ ]

0.1 mL: [SCN -] =  24.9  (0.100 M)  50.0  = 0.099 4 M

 25.0   50.1 
123 123 123
Fraction Original Dilution
remaining concentration factor

[Ag+] = K sp/[SCN-] = (1.1 × 10-12)/0.099 4 = 1.1 × 10-11 M

1
E = E+ - E- = { 0.799 - 0.059 16 log } - 0.241 = -0.090 V
1.1 × 10 -11
15.0 50.0
10.0 mL: [SCN -] =  25.0  (0.100 M)  60.0  = 0.050 0 M
   
+ -
[Ag ] = K sp/[SCN ] = (1.1 × 10 )/0.050 0 = 2.2 × 10-11 M
-12
1
E = E+ - E- = { 0.799 - 0.059 16 log } - 0.241 = -0.073 V
2.2 × 10 -11
25.0 mL: [Ag+] = [SCN -] ⇒ [Ag+] = Ksp = 1.1 × 10 -12 = 1.05 × 10-6 M
1
E = E+ - E- = { 0.799 - 0.059 16 log } - 0.241 = 0.204 V
1.0 5 × 10 -6
5.0
30.0 mL: This is 5.0 mL past Ve ⇒ [Ag+] =  80.0  (0.200 M) = 0.012 5 M
 
1
E = E+ - E- = { 0.799 - 0.059 16 log 0.012 5 } - 0.241 = 0.445 V

S15-4. (a) Ag+ (right) + e- = Ag E+̊ = 0.799 V

- Ag+ (left) + e- = Ag E-̊ = 0.799 V
Ag+ (right) = Ag+ (left) E˚ = 0

[Ag+ (left)]
E = -0.059 16 log
[Ag+ (right)]
(b) NH 3: Ve = 9.8 mL ⇒ NH 3/Ag+ = 1.99 ⇒ 2NH 3 + Ag+ = (NH 3)2Ag+
H2NCH 2CH2NH 2: Ve = 5.0 mL ⇒ H2NCH 2CH2NH 2/Ag+ = 1.15
⇒ H2NCH 2CH2NH 2 + Ag+ = (H2NCH 2CH2NH 2)Ag+
 Chapter 15: Supplementary Solutions SS 51

(c) At the equivalence point, E = -0.15 V and [Ag+ (left)] = 0.100 M.

0.100
-0.15 = -0.059 16 log ⇒ [Ag+ (right)] ≈ 0.03 M
[Ag+ (right)]

S15-5. right half-reaction : Zn2+ + 2e- = Zn(s) E˚ = -0.762 V

 0.059 16 1 
E =  -0.762 - log  - 0.241
 2 [Zn2+ ] 

MgY2- : Kf = 6.2 × 108; ZnY2- : Kf = 3.2 × 1016.

4 50
When 10 mL of EDTA has been added, [Mg2+ ] =  5 (0.100)  60
   
1 50
= 0.066 7 M and [MgY2-] =  5 (0.100)  60 = 0.016 7 M.
   
[MgY2-]
But = 6.2 × 108 ⇒ [Y4-] = 4.04 × 10-10 M.
[Mg2+ ][Y4-]
The concentration of [ZnY2-] is (50/60)(1.00 × 10-5) = 8.33 × 10-6 M.
[ZnY2-]
Because = 3.2 × 1016 and we know [Y4-] and [ZnY2-], we can
[Zn2+ ][Y4-]
compute that [Zn2+ ] = 6.44 × 10-13 M.
0.059 16 1
E = -0.762 - 
log - 0.241 = -1.364 V
 2 6.44 × 10 
-13

S15-6. Relative mobilities:

H+ → 36.30 Cl- → 7.91
4.01 ← Li+ 8.13 ← Br-
Anion diffusion from each side is nearly equal, while H+ diffuses much faster than
Li+ . Positive charge builds on the right, so the left side will be negative.

S15-7. Velocity = mobility × field = (20.50 × 10-8 m2/(s. V)) × (1000 V/m)
= 2.05 × 10-4 m s-1 for OH-
and (5.70 × 10-8)(1000) = 5.70 × 10-5 m s-1 for F-.
To cover 0.010 0 m will require (0.010 0 m)/(2.05 × 10-4 m s-1) = 48.8 s for OH-
and (0.010 0)/(5.70 × 10-5) = 175 s for NO3-.
0.059 16
S15-8. (a) E = constant + β log ALa3+ (outside).
3

(b) If the activity increases by a factor of 10, the potential will increase by
0.059 16/3 = 19.7 mV.
 SS 52 Chapter 15: Supplementary Solutions

0.059 16
(c) E1 = constant + (1.00) log (2.36 × 10-4)
3
0.059 16
E2 = constant + (1.00) log (4.44 × 10-3)
3
0.059 16 4.44 × 10 -3
∆E = E2 - E1 = log = +25.1 mV
3 2.36 × 10 -4
0.059 16 1 1/1
(d) E = constant + log { [La3+ ] + 1200 [Fe3+ ] }
3
0.059 16
0.100 = constant + log (1.00 × 10-4) ⇒ constant = 0.1789 mV
3
0.059 16 1
E = 0.178 9 + log { (1.00 × 10-4) + 1200 (0.010)} = +100.7 mV
3
[ML] 0.050
[M](0.50) ⇒ [M] = 2.8 × 10 M
S15-9. = 3.6 × 1010 = -12
[M][L]

S15-10. For the pure [Ca2+ ] solution we can write

(0.970)(0.059 16)
E = constant + log (1.00 × 10-3)
2
Putting in E = 0.300 0 V gives constant = 0.386 1 V. For the solution containing
the interfering ions we can say that
(0.970)(0.059 16)
E = 0.386 1 + log { (1.00 × 10-3) + (0.040)(1.00 × 10-3)
2
+ (0.021)(1.00 × 10-3) + (0.081)(5.00 × 10-4)} = 0.301 2 V

At equal concentrations, Zn2+ interferes the most.

0.057 1
S15-11. 0.194 6 = constant + log { [M2+ ]o + 0.020 0 (0.020 0)}
2
After making the standard addition, the concentration of M2+ is
100.0 [M 2+ ]o + 1.00 (0.030 7)
= (0.9901 [M2+ ]o + 3.040 × 10-4) M
101.0
0.057 1
0.200 7 = constant + log{ (0.9901 [M2+ ]o + 3.040 × 10-4) + 0.020 0 (0.020 0)}
2
0.057 1
= constant + log{ 0.990 1 [M2+ ]o + 7.040 × 10-4}
2
0.057 1 (0.9901 [M 2+ ]o + 7.04 0 × 10 -4)
∆E = (0.200 7 - 0.194 6) = log
2 [M2+ ]o + 4 . 0 0 × 10 -4
⇒ [M2+ ]o = 7.7 × 10-5 M
 Chapter 15: Supplementary Solutions SS 53

S15-12. For Mg(EDTA)2- , Kf = 6.2 × 108. This solution contains 30% more EDTA than
Mg2+ . Therefore [EDTA]/[Mg(EDTA)2-] = 0.30
[Mg(EDTA)2-]
= α Y4- Kf = 0.36 Kf
[Mg2+ ][EDTA]
[Mg(EDTA)2-] 1
[Mg2+ ] = = (0.30)(0.36)K = 1.49 × 10-8 M
[EDTA]α Y4- K f f

For Mn(EDTA)2- , Kf = 7.4 × 1013 and [Mn2+ ] = 1.25 × 10-13 M

S15-13. pH = -logAH+ = -log[H+]γH+ ⇒ γH+ = 10-pH / [H+ ]

At µ 0, we know γH+ = 1

µ (M) pH γH+ µ (M) pH γH+

0.10 2.13 0.74 1.60 1.96 1.10
0.30 2.16 0.69 1.80 1.92 1.20
0.50 2.16 0.69 2.00 1.86 1.38
1.00 2.09 0.81 2.40 1.76 1.74
1.20 2.05 0.89 2.50 1.73 1.86
1.50 1.99 1.02 3.00 1.59 2.57

2.50
Activity coefficient

2.00

1.50

1.00

0.50
0.00 1.00 2.00 3.00
µ (M)
 SS 54 CHAPTER 16: SUPPLEMENTARY SOLUTIONS
REDOX TITRATIONS

S16-1. (a) 2Cu2+ + In+ → 2Cu+ + In3+

(b) Cu2+ + e- = Cu+ E˚ = 0.161 V
-
In3+ + 2e = In+ E˚ = -0.444 V
[Cu+ ]
(c) E = { 0.161 - 0.059 16 log } - {0.241 } (A)
[Cu2+ ]
0.059 16 [In+ ]
E = { -0.444 - log } - {0.241 } (B)
2 [In3+ ]
(d) 1.00 mL : Use Equation B with [In+ ]/[In3+ ] = 39.0/1.00, since
Ve = 40.0 mL ⇒ E = -0.732 V
20.0 mL : [In+ ]/[In3+ ] = 20.0/20.0 ⇒ E = -0.685 V
39.0 mL : [In+ ]/[In3+ ] = 1.0/39.0 ⇒ E = -0.638 V
40.0 mL : This is Ve, where [Cu + ] = 2[In3+ ] and [Cu2+ ] = 2[In+ ].
Adding the two Nernst equations gives
[Cu+ ]
E+ = 0.161 - 0.059 16 log
[Cu2+ ]
[In+ ]
2E+ = -0.888 - 0.059 16 log 3+
[In ]
[In+ ][Cu+ ]
3E+ = -0.727 - 0.059 16 log
[In3+ ][Cu2+ ]
[In+ ]2[In3+ ]
3E+ = -0.727 - 0.059 16 log 3+
[In ]2[In+ ]
⇒ E+ = -0.242 V and E = -0.483 V.
41.0 mL : Use Equation A with [Cu+ ]/[Cu2+ ] = 40.0/1.0 ⇒ E = -0.175 V
80.0 mL : [Cu+ ]/[Cu2+ ] = 40.0/40.0 ⇒ E = -0.080 V

S16-2. (a) Fe3+ + Cu+ → Fe2+ + Cu2+

(b) Fe3+ + e- = Fe2+ E˚ = 0.771 V

Cu2+ + e- = Cu+ E˚ = 0.161 V
2+
(c) E = {0.771 - 0.059 16 log [Fe 3+
[Fe ]
]
} - {0.197 } (A)
+
[Cu ]
E = {0.161 - 0.059 16 log [Cu 2+ ] } - { 0.197 } (B)

(d) 1.0 mL : Use Equation A with [Fe2+ ]/[Fe3+ ] = 1.0/24.0, since

Ve = 25.0 mL ⇒ E = 0.656 V
12.5 mL : [Fe2+ ]/[Fe3+ ] = 12.5/12.5 ⇒ E = 0.574 V
24.5 mL : [Fe2+ ]/[Fe3+ ] = 24.5/0.5 ⇒ E = 0.474 V
 Chapter 16: Supplementary Solutions SS 55

25.0 mL : This is Ve, where [Cu 2+ ] = [Fe2+ ] and [Cu+ ] = [Fe3].

Adding the two Nernst equations gives
[Fe2+ ]
E+ = 0.771 - 0.059 16 log
[Fe3+ ]
[Cu+ ]
E+ = 0.161 - 0.059 16 log
[Cu2+ ]
[Fe2+ ][Cu+ ]
2E+ = 0.932 - 0.059 16 log
[Fe3+ ][Cu2+ ]
[Fe2+ ][Fe3+ ]
2E+ = 0.932 - 0.059 16 log
[Fe3+ ][Fe2+ ]
⇒ E+ = 0.466 V and E = 0.269 V.
25.5 mL : Use Equation B with [Cu+ ]/[Cu2+ ] = 0.5/25.0 ⇒ E = 0.065 V
30.0 mL : [Cu+ ]/[Cu2+ ] = 5.0/25.0 ⇒ E = 0.005 V

S16-3. Titration reactions:

V2+ + Ce4+ → V3+ + Ce3+
V3+ + Ce4+ + H 2O → VO2+ + Ce3+ + 2H +
VO2+ + Ce4+ + H 2O → VO+2 + Ce3+ + 2H +
[V2+ ]
-------
At 5.0 mL: E+ = -0.255 - 0.059 16 log 3+ ⇒ E = -0.496 V
[V ]
-------
[V3+ ]
-------
At 15.0 mL: E+ = 0.337 - 0.059 16 log ⇒ E = 0.096 V
[VO ](1.00)2
2+
---------
[VO2+ ]
---------
At 25.0 mL: E+ = 1.001 - 0.059 16 log ⇒ E = 0.760 V
[VO+2 ](1.00)2
--------
[Ce3+ ] 30.0
At 35.0 mL: E+ = 1.70 - 0.059 16 log = 1.70 - 0.059 16 log  5.0 
[Ce4+ ]  
⇒ E = 1.41 V

1.6
Potential (V versus S.C.E.)

1.2

0.8

0.4

-0.4

0 10 20 30
V Ce 4+ (mL)
 SS 56 Chapter 16: Supplementary Solutions

S16-4. 3MnO-4 + 5Mo3+ + 4H + → 3Mn2+ + 5MoO22+ + 2H 2O

(22.11 - 0.07) = 22.04 mL of 0.012 34 M KMnO 4 = 0.272 0 mmol of MnO-4
which will react with (5/3)(0.272 0) = 0.453 3 mmol of Mo3+ .
[Mo3+ ] = 0.453 3 mmol/50.00 mL = 9.066 mM.

S16-5. 2MnO-4 + 5H 2C2O4 + 6H + → 2Mn2+ + 10CO2 + 8H 2O

12.34 mL of 0.004 321 M KMnO4 = 0.053 32 mmol of MnO-4 which reacts with
(5/2)(0.053 32) = 0.133 3 mmol of H2C2O4 which came from (2/3)(0.133 3) =
0.088 87 mmol of La3+ . [La3+ ] = 0.088 87 mmol/25.00 mL = 3.555 mM.

S16-6. C3H8O3 + 3H 2O = 3HCO2H + 8e- + 8H +

glycerolformic acid
(average oxidation (oxidation number
number of C = -2/3) of C = +2)

8Ce4+ + 8e- = 8Ce3+

C3H8O3 + 8Ce4+ + 3H 2O = 3HCO2H + 8Ce3+ + 8H +
One mole of glycerol requires eight moles of Ce4+ .

50.0 mL of 0.089 9 M Ce4+ = 4.495 mmol

10.05 mL of 0.043 7 M Fe2+ = 0.439 mmol
Ce4+ reacting with glycerol = 4.056 mmol
glycerol = (1/8) (4.056) = 0.507 0 mmol = 46.7 mg ⇒ original solution = 30.5
wt % glycerol

S16-7.
NO + 4H+ + 4e - = NH 2 + H2 O

NO 2 + 6H+ + 6e - = NH 2 + 2H 2 O

One mole of nitrosobenzene reacts with 4 moles of Cr2+ and one mole of
nitrobenzene reacts with 6 moles of Cr2+ . Let x = mg of C6H5NO and
24.43 - x = mg of C 6H5NO2. We can write
4x 6(24.43 - x)
+ = mmol of Cr2+ = (21.57)(0.050 00)
107.112 123.111
x = 9.84 mg = 40.3%

S16-8. 0.139 2 g of KBrO3 = 0.833 5 mmol of BrO3- which generates 3(0.833 5) =

2.501 mmol of Br2 according to the reaction
BrO3- + 5Br- + 6H + → 3Br2 + 3H 2O
One mole of excess Br2 generates one mole of I2 by the reaction
 Chapter 16: Supplementary Solutions SS 57

Br2 + 2I- → 2Br- + I2

The I2 requires 19.18 mL of 0.050 00 M S2O2- 2-

3 = 0.959 0 mmol of S2O 3 .
Therefore there must have been (1/2)(0.959 0) = 0.479 5 mmol of I2 =
0.479 5 mmol of excess Br2. The Br2 that reacted with acetoacetanilide must have
been 2.501 - 0.479 5 = 2.021 mmol of Br 2. Since one mole of Br2 reacts with
one mole of acetoacetanilide there must have been 2.021 mmol of acetoacetanilide,
or (1/2)(2.021) = 1.010 mmol of Be 2+ = 9.107 mg of Be.

S16-9. Denote the average oxidation number of Bi as 3+b and the average oxidation
number of Cu as 2+c.
Bi3+b 2+ 2+ 3+ 2+c
2 Sr 2 Ca0.8 Y0.2 Cu 2 Ox
Positive charge = 6 + 2b +4 + 1.6 + 0.6 + 4 + 2c = 16.2 + 2b + 2c
The charge must be balanced by O2- ⇒ x = 8.1 + b + c
The formula weight of the superconductor is 760.37 + 15.999 4(8.1+b+c).
One gram contains 1/[770.14 + 15.999 4(8.1+b+c)] moles.

Experiment A: Initial Cu+ = 0.100 0 mmol; final Cu+ = 0.052 2 mmol. Therefore
110.6 mg of superconductor consumed 0.047 8 mmol Cu+ .
2× mmol Bi5+ + mmol Cu3+ in 110.6 mg superconductor = 0.047 8.

Experiment B: Initial Fe2+ = 0.050 0 mmol; final Fe2+ = 0.021 3 mmol.

Therefore 143.9 mg of superconductor consumed 0.028 7 mmol Fe2+ .
2 × mmol Bi5+ in 143.9 mg superconductor = 0.028 7.
Normalizing to 1 gram of superconductor gives
Expt A: 2( mmol Bi5+ ) + mmol Cu3+ in 1 g superconductor = 0.432 2
Expt B: 2(mmol Bi5+ ) in 1 g superconductor = 0.199 4

It is easier not to get lost in the arithmetic if we suppose that the oxidized bismuth is
Bi4+ and equate one mole of Bi5+ to two moles of Bi4+ . Therefore we can rewrite
the two equations above as
mmol Bi4+ + mmol Cu3+ in 1 g superconductor = 0.433 2 (1)
mmol Bi4+ in 1 g superconductor = 0.199 4 (2)
Subtracting Equation 2 from Equation 1 gives
mmol Cu3+ in 1 g superconductor = 0.233 8 (3)

Equations 2 and 3 tell us that the stoichiometric relationship in the formula of the
superconductor is b/c = 0.199 4/0.233 8 = 0.852 9.
Since 1 g of superconductor contains 0.789 4 mmol Cu3+ , we can say
mol Cu 3+
mol solid = 2c
 SS 58 Chapter 16: Supplementary Solutions

mol Cu 3+ / mol solid 2c

=
gram solid / mol solid 760.37+15.999 4(8.1+b+c)
mol Cu 3+ 2c
gram solid = 770.14+15.999 4(8.1+b+c) = 2.338 × 10
-4 (4)

Substituting b = 0.852 9c in the denominator of Equation 4 allows us to solve for c:

2c
770.14 + 15.999 4(8.1+1.852 9c) = 2.338 × 10 ⇒ c = 0.105 5
-4

⇒ b = 0.852 9c = 0.0900

The average oxidation numbers are Bi+3.090 0 and Cu+2.105 5 and the formula of the
compound is Bi2Sr2Ca0.8 Y0.2 Cu2O8.295 5 , since the oxygen stoichiometry derived
at the beginning of the solution is x = 8.1 + b + c.

S16-10. Coefficients of the balanced equations are :

(a) 1 , 1 → 1 (f) 1 , 1 → 1 , 1 , 1

(b) 2 , 1 , 2 → 1 , 2 , 5 (g) 1 , 1 → 2 , 1 , 2

(c) 1 , 24 , 24 → 6 , 6 , 42 , 48 , 1 (h) 1 , 5 , 6 → 3 , 3

(d) 1 , 1 , 1 → 1 , 1 (i) 1 , 2 , 1 → 1 , 1 , 1

(e) 3 , 1 , 3 → 1 , 6 , 6

One mole of Be3+ requires 228 moles of thiosulfate.

CH=O
S16-11. (a)
H C OH
5HCO2 H
HO C H
→ +
H C OH
H2 C=O
H C OH
CH2 OH
To balance this reaction we can write
C6H12O6 + 5H 2O = C6H12O11 + 10H + + 10e-
glucose 5HCO2 H+H 2 CO
5[IO4 + 2H + 2e = IO-3 + H 2O]
- + -

5IO-4 + C6H12O6 → 5HCO2H + H 2CO + 5IO-3

Chapter 16: Supplementary Solutions SS 59

CHO
(b)
H C NH 2
5HCO2 H
HO C H
→ + + NH 3
H C OH
H2 C=O
H C OH
CH2 OH

C6H13O5N + 6H 2O = C6H15O11N + 10H + + 10e-

5HCO2 H+H 2 CO+NH3

5[IO4+ 2H + + 2e = IO-3 + H 2O]
- -

C6H13O5N + H 2O + 5IO-4 → 5HCO2H + H 2CO + NH3 + 5IO-3

(c) H2 C OH H2 C=O
+
O=C → HO2 C
H2 C OH H2 COH
C3H6O3 + H 2O = C3H6O4 + 2H + + 2e-

HCO+C2 H4 O3
IO4 + 2H + + 2e = IO-3 + H 2O
- -

C3H6O3 + IO-4 → H2CO + HO2CCH2OH + IO-3

 SS60 CHAPTER 17: SUPPLEMENTARY SOLUTIONS
ELECTROGRAVIMETRIC AND COULOMETRIC ANALYSIS

C C
S17-1. (0.100 mol) 96 485 mol = I . (3 600 s) ⇒ I = 2.680 s = 2.680 A
 

S17-2. (a) E(cathode) = -0.828 - 0.059 16 log(0.033)1/2(1.0) = -0.7842 V

E(anode) = 1.078 - 0.059 16 log (0.010) = 1.1963 V
(Note that E(anode) is calculated for a reduction half-reaction.)
-ENernst = E(cathode) - E(anode) = -1.981 V
(b) Ohmic potential = I. R = (0.052 A)(4.3 Ω) = 0.224 V
Eelectrolysis = -ENernst - IR = -2.205

(c) Eelectrolysis = -ENernst - IR - overpotentials = -1.981 - 0.224 - 0.30 - 0.08 =

-2.585 V

(d) concentration polarization changes the electrode potentials:

E(cathode) = -0.828 - 0.059 16 log (0.033)1/2(2.0) = -0.8020
E(anode) = 1.078 - 0.059 16 log (0.002 0) = 1.2377
-ENernst = -0.8020 -1.2377 = -2.040 V
Eelectrolysis = -2.040 - 0.22 - 0.30 - 0.08 = -2.64 V

S17-3. (a) Let us assume that the left electrode is the anode:
cathode: 12 Cl2 (g) + e- = Cl- E˚ = 1.360 V
anode: 12 Hg2Cl2 (s) + e- = Hg(l) + Cl- E˚ = 0.268 V
[Cl-] 0.080
E(cathode) = 1.360 - 0.059 16 log = 1.360 - 0.059 16 log = 1.395 V
PCl 2 0.10
E(anode) = 0.241 V (saturated calomel electrode.)
ENernst = E(cathode) - E(anode) = 1.395 - 0.241 = 1.154 V
Since ENernst is positive, we guessed the direction of the reaction correctly.
The net reaction is 12 Cl2(g) + Hg(l) + Cl- = Cl- + 12 Hg2Cl2 (s)

(b) Egalvanic = ENernst - I. R = 1.154 - (0.025 A)(2.12 Ω) = 1.101 V

(c) Eelectrolysis = -ENernst - I. R = -1.154 - (0.025 A)(2.12 Ω) = -1.207 V

0.040
(d) E(cathode) = 1.360 - 0.059 16 log = 1.422 V
0.20
-ENernst = E(cathode) - E(anode) = 1.422 - 0.241 = 1.181 V
Eelectrolysis = -ENernst - I. R = -1.181 - (0.025 A)(2.12 Ω) = -1.234 V

(e) Eelectrolysis = -1.234 - 0.15 = -1.38 V

 Chapter 17: Supplementary Solutions SS 61

S17-4. For oxidation of Pb2+ , the oxidation half-reaction is

Pb2+ + 2H 2O = PbO2 + 4H + + 2e- E˚ = -1.458 V
and the oxidation electrode potential is
0.059 16 [2.00]4
E = -1.458 - log
2 [0.005 00] = -1.562 V
For oxidation of H2O, the oxidation half reaction is
H2O = 12 O2 + 2H + + 2e- E˚ = -1.229 V
and the oxidation electrode potential is
0.059 16
E = -1.229 - log [1.00] 1/2[2.00]4 = -1.265 V
2
(assuming that the partial pressure of O2 is 1 atm). The potential for the oxidation
of water is more positive than the potential for oxidation of Pb2+ , so we expect
water to be preferentially oxidized. If it is not, the reason is probably that the
overpotential for oxidation of water (liberation of O2) is greater than the
overpotential for oxidation of Pb2+ .

S17-5. Pb(tartrate) + 2H2O → PbO2(s) + tartrate2- + 4H + + 2e-

Pb 2+ Pb 4+
Oxidation occurs at the anode.
The mass of Pb (tartrate) (FW 355.3) giving 0.122 1 g of PbO2 (FW = 239.2)
is (355.3/239.2)(0.122 1 g) = 0.181 4 g.
0.181 4
% Pb = 0.531 4 × 100 = 34.13%

S17-6. (a) Fe2+ + e- = Fe(s) E˚ = -0.44 V

1
E(cathode) = -0.44 - 0.059 16 log = -0.854 V
1.0 × 10 -7

(b) E(cathode, vs Ag | AgCl) = -0.854 - 0.197 = -1.05 V

(c) Concentration polarization means that Fe2+ cannot diffuse to the cathode as fast
as it is consumed. The concentration of Fe2+ at the electrode surface would be
< 0.10 µM, so the potential would be more negative.

S17-7. When 99% of Hg(II) is reduced, the formal concentration will be 1.0 × 10-5 M, and
the predominant form is Hg(NH3)2+4.
[Hg(NH3)2+
4 ] = (1.0 × 10 -5) ⇒ [Hg 2+ ] = 5 × 10-25 M
β4 =
[Hg2+ ][NH 3]4 [Hg2+ ](1.0)4
Hg2+ + 2e- = Hg(l) E˚ = 0.852
0.059 16 1
E(cathode) = 0.852 - log = 0.133 V
2 5 × 10 -25
 SS 62 Chapter 17: Supplementary Solutions

S17-8. Relevant information :

Fe2+ + 2e- = Fe(s) E˚ = -0.44 V
Co2+ + 2e- = Co(s) E˚ = -0.282 V
CoY2- Kf = 2.0 × 1016
FeY2- Kf = 2.1 × 1014
α Y4- = 3.8 × 10-9 at pH 4.0

When 99% of FeY2- is removed, [FeY2-] = 1.0 × 10-8 M.

[FeY2-] 1.0 × 10 -8
[Fe2+ ] = = = 1.3 × 10-12
Kf α Y4- [EDTA] (2.1 × 10 14 )(3.8 × 10 -9)(0.010)

The cathode potential required to reduce FeY2- to this level is

0.059 16 1
E(cathode) = -0.44 - log = -0.79 V
2 1.3 × 10 -12
Will this cathode potential reduce Co2+ ?
[CoY2-]
α Y4- Kf (for CoY2-) = ⇒ [Co2+ ] = 1.3 × 10-8 M
[Co2+ ][EDTA]
0.059 16 1
E(cathode, Co2+ ) = -0.282 - log = -0.515 V
2 1.3 × 10 -8

Since E(cathode) < -0.515 V, CoY2- will be reduced. The separation is not feasible.

I. t (4.11 × 10 -3 C/s)(834 s)
S17-9. (a) mol e- = F = = 3.55 × 10-5 mol
96 485 C/mol

(b) One mol e- reacts with 12 mol Br2, which reacts with 12 mol cyclohexene ⇒
1.78 × 10-5 mol cyclohexene.

(c) 1.78 × 10-5 mol/3.00 × 10-3 L = 5.92 × 10-3 M

2.03 mg Ti/47.88 mg/mmol µmol Ti

S17-10. Step 1: Total Ti = = 1.00 0
42.37 mg unknown mg unknown
9.27 C/96 485 C/mol 1.87 µmol
Step 2: Reducing equivalents of Ti = 51.36 mg unknown = mg unknown

1.87 µmol/mg unknown

Reducing equivalents per mol of Ti = 1.00 µmol Ti/mg unknown

= 1.87 equivalents/mol Ti

This represents the degree of reduction below Ti4+ .

The average oxidation state is Ti+2.13 (= 0.87 TiCl2 + 0.13 TiCl3)
 CHAPTER 18: SUPPLEMENTARY SOLUTIONS SS 63
VOLTAMMETRY

S18-1. Slope = 11.91 standard deviation = 0.12

intercept = -0.012 standard deviation = 0.017
σy = 0.033 = standard deviation of current
The concentration of Al3+ , when Id = 0.904 µA, is found as follows :
I(mA) = m[Al3+ ] + b
I-b
[Al3+ ] = m
[0.904 (±0.033)] - [-0.012 (±0.017)]
[Al3+ ] = 11.91 (±0.12)
0.916 (±0.037 1)] 0.916 (±4.05%)
[Al3+ ] = =
11.91 (±0.12) 11.91 (±1.01%)
[Al3+ ] = 0.076 9 (±4.17%) = 0.076 9 ±0.003 2 mM
Equation 4-24 gives an uncertainty of ±0.002 9 mM
[X]i IX
S18-2. [S]f + [X] f = IS+X
x(ppm) 152 nA
= 206 nA ⇒ x = 0.760 ppm
0.500 3.00
2.65  3.50  + x  3.50 
   

S18-3. Use the internal standard equation with X = DDT and S = chloroform. From the
standard mixture we find the response factor, F:
signalX  signalS  1.00  1.40 
[X] = F  [S]  ⇒ [1.00 mM] = F  [1.00 mM] ⇒ F = 0.7143

For the unknown mixture, we can say

signalX  signalS  ⇒ 1.00 = 0.7143  0.86 
= F
[X]  [S]  [DDT]  [0.500 mM]
⇒ [DDT] = 0.81 mM

S18-4. If the conditions were perfectly reproducible, the diffusion current for Tl+ in
experiment B would be (1.21/1.15)(6.38) = 6.71 µA. The observed current in
experiment B is only 6.11/6.71 = 91.1% of the expected value. That is, in
experiment B the response is only 91.1% as great as in experiment A. Therefore,
the responses to Cd2+ and Zn2+ in experiment B are expected to be only 91.1% as
great as they are in experiment A
(4.76/6.48)
[Cd2+ ] = (1.02) = 0.82 mM
0.911
(8.54/6.93)
[Zn2+ ] = (1.23) = 1.66 mM
0.911
 SS 64 Chapter 18: Supplementary Solutions

S18-5. The graph of current vs. scan rate gives a straight line with an intercept reasonably
near zero. The analyte is confined to the electrode surface. Otherwise, the graph of
current vs. scan rate would give the better straight line.
4

scan
3 rate
Peak current (µA)

1
1/2
(scan rate)

0
0.0 0.1 0.2 0.3 0.4 0.5 0.6
Scan rate (V/s) or (scan rate) 1/2

S18-6. (a) Slope = +0.049 V = 0.059(q-p) ⇒ q-p ≈ +1. That is, the oxidized species
has one more imidazole ligand than the reduced species. The chemistry is either
ML+ + L + e- → ML2 or M+ + L + e- → ML.
Intercept = 0.029V = E 1free ox red
/ 2 - 0.059 log (β p /β q ).
Putting in E 1free ox red
/ 2 = -0.18 V gives log (β p /β q ) = -3.5.
(b) Since the slope is zero, the reaction is either ML+2 + e- → ML2 or
ML+ + e- → ML. It cannot be M+ + e- → M because the product has one
fewer ligand at lower free ligand concentration (-3.4 < log [L] < -2.1), and the
product cannot have a negative number of ligands.
The reaction sequence in parts (a) and (b) has been interpreted as
(a) ML+ + L + e- → ML2 (b) ML+2 + e- → ML2

S18-7. The end point (0.675 mL) in the figure below is where the linear current increase
extrapolates back to zero. Two moles of NH3 require 3 moles of OBr-
(30.0 mL)(4.43 × 10 -5 mmol/mL)
[OBr-] = (3/2) = 2.95 mM.
0.675 mL
 Chapter 18: Supplementary Solutions SS 65

10

Current (µA)
6

2 End point

0
0.0 0.2 0.4 0.6 0.8
OBr - (mL)

S18-8. 34.61 mL of methanol with 4.163 mg of H2O/mL contains 144.08 mg H2O =

7.997 8 mmol of H2O. The titration of "dry" methanol tells us that 25.00 mL of
methanol reacts with 3.18 mL of reagent. Therefore, 34.61 mL of methanol will
react with (34.61/25.00)(3.18) = 4.40 mL of Karl Fischer reagent. The titer of
the reagent is
7.997 8 mmol H 2O mmol H 2O
(25.00 - 4.40) mL reagent = 0.388 24 mL reagent
Reagent needed to react with 1.000 g of salt in 25.00 mL of methanol = (38.12 -
3.18) = 34.94 mL. H2O in 1.000 g of salt = (0.388 24)(34.94) = 13.565 mmol =
244.38 mg of H2O = 24.44 wt % of the crystal.
 SS 66 Chapter 18: Supplementary Solutions

S18-9. Spreadsheet for weighted least squares

A B C D E F G H I J
1 n x y std dev weight(w) w*x*y w*x w*y w*x^2 w*d^2
2 1 1.00E-04 6995 112 8E-05 6E-05 8E-09 6E-01 8E-13 6E-02
3 2 5.00E-05 3510 74 2E-04 3E-05 9E-09 6E-01 5E-13 1E-01
4 3 1.00E-05 698 11 8E-03 6E-05 8E-08 6E+00 8E-13 2E-02
5 4 5.00E-06 345 18 3E-03 5E-06 2E-08 1E+00 8E-14 3E-02
6 5 1.00E-06 64.4 3.9 7E-02 4E-06 7E-08 4E+00 7E-14 2E+00
7 6 5.00E-07 32.4 1.8 3E-01 5E-06 2E-07 1E+01 8E-14 1E+00
8 7 1.00E-07 6.88 0.64 2E+00 2E-06 2E-07 2E+01 2E-14 2E-01
9 8 5.00E-08 3.17 0.32 1E+01 2E-06 5E-07 3E+01 2E-14 2E-02
10 9 2.00E-08 1.03 0.2 3E+01 5E-07 5E-07 3E+01 1E-14 8E-04
11 n=
12 9
13 1.667E-4 11656 4E+01 2E-04 2E-06 1E+02 2E-12 3E+00
14 |<---------------------------------Column sums (B-J)---------------------------------->|
15 D= sigma(y)= Example: E13 = Sum(E2:E10)
16 8.623E-11 6.93E-01
17 m= sigma(m)= E2 = 1/D2^2 H2 = E2*C2
18 6.967E+07 4.58E+05 F2 = E2*B2*C2 I2 = E2*B2*B2
19 b= sigma(b)= G2 = E2*B2 J2 = E2*(C2-$A$18*B2-$A$20)^2
20 -3.578E-01 1.15E-01
21
22 D = E13*I13-G13*G13 sigma(y) = Sqrt(J13/(A12-2))
23 m = (E13*F13-G13*H13)/A16 sigma(m) = B16*Sqrt(E13/A16)
24 b = (H13*I13-G13*F13)/A16 sigma(b) = B16*Sqrt(I13/A16)

Unweighted parameters: Weighted parameters:

m = 7.002 (±0.005) × 107 m = 6.967 (±0.046) × 107
b = -1.5 (±1.9) b = -0.36 (±0.12)
sy = 5.0 sy = 0.693

S18-10. (a) A = 0.97 ± 0.95 B = 1.385 ± 0.027 C = -0.001 23 ± 0.000 14 sy = 0.919

200
(b)

160
Current (µA)

120

80

40

0
0 20 40 60 80 100 120 140 160
Concentration (µg/mL)
 Chapter 18: Supplementary Solutions SS 67

(c) Current = A + B[α-tocopherol] + C[α-tocopherol]2

170 = 0.967 + 1.385 [α-tocopherol] - 0.001 23 [α-tocopherol]2
⇒ [α-tocopherol] = 139.3 µg/mL
171 = 0.967 + 1.385 [α-tocopherol] - 0.001 23 [α-tocopherol]2
⇒ [α-tocopherol] = 140.2 µg/mL
169 = 0.967 + 1.385 [α-tocopherol] - 0.001 23 [α-tocopherol]2
⇒ [α-tocopherol] = 138.3 µg/mL
Answer: [α-tocopherol] = 139 ± 1 µg/mL

S18-11. To find the unknown concentration, we set up a proportionality:

[Pb2+ ]unknown (stripping time)unknown
= (stripping time)
[Pb ]unknown + [Pb 2+ ]standard
2+ unknown + standard

[Pb2+ ]unknown 4.8 s

2+ = 8.8 s
[Pb ]unknown + 0.5 µg/L
⇒ [Pb2+ ]unknown = 0.6 µg/L = 2.9 × 10-9 M
[Cu2+ ]unknown (stripping time)unknown
S18-12. 2+ 2+ = (stripping time)
[Cu ]unknown + [Cu ]standard unknown + standard

[Cu2+ ]unknown 8.6 s

=
[Cu2+ ]unknown + 0.5 µg/L 13.4 s
⇒ [Cu2+ ]unknown = 0.90 µg/L = 1.4 × 10-8 M

S18-13.
12

10

8
Time (s)

0.53 µg/L
6

0
-0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0
Concentration (µg/L)

[Cd2+ ]unknown (stripping time)unknown

S18-14. 2+ 2+ = (stripping time)
[Cd ]unknown + [Cd ]standard unknown + standard

[Cd2+ ]unknown 1.0 s

= 3.7 s ⇒ [Cd2+ ]unknown = 0.19 µg/L = 1.6 × 10-9 M
[Cd ]unknown + 0.5 µg/L
2+
 SS 68 Chapter 18: Supplementary Solutions

S18-15. The equation of the straight line is time (s) = 8.00 [Cu2+ ] (µg/L) + 8.57
The x-intercept gives the concentration in the unknown = 1.07 µg/L

S18-16. The initial solution has a high concentration of Fe2+ and a low concentration of
Fe3+ , so the current is low. As titrant is added, Fe2+ is converted to Fe3+ and the
Fe3+ | Fe2+ redox couple carries maximum current near the middle of the titration.
As we approach the equivalence point, there is a high concentration of Fe3+ and
little Fe2+ , so the current decreases (to near zero at the equivalence point). After the
equivalence point, excess Ce4+ is added to the pot containing Ce3+ from the
titration reaction. The current increases again as the Ce4+ | Ce3+ couple reacts at the
two electrodes.

S18-17. (a) The initial solution contains H3AsO3 and Br-, neither of which can support a
substantial current between two Pt electrodes. Only a small residual current is
expected. As BrO3- is added, it is converted to Br2 and then to Br- by reaction
with H3AsO3. Since the H3AsO4 | H3AsO3 does not conduct current, the
current remains small. After the equivalence point, when both Br2 and Br- are
present, substantial current flows by virtue of oxidation of Br- at one electrode
and reduction of Br2 at the other.. The expected titration curve is level near zero
current until the end point, and then it increases steadily.

(b) Initially there is no easy mechanism for carrying current, so the voltage will be
high. As I2 is added, it is converted to I- and H3AsO3 is oxidized to H3AsO4.
Since the H3AsO3 | H3AsO4 couple does not carry current (as stated in part a),
the voltage remains high. Only after the end point, when both I2 and I- are
present, does the voltage drop to near zero. The titration curve is expected to
look like the one in Demonstration 18-1.
 CHAPTER 19: SUPPLEMENTARY SOLUTIONS SS 69
FUNDAMENTALS OF SPECTROPHOTOMETRY

S19-1. Using ν = c/λ , ν̃ = 1/λ, and E = hν , we find

250 nm 10 µm
ν (hz) 1.20 × 1015 3.00 × 1013
~
ν (cm-1) 4.00 × 104 1 000
J/photon 7.95 × 10-19 1.99 × 10-20
kJ/mol 479 12.0

15.0 × 10 -3 g
S19-2. (a) = 7.80 × 10-3 M
(384.63 g/mol)(5 × 10 -3 L)
(b) One tenth dilution ⇒ 7.80 × 10-4 M

(c) ε = A/bc = 0.634/[(0.500 cm)(7.80 × 10-4 M )] = 1.63 × 103 M -1 cm-1

(0.267 g) / (337.69 g/mol)
S19-3. Original concentration = = 7.91 × 10-3 M
(0.100 0 L)
2.000
Diluted concentration =  100.0  (7.91 × 10-3 M ) = 1.58 × 10-4 M
 
A 0.728
ε = bc = = 2.30 × 103 M -1 cm-1
(1.58 × 10 -4 M )(2.00 cm)

S19-4. A = -log T = 0.085 1 for T = 82.2% and 0.295 for T = 50.7%.

Ratio = 0.085 1/0.295 = 0.288.
A 0.494 - 0.053
S19-5. (a) ε = cb = = 1.182 × 10-4 M -1 cm-1
(3.73 × 10 -5 M )(1.000 cm)

A 0.777 - 0.053
(b) c = = = 6.125 × 10-5 M
εb (1.182 × 10 4 M -1 cm -1)(1.000 cm)
250.0
Original concentration was 5.00 times as great = 3.06 mM

S19-6. (a) The concentration of phosphorus in solution A is 1.196 × 10-3 M . When 0.140
mL of A is diluted to 5.00 mL, [P] = 3.349 × 10-5 M .
ε = A/bc = (0.829 - 0.017)/[(1.00 cm)(3.349 × 10-5 M )] =
2.42 5 × 104 M -1 cm-1.
A (0.836 - 0.038)
(b) [P] in analyte = = = 3.291 × 10-5 M
εb (2.425 × 10 4 M -1 cm -1)(1.00 cm)
5.00
[P] in 1.00 mL of undiluted analyte =  0.300  (3.291 × 10-5 M )
 
= 5.485 × 10-4 M .
1.00 mL contains 5.485 × 10-7 mol P = 1.699 × 10-5 g = 1.26% phosphorus.
 SS 70 Chapter 19: Supplementary Solutions

S19-7. If self absorption is negligible, Equation F reduces to I = k'P 0(1 - 10-εexb2c). At

low concentration, this expression reduces to I = k'P 0(eexb2c ln 10) (using the first
term of a power series expansion). As the concentration increases, the second
expression becomes greater than the first expression. When the first expression is
5% below the second, we can say
k'P0(1 - 10-εexb2c) = 0.95 k'P0(eexb2c ln 10)
or 1 - 10-A = 0.95 A ln 10
By trial and error, this equation can be solved to find that when A = 0.045, 1 - 10-A
= 0.95 A ln 10. (Alternatively, you could make a graph of 1 - 10-A versus A and
0.95 A ln 10 versus A. The solution is the intersection of the two curves.)

S19-8. Move the cell diagonally toward the upper right hand side, so that only the lower left
corner is illuminated. Then b1 = 0 and b3 is minimized.

S19-9. C(M) I (multiples of k'P o) C I

10-7 0.000 070 4 10-4 0.055 8
10-6 0.000 703 10-3 0.069 9
10-5 0.006 88 10-2 2.54 × 10-9

S19-10. Spreadsheet for florescence intensity with self quenching

A B C
1 E(excitation) = Concentration Relative Intensity
2 2120 0.0000001 1.95E-04
3 E(emission) = 0.000001 1.95E-03
4 810 0.00001 1.89E-02
5 b1 = 0.0001 1.40E-01
6 0.3 0.001 7.81E-02
7 b2 = 0.01 3.89E-11
8 0.4
9 b3 =
10 0.5
 CHAPTER 20: SUPPLEMENTARY SOLUTIONS SS 71
APPLICATIONS OF SPECTROPHOTOMETRY

S20-1. Using Equations 20-7 and setting b = 0.100 cm, we find

0.282 387
| 0.303 642 | (0.282)(642) - (387)(0.303)
[X] = 1 640 387 = (1 640)(642) - (387)(399) = 7.10 × 10-5 M
| 399 642 |
1 640 0.282
| 399 0.303 |
[Y] = 1 640 387 = 4.28 × 10-4 M
| 399 642 |
 12 200 3 210 290 
S20-2. Coefficient matrix:  4 140 6 550 990 
 3 000 2 780 8 080 

 0.846 
Constant vector:  0.400 
 0.555 

 [X]   6.47 × 10 -5 
Solution vector:  [Y]  =  1.42 × 10 -5 
 [Z]   3.98 × 10 -5 

S20-3. We can use the spreadsheet from the previous problem if we divide the absorbances
by 2 to change from a 2.000-cm cell to a 1.000-cm cell. Putting in absorbances of
0.333, 0.249 and 0.180 gives [X] = 2.086 × 10-5 M, [Y] = 2.387 × 10-5, and [Z] =
6.317 × 10-6 M.

S20-4. A graph of ∆A/[X] versus ∆A is a scattered straight line with a slope of -1.401 5
and an intercept of 5.943 2.
intercept 5.943 2
K = -slope = 1.40. ∆ε = -1 -1
KP 0 = 1.40 × 0.001 00 = 4 240 M cm

[X] (M) ∆A ∆A/[X]

0 0 ---
0.005 09 0.030 5.894
0.008 52 0.050 5.869
0.017 3 0.100 5.780
0.029 5 0.170 5.763
0.038 7 0.220 5.685
0.050 9 0.280 5.501
0.065 0 0.350 5.385
0.077 9 0.420 5.392
0.093 2 0.490 5.258
0.106 2 0.550 5.179
 SS 72 Chapter 20: Supplementary Solutions

S20-5. For Zn2+ , the maximum absorbance occurs at a mole fraction of metal of 0.33,
indicating formation of a 2:1 ligand:metal complex. For Ga3+ , the maximum
absorbance at a mole fraction of 0.25, indicates formation of a 3:1 ligand:metal
complex.

c 2.997 9 × 10 8 m/s
S20-6. 340 nm: E = hν = h = (6.626 1 × 10-34 J. s) = 5.84 × 10-19 J
λ 340 × 10 -9 m
To convert to J/mol, multiply by Avogadro's number:
5.84 × 10-19 J/molecule × 6.022 × 1023 molecules/mol = 352 kJ/mol.
2.997 9 × 10 8 m/s
613 nm: E = (6.626 1 × 10-34 J. s) = 3.24 × 10-19 J
613 × 10 -9 m
kJ
= 195 mol .

The difference between the irradiation energy and the fluorescence energy is
352 - 195 = 157 kJ/mol.

S20-7. (a) The equation for intensity can be solved for K, giving
[S] (1-I s/Is+x )
K = I /I
s s+x - [S]/([S] + [X])
Putting in Is/Is+x = 58.7/74.5, [S] = 250 µM and [X] = 200 µM
gives K = 228 µM.

(b) Solving the intensity equation for [X] gives

K[S]
[X] = (I /I )(K + [S]) - [S] - [S]
s s+x
Using the values Is/Is+x = 63.5/74.6, [S] = 250 + 200
= 450 µM and K = 228 µM gives [X] = 357 µM.
 CHAPTER 21 SUPPLEMENTARY SOLUTIONS SS 73
SPECTROPHOTOMETERS

S21-1. T + a + R = 0.70 + a + 0.08 = 1 ⇒ a = 0.22

S21-2. P2/P1 = e-αb = e-(1.40 cm-1 )(0.200 cm) = 0.756

1 - n 2 1 - 1.62 2
S21-3. (a) R =  1 + n  =  1 + 1.62  = 0.056 0
   
1 - R
T = 1 + R = 0.894 (independent of thickness if absorption = 0)

(1-R)2 e-αb (1-0.056 0)2 e-(0.85 cm-1 )(0.500 cm)

(b) T = = = 0.583
1-R2 e-2αb 1-0.056 02 e-2(0.85 cm-1 )(0.500 cm)

S21-4. (a) The critical angle, θ c, is such that (n1/n2)sin θ c = 1. For n1 = 2.7 and n 2 =
2.0, θ c = 48°. That is θ must be ≥ 48° for total internal reflection.
power out
(b) power in = 10-” (dB/m) / 10 = 10-(0.50 m)(0.012 0 dB/m)/10 = 0.998 6

S21-5. At 13 µm the slope dn/dλ is greater for NaCl than for KBr. Therefore a NaCl
prism will have greater dispersion than a KBr prism.

S21-6. n1 sin θ 1 = n2 sin θ 2, where n 1 = 1.46 and n 2 = 1.63

(a) If θ 1 = 30˚, θ 2 = 26.6˚
(b) If θ 1 = 0˚, θ 2 = 0˚ (no refraction)

nprism sin α
S21-7. (a) For incident light: nair sin θ = nprism sin α ⇒ sin θ = nair
n sin α
For exiting light: nprism sin α = nair sin θ ⇒ sin θ = prismn
air
Therefore entrance and exit angles are the same.
(b) α = 30˚ if light is parallel to the prism base.
(1.500) sin 30˚
Therefore sin θ = ⇒ θ = 48.59˚
1.000

exitance at 900 K 4
S21-8. Since exitance is proportional to T4, =  900 = 81
exitance at 300 K  300
W W
Exitance at 900 K =  5.669 8 × 10 -8 2 4 (900 K)4 = 3.72 × 104 2
 mK  m

S21-9. (a) The mass of a 1-cm length of the cylinder is: (volume) (density) =
πr2(length)(7.89 g/cm3) = π(0.32 cm)2(1 cm)(7.86 g/cm3) = 2.53 g
The surface area of the 1-cm length of cylinder is π(diameter)(length)
= π(0.64 cm)(1 cm) = 2.0 1 cm2
 SS 74 Chapter 21: Supplementary Solutions

W W
Exitance from iron =  5.669 8 × 10 -8 2 4 (1 373 K)4 = 2.01 × 105 2
 mK  m
W
Exitance from surroundings into iron =  5.669 8 × 10 -8 2 4 (300 K)4
 mK 
W
= 459 2
m
W W
Net energy loss from iron = (2.01 × 105 - 459 2 ) = 2.01 × 105 2
m m
W J
= 20.1 2 = 20.1 . 2
cm s cm
J 
Energy loss rate (J/s) =  exitance  2
2  [surface area (cm )]
  s cm
J
=  20. 1 . 2  (2.01 cm2) = 40.4 J/s
 s cm 
J 
Heat capacity of 1-cm length is [mass (g)]  heat capacity  =
  K
g
J
(2.53 g)  0.606 .  = 1.53 J/K
 g K
energy loss rate 40. 4 J/s
Cooling rate = heat capacity = 1.5 3 J/K = 26 K/s

(b) The ratio of surface area/volume is 10 times greater so the cooling rate is also
10 times greater = 260˚C/s.

S21-10. (a) nλ = d(sin θ - sin φ)

1 . 400 × 10-9 m = d(sin 20˚ - sin 10˚) ⇒ d = 2.38 × 10-6 m
Lines/cm = 1/(2.38 × 10-4 cm) = 4.21 × 103 lines/cm
(b) λ = 1/(1 000 cm-1) = 10-3 cm ⇒ d = 5.94 × 10-3 cm ⇒ 168 lines/cm

λ 443.531
S21-11. (a) Resolution = = 0.072 = 6.2 × 103
∆λ

For λ = 443.495 nm, ~

ν = 1/λ = 2.254 82 × 106 m-1 = 2.254 82 × 104 cm-1.

For λ = 443.567 nm, ~

ν = 2.254 45 × 104 cm-1 Difference = 3.7 cm-1.

For λ = 443.495 nm, ν = c/λ = 6.759 77 × 1014 Hz.

For λ = 443.567 nm, ν = 6.758 67 × 1014 Hz Difference = 1.10 × 1011 Hz.

λ 443.495
(b) ∆λ = 4 = = 0.04 nm
10 104

(c) Resolution = nN = (2)(6.00 cm × 2 120 cm-1) = 2.54 × 104

 Chapter 21: Supplementary Solutions SS 75

(d) 200 lines/mm = 5 µm/line = d

∆φ 2 1 radians
= = (5 µm) cos 10° = 0.406 µm = 23.3°/µm
∆λ d cos φ
For ∆λ = 0.072 nm, ∆φ = (23.3°/µm)(7.2 × 10-5 µm) = 1.7 × 10-3 degrees
For 20th order diffraction, the dispersion will be 10 times greater, or 0.017°.

S21-12. True transmittance = 10-1.26 = 0.055. With 0.4% stray light, the apparent
transmittance is 0.055 + 0.004 = 0.059. The apparent absorbance is
- log 0.059 = 1.23.

S21-13. (a) ∆ = ±4 cm
(b) Resolution ≈ 1/∆ = 0.25 cm -1
(c) δ = 1/(2∆ν) = 1/(2 . 4 000 cm-1) = 1.25 µm

S21-14. To increase the ratio from 3/1 to 9/1 ( a factor of 9/3 = 3) requires 32 = 9 scans.

S21-15. 60

y = 4.08x + 9.3
50
Detector signal

40

30

20 2.3 nM

10

0
-4 -2 0 2 4 6 8 10 12
Concentration (nM)
 CHAPTER 22: SUPPLEMENTARY SOLUTIONS SS 76
ATOMIC SPECTROSCOPY

S22-1. The Doppler linewidth is given by

∆λ = λ (7 × 10-7) T/M
= 0.0013 nm for Fe at 3 000 K (with λ = 248 nm and M = 56)
= 0.0018 nm for Fe at 6 000 K (with λ = 248 nm and M = 56)
= 0.000 7 nm for Hg at 3 000 K (with λ = 254 nm and M = 201)
= 0.0010 nm for Hg at 6 000 K (with λ = 254 nm and M = 201)

hc (6.626 1 × 10 -34 J . s)(2.997 9 × 10 8 m/s)

S22-2. (a) ∆E = hν = =
λ 327 × 10 -9 m

= 6.07 × 10-19 J/molecule = 366 kJ/mol

N* g*
(b) N = g e-∆E/kT = 3e-(6.07 × 10 -19 J)/(1.381 × 10 -23 J/K)(2 400K) = 3.29 × 10-8
o o

(c) At 2 415 K, N*/No = 3.69 × 10-8 ⇒ 12% increase from 2 400 to 2 415 K

(d) At 6 000 K, N*/No = 0.002 0

S22-3. Sensitivity = concentration of Mo giving A = 0.004 36 (= 99% T)

[Mo] giving A = 0.004 36 0.004 36
=
[Mo] giving A = 0.025 0.025
x 0.004 36
= 0.025 ⇒ x = 4.1 µg/mL
23.6 µg/mL

S22-4. (a) µg/mL A422.7 /A324.7

1.00 0.6056
2.00 0.6062 average = 0.6019
3.00 0.5913
4.00 0.6045
(b) Standard mixture has equal concentrations of Ca and Cu:
ACa  ACu  ⇒ 0.6019 = F  1.000  ⇒ F = 0.6019
= F
[Ca]  [Cu] [Ca
---]  [Cu
---] 
Unknown mixture:
ACa  ACu  ⇒ 0.218 = 0.6019  0.269 
= F
[Ca]  [Cu] [Ca]  [2.47 µg/mL] 
⇒ [Ca] = 3.33 µg/mL
 Chapter 22: Supplementary Solutions SS 77

S22-5. (a) The graph below shows the quadratic fit to the calibration data.
400
y = - 0.17902 + 51.258x
- 1.3562x^2
300

Signal
200

100

0
0 2 4 6 8 10
Analyte concentration (µg/mL)

(b) 344.0 = -0.179 02 + 51.258x -1.356 2x2 ⇒ x = 8.73 µg/mL

(by solving quadratic equation and using the root that lies on this graph)
346.2 = -0.179 02 + 51.258x -1.356 2x2 ⇒ x = 8.81 µg/mL
341.8 = -0.179 02 + 51.258x -1.356 2x2 ⇒ x = 8.65 µg/mL
Concentration of unknown = 8.73 ± 0.08 µg/mL

S22-6. Emission is observed only if the narrow laser excitation frequency overlaps the
even narrower atomic absorption line. The laser bandwidth is narrow enough to
excite Mn without exciting Ga.
 CHAPTER 23: SUPPLEMENTARY SOLUTIONS SS 78
INTRODUCTION TO ANALYTICAL SEPARATIONS

V
S23-1. (a) Fraction remaining = V + 1KV
1 2
100
0.005 = 100 + (610)V ⇒ V2 = 32.6 mL
2
4
100
(b) 0.005 =  100 + (610)V  ⇒ V2 = 0.453 mL. 4 × V2 = 1.81 mL
 2

[HA]ether + [A -]ether [HA]ether

S23-2. (a) D ≡ - ≈
[HA]aq + [A ]aq [HA]aq + [A -]aq
[HA]
K ≡ [HA]ether
aq
K . [H + ] 92 . 10 -4.00
(b) D = = = 17.7
[H+ ] + K a 10-4.00 + 4 . 2 × 10 -4

(c) At pH 3.50, more of the acid will be in the form HA, which is the extractable
species. Therefore the distribution coefficient will be greater than at pH 4.00.
92 . [H + ]
(d) 1 = ⇒ [H+ ] = 4.62 × 10-6 M ⇒ pH = 5.34
[H+ ] + 4 . 2 × 10 -4

S22-3. (a) t'r = 13.81 - 1.06 = 12.75 min. k' = 12.75/1.06 = 12.03
5.55 t r2 5.55 (13.81) 2
(b) w1/2 = 0.172 min ⇒ N = 2 = = 3.58 × 104 plates
w1/2 0.172 2
16 t r2 16 (13.81) 2
(c) w = 0.302 min ⇒ N = = = 3.35 × 104 plates
w2 0.302 2

(d) H = (30.0 × 103 mm)/(3.35 × 104 plates) = 0.896 mm

(e) Volume of 30.0 m of column = πr2 × length = π(0.026 2 cm)2 × 3 000 cm
= 6.47 mL.
Volume flow rate = (6.47 mL) / (1.06 min) = 6.10 mL/min

16 t r2 16 (12.83 min) 2
S23-4. (a) N = = = 2.80 × 104 plates
w2 (0.307 min)2

(b) H = (158 mm)/(2.80 × 104 plates) = 5.64 µm

S23-5. (a) Volume of mobile phase per cm of column = (0.426)πr2 × (1 cm) =

(0.426)π(0.960 cm)2 × (1 cm) = 1.23 mL
Linear flow rate = (2.22 mL/min) / (1.23 mL/cm) = 1.80 cm/min

(b) tm = (50.6 cm) / 1.80 cm/min) = 28.1 1 min

 Chapter 23: Supplementary Solutions SS 79

t - t t - 28.11
k' = r t m ⇒ 8.04 = r 28.11 ⇒ tr = 254 min
m

S23-6. α = (k'2) / (k'1) = 1.02; k'2 = 5.10; k'av = 5.05

N α-1  k'2 
Resolution = 4  
 α   1 + kav
'

N 1.02 - 1   5.10 
1.00 = 4   ⇒ N = 5.86 × 104 plates
 1.02   1 + 5.05 

(5.86 × 104 plates)(155 µm/ plate) = 9.08 m

To double the resolution requires four times as many plates = 36.3 m.

S23-7. (a) Heptane: t'r = 14.56 - 1.06 = 13.50 min. k' = 13.50/1.06 = 12.74

C6H4F2: t'r = 14.77 - 1.06 = 13.71 min. k' = 13.71/1.06 = 12.93

(b) α = 12.93/12.74 = 1.015

(c) w1/2 (heptane) = 0.126 min; w1/2 (C6H4F2) = 0.119 min

5.55 t r2 5.55 (14.56) 2
N = 2 = = 7.41 × 104 plates for heptane
w1/2 0.126 2
5.55 (14.77) 2
N = = 8.55 × 104 plates for C6H4F2
0.119 2

(d) w (heptane) = 0.216 min; w (C6H4F2) = 0.196 min

16 t r2 16 (14.56) 2
N = = = 7.27 × 104 plates for heptane
w2 0.216 2
16 (14.77) 2
N = = 9.09 × 104 plates for C6H4F2
0.196 2
∆t 14.77 - 14.56
(e) Resolution = w r = = 1.019
av 0.206

(f) N = (7.27 × 10 4)(9.09 × 10 4) = 8.13 × 104 plates

N α-1  k'2 
Resolution = 4  
 α   1 + kav
'

8.13 × 10 4  1.015-1  12.93 

= = 0.984
4  1.015   1 + 12.84 
t k't
(g) Fraction of time in stationary phase = t +s t = k't +m t =
s m m m
k' 12.74
k' + 1 = 12.74 + 1 = 0.927
 SS 80 Chapter 23: Supplementary Solutions

2
Large load  large column radius 
S23-8. =
Small load  small column radius
2
72.4 mg  3.00 cm  ⇒ diameter = 1.11 cm
=
10.0 mg  small column diameter

Use the same concentration ⇒ volume = 10.0 (0.500 mL) = 0.069 1 mL

72.4

dc m2 mol
S23-9. Flux = -D dx = - 2.0 × 10 -9 s   -3.4 . 
  L cm

m2 100 cm 2 mol 0.001 L  mol/s

=  2.0 × 10 -9 s   m   3.4 .   = 6.80 × 10-8
    L cm  cm 
3 cm2
ions/s
= 4.09 × 1016
cm2

In 5.5 s, 2.3 × 1017 ions will cross each square centimeter.

 CHAPTER 24: SUPPLEMENTARY SOLUTIONS SS 81
GAS CHROMATOGRAPHY

S24-1. [ log(6.45) - log(6.12)

I = 100 6 + (7 - 6) log(7.20) - log(6.12) ] = 632

S24-2. (a) hexane < benzene < heptane < nitropropane < pyridine < octane < nonane

(b) hexane < heptane < benzene < octane < pyridine < nitropropane < nonane

(c) hexane < heptane < octane < nonane < benzene < pyridine < nitropropane

18.5 - 14.3
S24-3. TZ = 0.5 + 0.5 - 1 = 3.2
 SS 82 CHAPTER 25: SUPPLEMENTARY SOLUTIONS
LIQUID CHROMATOGRAPHY

AreaC  AreaD 4.42  5.52 

[C] = F  [D]  ⇒ [236] = F  [337]
S25-1. ⇒ F = 1.143

The concentration of internal standard (D) mixed with unknown (C) is

1 230 µg/25.00 mL = 49.2 0 µg/mL

3.33  2.22 
[C] = 1.143  [49.20] ⇒ [C] = 64.57 µg/mL
25.00
[C] in original unknown = 10.00 (64.57 µg/mL) = 161 µg/mL

S25-2. The more polar the solvent, the greater the eluent strength on a polar column, and
the shorter the retention time. Since 60 vol % acetonitrile is less polar than 40 vol
% acetonitrile, the retention time will be greater for the 60 vol % eluent.

t - t t - 1.33
S25-3. k' = r t m ⇒ 3.50 = r 1.33 ⇒ tr = 5.99 min
m
Number of plates = N = (0.150 m)/(10.6 × 10-6 m/plate) = 1.42 × 104
t 2 5.99 2
N = 5.55  w r  ⇒ 1.42 × 104 = 5.55  w  ⇒ w1/2 = 0.118 min
 1/2  1/2

Raise the temperature to get the same separation efficiency at a faster linear flow
rate, as in Figure 23-17.
 CHAPTER 26: SUPPLEMENTARY SOLUTIONS SS 83
CHROMATOGRAPHIC METHODS AND CAPILLARY ELECTROPHORESIS

S26-1. Vt = πr2l = π(1.27 cm)2(28.4 cm) = 143.9 mL

V - V 98.6 - 43.4
Kav = Vr - V 0 = 143.8 - 43.4 = 0.550
t 0

S26-2. The calibration curve follows the equation log (MW) = 12.590 - 0.607 6 t. For t =
13.00 min, MW = 4.9 × 104.

7
y = 12.590 - 0.6076x
6
log (MW)

3
9 10 11 12 13 14 15
Elution time (min)

S26-3. Observed current - extrapolated current = 0.05(extrapolated current)

(3V + 0.01V2 + 0.000 2V3) - (3V) = (0.05)3V ⇒ V = 12.08 kV

S26-4. The 13-cis isomer is a slightly more compact molecule, and ought to have a smaller
effective hydrodynamic radius.

unet L / t 0.82 m / 408 s 2

S26-5. (a) µ app = E = Vd/ L = = 7.6 × 10 -8 m
t 25.4 × 10 3 V / 0.96 m s. V
κ
(b) Moles injected = µ app  E b tπr2C
 κs 
m2 5.0 × 103 V mol
=  7.6 × 10 -8 .   0.96 m  (2)(3.0 s)(π)(25× 10-6 m)2 2.4 × 10-3 3 
 s V    m 
= 11 fmol

S26-6. For the acid HA, the charge is α A-, where α is the fraction of dissociation:
KA
α A- = +
[H ] + K A
Let's designate acetic acid as HA and formic acid as HF with acid dissociation
constant KF . The difference in charge between the two acids is
KA KF
∆ = α A- - α F - = -
[H+ ] + K A [H+ ] + K F
 SS 84 Chapter 26: Supplementary Solutions

We are seeking the maximum D, for which d∆/d[H+ ] = 0:

d∆ -KA KF
+ = 0 = + 2 +
d[H ] ([H ] + K A) ([H ] + K F )2
+

KA([H+ ] + K F )2 = K F ([H+ ] + K A)2

KA[H+ ]2 + 2K AKF [H+ ] + K AKF 2 = K F [H+ ]2 + 2K AKF [H+ ] + K F KA2
(KA - KF )[H+ ]2 = K F KA2 - KAKF 2
(KA - KF )[H+ ]2 = K F KA(KA - KF ) ⇒ [H+ ] = KF KA
Inserting the values KA = 1.75 × 10-5 and KF = 1.80 × 10-4 gives pH = 4.25

S26-7. (a) At pH 12, the mixture contains RCO2- , RNH2, Na+ and OH-. All of these
species pass directly through the cation-exchange column (which is in the Na+
form). There is no retention of any component.
(b) At pH 2, the mixture to be separated contains RCO2H, RNH+3 , H + and Cl-.
The RNH+3 cation will be retained by the column and the other species will be
eluted.
 CHAPTER 27: SUPPLEMENTARY SOLUTIONS SS 85
GRAVIMETRIC AND COMBUSTION ANALYSIS

S27-1. One mole of product (206.243 g) comes from one mole of piperazine (86.137 g).
Grams of piperazine in sample =
(0.793 3 g of piperazine / g of sample) × (0.123 4 g of sample) = 0.097 89 g.
206.243
Mass of product =  86.137  (0.097 89 g) = 0.234 4 g.
 

S27-2. 2.188 g bis(dimethylglyoximate)nickel (II) = 7.573 × 10-3 mol Ni = 0.444 5 g Ni =

39.44% Ni.

1.003 g
S27-3. Mol K+ in unknown = mol K+ B(C6H5)4- = 358.33 g/mol = 2.799 mmol

= 0.109 4 g K = 8.665 wt % K.

16.432 mg
S27-4. (a) mmol C = mmol CO2 = 44.010 mg/mmol = 0.373 37 mmol = 4.484 5 mg C
4.484 5 mg C
8.732 mg unknown × 100 = 51.36 wt % C
2 × 2.840 mg
mmol H = 2 × mmol H2O = 18.015 mg/mmol = 0.315 29 mmol

= 0.317 80 mg H = 3.639 wt % H

(b) Atomic ratio (C:H) = 0.373 37 / 0.315 29 = 1.184

A small integer ratio is 6:5.

S27-5. In step (1) we make 0.726 8 g of lead piperazine dithiocarbamate, which equals
(0.726 8 / 527.77) = 1.377 1 × 10-3 mol of Pb. The PbCl2 in 100.00 mL will be
twice as much, since only 50.00 mL was treated in step (1). Moles of PbCl2 in 100
mL = 2.754 × 10-3 mol.
In step (2), the grams of Pb(IO3)2 formed will be

1
(2.754 × 10-3 mol)(557.0 g/mol) = 0.383 5 g
4
1442443
moles PbCl2

The Cu(IO3)2 from 25.00 mL is 0.838 8 - 0.383 5 = 0.455 3 g.

The moles of Cu in 0.455 3 g of Cu(IO3)2 are (0.455 3/413.35) =
1.101 × 10-3 mol. The moles of Cu in 100.0 mL are 4 (1.101 × 10-3) = 4.404 ×
10-3 mol = 0.279 9 g = 13.99%.

100˚C
S27-6. (a) 2NaHCO3 Na2CO3 + H 2O + CO2
150˚C
2KHCO3 K2CO3 + H 2O + CO2
 SS 86 Chapter 27: Supplementary Solutions

(b) 2 mol NaHCO3 (168.014 g) would produce 1 mol (105.989 g) of Na 2CO3.

105.989
Therefore 50.0 g of NaHCO3 produces 168.014 × 50.0 = 31.5 g Na2CO3,

losing 18.5 g in the process.

2 mol KHCO3 (200.230 g) would produce 1 mol (138.206 g) of K2CO3.
138.206
Therefore 50.0 g of KHCO3 produces 200.230 × 50.0 = 34.5 g K2CO3,

losing 15.5 g in the process.

(c) Starting with 100 mg, the mixture will lose 18.5 mg (18.5 wt %) of its mass
near 100°C and another 15.5 mg (15.5 wt %) at 150°C. There will be a plateau
between 100 and 150 °C at 81.5 wt % (= 100 - 18.5) and a second plateau
above 150°C at 66.0 wt % (= 100 - 15.5 - 18.5).

S27-7. The atomic ratio H:C is

 6.84 ± 0.10 g 
 1.008 g/mol  6.786 ± 0.099 6.786 ± 1.46%
= 5.930 ± 0.091 6 = 5.930 ± 1.54% = 1.144 ± 0.024
 71.22 ± 1.1 g 
 12.011 g/mol 
If we define the stoichiometry coefficient for C to be 8, then the stoichiometry
coefficient for H is 8(1.144 ± 0.024) = 9.15 ± 0.19.
The atomic ratio N:C is

 10.33 ± 0.13 g 
 14.007 g/mol  0.737 5 ± 0.009 3 0.737 5 ± 1.26%
= 5.930 ± 0.091 6 = 5.930 ± 1.54%
 71.22 ± 1.1 g 
 12.011 g/mol 
= 0.124 4 ± 0.002 5
If we define the stoichiometry coefficient for C to be 8, then the stoichiometry
coefficient for N is 8(0.124 4 ± 0.002 5) = 0.995 ± 0.020.
The empirical formula is reasonably expressed as C8H9.15±0.19N0.995±0.020

S27-8. We will use mmol and mg, instead of mol and g, for our calculations. From the
formula weight of YBa2Cu3O7-x, we can say
28.19 mg
mmol of YBa2Cu3O7-x in experiment = (666.19-16.00x) mg/mmol

All mass lost represents loss of oxygen from YBa2Cu3O7-x.

(28.19 - 25.85) mg
mmol of O lost = 16.00 mg/mmol = 0.14625 mmol

From the reaction stoichiometry, we can say

 Chapter 27: Supplementary Solutions SS 87

mmol of O lost 3.5-x

mmol YBa2Cu3O7-x = 1

0.146 25 mmol
------
= 3.5-x
 28.19 mg
--- 
 (666.19-16.00x) mg/mmol
--- -------
This terrible expression can be solved for the dimensionless stoichiometry
coefficient, x, by cross multiplication:
(28.19)
0.146 25 =  (666.19-16.00x) (3.5-x)
 
(0.14625)(666.19-16.00x) = (28.19)(3.5-x)
97.4 30 - 2.3400x = 98.6650 - 28.19x
28.19x - 2.3400x = 98.6650 - 97.430
25.85 00x = 1.2350
x = 0.048
Note that the number 3.5 is exact, since it comes from the stoichiometry.

S27-9. mol Br = mol Ag+ at 1st end point = (0.405 × 10-3 kg)(0.093 84 mol/kg)
= 3.80 × 10-5 mol
mol Cl = mol Ag+ at 2nd end point = (0.787 × 10-3 kg)(0.093 84 mol/kg)
= 7.39 × 10-5 mol
(3.80 × 10 -5 mol)(79.904 g/mol)
wt % Br = × 100 = 35.9%
8.463 x 10 -3 g sample
(7.39 × 10 -5 mol)(35.453 g/mol)
wt % Cl = × 100 = 30.9%
8.463 x 10 -3 g sample
3.80 × 10 -5 mol
Br/Cl atomic ratio = = 0.514
7.39 × 10 -5 mol

S27-10. Balanced combustion equation: CH2O + O2 → CO2 + H 2O

FW 30.026
0.100 g CH2O = 3.330 mmol, requiring 3.330 mmol O2.
This volume of O2 is contained in
nRT (3.330 × 10 -3 mol)(0.082 06 L . atm/mol. K)(298 K)
V = P = = 81.4 mL
1.00 atm
 SS 88 CHAPTER 28: SUPPLEMENTARY SOLUTIONS
SAMPLE PREPARATION

S28-1. Use Equation 28-7 with ss = 0.06 and e = 0.03. The initial value of t for 95%
confidence in Table 4-2 is 1.960. n = t2s2s / e2 = 15.4 For n = 15, there are 14
degrees of freedom, so t ≈ 2.15, which gives n = 18.5. For 17 degrees of
freedom, t ≈ 2.11, which gives n = 17.8. It appears that the calculation will
oscillate near 18 samples. For 90% confidence, the initial t is 1.645 in Table 4-2
and the same series of calculations gives n = 13 samples.

S28-2. (a) Mass (m, g) Standard deviation (R, %) Ks = mR2 (g)

0.54 6.33 21.6
1.78 3.21 18.3
4.22 2.00 16.9
8.63 1.55 20.7
average 19.4
(b) mR2 = K s. For R = 1 and Ks = 19.4 g, we find m = 19.4 g.

(c) Use Equation 28-7 with ss = 0.01 and e = 0.007 5. The initial value of t for
90% confidence in Table 4-2 is 1.645. n = t2s2s / e2 = 4.8 For n = 5, there are
4 degrees of freedom, so t = 2.132, which gives n = 8.1. For 7 degrees of
freedom, t = 1.895, which gives n = 6.4. Continuing, we find t = 2.015
⇒ n = 7.2. This gives t = 1.943 ⇒ n = 6.7. Use 7 samples.

S28-3. (a) Volume = (4/3)πr3, where r = 0.100 mm = 0.010 0 cm.

Volume = 4.189 × 10-6 mL.
Mass of diamond particle = (4.189 × 10-6 mL)(3.51 g/mL) = 1.470 × 10-5 g.
Mass of SiC particle = (4.189 × 10-6 mL)(3.23 g/mL) = 1.353 × 10-5 g.
Number of particles of diamond in 1.00 g of mixture
= (0.870 g)/(1.470 × 10-5 g/particle) = 5.92 × 104.
Number of particles of SiC in 1.00 g of mixture
= (0.130 g)/(1.353 × 10-5 g/particle) = 9.61 × 103.

(b) The fraction of each type of particle is

pdiamond = (5.92 × 104)/(5.92 × 104 + 9.61 × 103) = 0.860
qSiC = (9.61 × 103)/(5.92 × 104 + 9.61 × 103) = 0.140.
(i) 1.00 g:
Number of particles in 1.00 g is n = 5.92 × 104 + 9.61 × 103 = 6.88 × 104.
Expected number of diamond particles in 1.00 g is np = 5.92 × 104.
Expected number of SiC particles in 1.00 g is nq = 9.61 × 103.
Sampling standard deviation = npq = (6.88 × 10 4)(0.860)(0.140) = 91.0.
Chapter 28: Supplementary Solutions SS 89

91.0
Relative sampling standard deviation for diamond = = 0.154%
5.92 × 10 4
91.0
Relative sampling standard deviation for SiC = = 0.947 %.
9.61 × 10 3
(ii) 0.100 g:
Number of particles in 0.100 g is n = 5.92 × 103 + 9.61 × 102 = 6.88 × 103.
Expected number of diamond particles in 0.100 g is np = 5.92 × 103.
Expected number of SiC particles in 0.100 g is nq = 9.61 × 102.
Sampling standard deviation = npq = (6.88 × 10 3)(0.860)(0.140) = 28.8.
28.8
Relative sampling standard deviation for diamond = = 0.486%
5.92 × 10 3
28.8
Relative sampling standard deviation for SiC = = 3.00 %.
9.61 × 10 2