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Fundamentals of Analytical Chemistry: 8th ed.

Chapter 30

Chapter 30

30-1 A masking agent is a complexing agent that reacts selectively with one or more

components of a solution to prevent them from interfering in an analysis.

30-2 Transport of material and spatial redistribution of the components.

30-3 Precipitation, extraction, distillation, ion exchange.

30-4 Strong acid type exchangers have sulfonic acid groups (-SO3-H+)attached to the polymeric

matrix and have wider application than weak acid type exchangers, which owe their action to

carboxylic acid (-COOH) groups.

30-5 (a) Elution is a process in which species are washed through a chromatographic column

by additions of fresh mobile phase.

(b) The mobile phase in chromatography is the one that moves over or through an

immobilized phase that is fixed in place in a column or on the surface of a flat plate.

(c) The stationary phase is chromatography is a solid or liquid phase that is fixed in

place. The mobile phase then passes over or through the stationary phase.

(d) The partition ratio in chromatography is the ratio of the concentration of the analyte

in the stationary phase to its concentration in the mobile phase.

(e) The retention time for an analyte is the time interval between its injection onto a

column and its appearance at the detector at the other end of the column.

(f) The retention factor k is defined by the equation k = KAVS / VM where KA is the

partition ratio for the species A and VS and VM are the volumes of the stationary and

mobile phases, respectively.


Fundamentals of Analytical Chemistry: 8th ed. Chapter 30

(g) The selectivity factor  of a column toward two species is given by the equation  =

KB/KA, where KB is the distribution constant for the more strongly retained species B and

KA is the constant for the less strongly held or more rapidly eluting species A.

(h) The plate height, H, of a chromatographic is defined by the relationship H = 2 / L

where 2 is the variance obtained from the Gaussian shaped chromatographic peak and L

is the length of the column packing in centimeters.

30-6 The variables that lead to zone broadening include: (1) large particle diameters for

stationary phases; (2) large column diameters; (3) high temperatures (important only in

gas chromatography); (4) for liquid stationary phases, thick layers of the immobilized

liquid; and (5) very rapid or very slow flow rates.

30-7 In gas-liquid chromatography, the mobile phase is a gas, whereas in liquid-liquid

chromatography, it is a liquid.

30-8 In liquid-liquid chromatography, the stationary phase is a liquid which is immobilized by

adsorption or chemical bonding to a solid surface. The equilibria that cause separation

are distribution equilibria between two immiscible liquid phases. In liquid-solid

chromatography, the stationary phase is a solid surface and the equilibria involved are

adsorption equilibria.

30-9 Determine the retention time tR for a solute and the width of the solute peak at its base, W.

The number of plates N is then N = 16(tR/W)2.

30-10 Two general methods for improving the resolution of a column are to increase the column

length and to reduce the plate height.


Fundamentals of Analytical Chemistry: 8th ed. Chapter 30

i
 Vaq 
30-11 [A]i    [A]0

 Vorg K  Vaq 

 50.0 
(a) [A ]i    0.150 = 0.0173 M
 40 .0  9 . 6  50 . 0 

2
 50.0 
  0.150  = 6.4010 M
-3
(b) [ A ]i  
 20. 0  9 . 6  50. 0 

4
 50.0 
(c) [A]i     0.150  = 2.0610-3 M
 10.0  9.6  50.0 

8
 50.0 
(d) [A ]i     0.150 = 6.8910-4 M
 5.0  9.6  50.0 

 25.0 
30-12 (a) [A ]i    0.0600 = 8.2810-3 M
 25.0  6. 25  25.0 

% Z = 8.2810-3  100% / 0.0600 = 13.8%

2
 25.0 
(b) [ A]i     0.0600 = 3.5310-3 M
 12. 5  6 . 25  25. 0 

% Z = 3.5310-3  100% / 0.0600 = 5.88%

5
 25.0 
(c) [ A]i     0.0600  = 1.0410-3 M
 5.00  6.25  25.0 

% Z = 1.0410-3  100% / 0.0600 = 1.73%


Fundamentals of Analytical Chemistry: 8th ed. Chapter 30

10
 25.0 
(d) [ A ]i     0.0600 = 4.6710-4 M
 2 . 50  6 . 25  25. 0 

% Z = 4.6710-4  100% / 0.0600 = 0.78%

log  A i /  A 0 
 Vaq 
i
i
30-13 [A]i    [A]0  Vaq 
 Vorg K  Vaq
 log 
 V K V 
 org aq 

 1.00  10 4 
log 
 0.0500 
(a) i  = 2.8  3 extractions
 25.0 
log 
 25.0(9.6)  25.0 

3 extractions requires 3  25.0 = 75.0 mL of n-hexane

(b) As in part (a): i = 3.9  4 extractions

4 extractions requires 4  10.0 = 40.0 mL of n-hexane

(c) As in part (a): i = 10.9  11 extractions

11 extractions requires 11  2.0 = 22.0 mL of n-hexane

 1.00  10 5 
log 
 0.0200 
30-14 (a) i  = 3.5  4 extractions
 40.0 
log 
 50.0(6.25)  40.0 

4 extractions requires 4  50.0 = 200.0 mL of n-hexane

(b) As in part (a): i = 4.8  5 extractions

5 extractions requires 5  25.0 = 125.0 mL of n-hexane


Fundamentals of Analytical Chemistry: 8th ed. Chapter 30

(c) As in part (a): i = 8.1  9 extractions

9 extractions requires 9  10.0 = 90.0 mL of n-hexane

30-15 If 99% of the solute is removed then 1% of solute remains and [A]i / [A]0 = 0.01

2
[ A ]i  50.0 
(a) 0.01 =  
[ A ] 0  25.0 K  50.0 

(0.01)1/2(25.0K + 50.0) = 50.0

2.5K + 5.0 = 50.0

K = (50.0 – 5.0)/2.5 = 18.0

5
[ A ]i  50.0 
(b) 0.01 =  
[ A]0  10.0 K  50.0 

(0.01)1/5(10.0K + 50.0) = 50.0

3.98K + 19.9 = 50.0

K = (50.0 – 19.9)/3.98 = 7.56

30-16 If 1.0010-4 % of the solute remains, [A]i / [A]0 = 1.0010-6

4
[ A ]i  30.0 
-6
(a) 110 =  
[ A ]0  10.0 K  30.0 

(110-6)1/4(10.0K + 30.0) = 30.0

0.316K + 0.949 = 30.0

K = (30.0 – 0.949)/0.316 = 91.9

4
[A]i  30.0 
-5
(b) 110 =  
[ A ]0  10.0 K  30.0 
Fundamentals of Analytical Chemistry: 8th ed. Chapter 30

(110-5)1/4(10.0K + 30.0) = 30.0

0.562K + 1.69 = 30.0

K = (30.0 – 1.69)/0.562 = 50.3

4
[A]i  30.0 
(c) 110 =-4  
[ A ]0  10.0 K  30.0 

(110-4)1/4(10.0K + 30.0) = 30.0

1.00K + 3.00 = 30.0

K = (30.0 – 3.00)/1.00 = 27.0

30-17 (a) Recognizing that in each of the Solutions [HA] = 0.0750 due to dilution, from the

data for solution 1,

[HA]org = 0.0454 M

25.0(0.0750)  25.0(0.0454)
[HA]aq = = 0.0296 M
25.0

K = [HA]org/[HA]aq = 0.0454/0.0296 = 1.53

(b) For solution 3, after extraction

[HA]aq = [HA]org / K = 0.0225 / 1.53 = 0.0147 M

[A-] = (mols HAtot – mols HAaq – mols HAorg)/(25.0 mL)

(25.0)(0.0750)  ( 25.0)(0.0147)  ( 25.0)(0.0225)


[A-] = = 0.0378 M
25.0

(c) Since [H+] = [A-], Ka = (0.0378)2/(0.0147) = 0.0972

30-18 (a) [I2]aq = 1.1210-4 M

[I2]org = (mols I2tot – mols I2aq)/(10.0 mL)


Fundamentals of Analytical Chemistry: 8th ed. Chapter 30

( 25.0)(0.0100)  ( 25.0)(1.12  10 4 )
[I2]org = = 0.0378 M
10.0

[I2]org = 0.0247 M

K = [I2]org / [I2]aq = 0.0247 / (1.1210-4) = 221

(b) after extraction, [I2]aq = [I2]org/K = (1.0210-3)/221 = 4.6210-6 M

[I(SCN)2-] = [I-] = (mmols I2tot – mmols I2aq - mmols I2org)/(25.0 mL)

(25.0)(0.0100)  (25.0)(4.62  10 6 )  (10.0)(1.02  10 3 )


[I(SCN)2-] = [I-] = =
25.0

0.0095874 M

[SCN-] = (mmols SCN-tot - 2mmols I(SCN)2-)/(25.0 mL)

(25.0)(0.100)  2  (25.0)(0.0095874)
[SCN-] = = 0.080825
25.0

[I(SCN) -2 ][I - ]
Kf = = (0.0095874)2/(4.6210-6(0.080825)2) = 3.05103
[I 2 ][SCN - ] 2

30-19 (a) mols H+ resulting from exchange = (0.0153 L)(0.0202 mol/L) = 3.09110-4 mol

mmols H+ = meq cation = 0.3091 in 0.0250 L sample

0.3091 meq cation/0.0250 L = 12.4 meq cation / L

12.4 meq CaCO 3 (100.087 mg/mmol)/( 2 mmol -1 )


(b)  = 619 mg CaCO3 / L
L 1 meq CaCO 3

30-20 (a) mols H3O+ resulting from exchange = (0.0181 L)(0.1006 mol/L)

= 0.001821 mol = eq cation


Fundamentals of Analytical Chemistry: 8th ed. Chapter 30

eq. wt. = (0.393 g acid)/(0.001821 eq.) = 216 g Ba salt / eq.

To obtain the mass of acid per equivalent of acid we subtract the weight of ½ mol Ba and

add the weight of 1 mol H. Thus,

215.8 g Ba salt 137.3 g Ba 1.008 g H


eq. wt. acid =   = 148 g/eq acid
eq. acid 2 eq acid eq. acid

(b) Since two end points are observed in the titration a diprotic acid is indicated. Thus,

FW = 2  148 g/eq. = 296 g/mol

0.1500 mol HCl 1 mol NaCl 58.4425 g NaCl


30-21 2.00 L    = 17.53 g NaCl
L 1 mol HCl mol NaCl

Dissolve 17.53 g of NaCl in about 100 mL water and pass through the column packed

with a cation exchange resin in its acid form. Wash with several hundred milliliters of

water, collecting the liquid from the original solution and washings in a 2.00-L

volumetric flask. Dilute to the mark and mix well.

0.02762 mmol NaOH 1 mmol HCl 1


30-22 [HCl] = 18.96 mL    = 0.02095
mL 1 mmol NaOH 25.00 mL

mmol/mL

mmol H3O+ /mL resulting from exchange = 36.54 mL0.02762 mmol/mL/10.00 mL

= 0.10092 mmol H3O+ /mL = eq cation

mmol MgCl2 /mL = (0.1009 – 0.02095)/2 = 0.039988

Thus, the solution is 0.02095 M in HCl and 0.04000 M in MgCl2.


Fundamentals of Analytical Chemistry: 8th ed. Chapter 30

30-23 (Note: In the first printing of the text, the answer in the back of the book was in error.)

From equation 30-12

1.0 cm 3 /min
 1 min 
2 2
 2 
u0 = F / πr = F / π(d/2) =  0.025 cm   60 s  = 34 cm/s
3.1415   
 2 

30-24 From equation 30-13

50 cm 3 /min  1 min 
2 2
 2 
u0 = F / επr = F / επ(d/2) =  0.50 cm   60 s  = 9.4 cm/s
0.45  3.1415   
 2 
Fundamentals of Analytical Chemistry: 8th ed. Chapter 30

30-25 N = 16(tR / W)2

(a) N N2

A 16(5.4/0.41)2 = 2775 7.7033  106

B 16(13.3/1.07)2 = 2472 6.1110  106

C 16(14.1/1.16)2 = 2364 5.5884  106

D 16(21.6/1.72)2 = 2523 6.3671  106

N = 10135 N 2 = 25.7654  106

(b) N = 10135 / 4 = 2534 = 2.5  103

25.7654  10 6  (10135) 2 / 4
s = = 169 = 0.2  103
4 1

N = 2.5(±0.2)  103

(c) H = 24.7 cm / 2534 plates == 9.747  10-3 = 0.0097 cm

30-26 (a) k = (tR – tM) / tM

For compound A: kA = (5.4 – 3.1)/3.1 = 0.742 = 0.74

For compound B: kB = (13.3 – 3.1)/3.1 = 3.29 = 3.3

For compound C: kC = (14.1 – 3.1)/3.1 = 3.55 = 3.5

For compound D: kD = (21.6 – 3.1)/3.1 = 5.97 = 6.0

(b) K = k VM / VS

For compound A: KA = 0.742  1.37 / 0.164 = 6.2

For compound B: KB = 3.29  1.37 / 0.164 = 27

For compound C: KC = 3.55  1.37 / 0.164 = 30

For compound D: KD = 5.97  1.37 / 0.164 = 50


Fundamentals of Analytical Chemistry: 8th ed. Chapter 30

30-27 (a) RS = 2[(tR)C – (tR)B] / (WB + WC)

RS = 2(14.1 – 13.3) / (1.07 + 1.16) = 0.717 = 0.72

(t R ) C  t M 14.1  3.1
(b) C,B =  = 1.08 = 1.1
(t R ) B  t M 13.3  3.1

( RS )1 N1 0.717 2534
(c)   
( RS ) 2 N2 1 .5 N2

N2 = 2534  (1.5)2 / (0.717)2 = 11090 = 1.11  104

From solution 30-25 (c), H = 9.75  10-3 cm/plate

L = 11090  9.75  10-3 = 108 cm

(t R )1 ( RS )1 14.1 (0.717) 2
(d)   
(t R ) 2 ( RS ) 2 (t R ) 2 (1.5) 2

(tR)2 = 14.1 (1.5)2 / (0.717)2 = 61.7 = 62 min

30-28 (a) RS = 2[(tR)D – (tR)C] / (WD + WC)

RS = 2(21.6 – 14.1) / (1.72 + 1.16) = 5.21 = 5.2

( R S )1 N1 1.5 N1
(b)   
( RS ) 2 N2 5.21 2534

N1 = 2534  (1.5)2 / (5.21)2 = 210

L = 210  9.75  10-3 = 2.0 cm


Fundamentals of Analytical Chemistry: 8th ed. Chapter 30

30-29 through 30-32

A B C D E F
1 Problem 30-29
2 Compound tR, min W1/2, min N
3 Air 1.9
4 Methylcyclohexane 10 0.76 2770.083
5 Methylcyclohexene 10.9 0.82 2827.127
6 Toluene 13.4 1.06 2556.924
7
8 Average N 2718.045
9 Stan. Dev. N 142.4196
10 Column Length, L 40
11 Plate Height, H 0.014716
12 Spreadsheet Documentation
13 D4 = 16*(B4/C4)^2
14 D8 = AVERAGE(D4:D6)
15 D9 = STDEV(D4:D6)
16 D11 = D10 / D8
17
18 Problem 30-30
19 Resolution (methylcyclohexene - methylcyclohexane) 1.14
20 Resolution (methylcyclohexene - toluene) 2.66
21 Resolution (toluene - methylcyclohexane) 3.74
22 Spreadsheet Documentation
23 E19 = 2*(B5-B4)/(C5+C4)
24
25 Problem 30-31
26 To obtain RS = 1.5, N2 = 4712.032
27 Column Length, L 69.34444
28 Retention time, tR 18.89636
29 Spreadsheet Documentation
30 C26 = D8*1.5^2/E19^2
31 C27 = C26*D11
32 C28 = B5*1.5^2/E19^2
33
34 Problem 30-32
35 k (methylcyclohexane) 4.263158
36 k (methylcyclohexene) 4.736842
37 k (toluene) 6.052632
38
39 VM 19.6
40 VS 62.6
41 K (methylcyclohexane) 13.62
42 K (methylcyclohexene) 15.13
43 K (toluene) 19.33
44
45  (methylcyclohexane-methylcyclohexene) 1.11
Fundamentals of Analytical Chemistry: 8th ed. Chapter 30

46 Spreadsheet Documentation
47 E35 = (B4-B3)/B3
48 E41 = E35*E40/E39
49 F45 = (B5-B3)/(B4-B3)

30-33 and 30-34

A B C D E F G H I J
1 Problem 30-33 Problem 30-34
2 M N M N
3 K 5.93 6.11 K 5.81 6.20
4
5 VS / VM 0.398 VS / VM 0.398
6 k (M) 2.36014 k (M) 2.31238
7 k (N) 2.43178 k (N) 2.46760
8
9  1.0304  1.0671
10
11 R 1.5 R 1.5
12 N 82609.54 N 17966.57
13
14 H 0.0019 H 0.0019
15 L 156.9581 L 34.13648
16
17 (tR)N 82.86858 (tR)N 18.21102
18
19 Spreadsheet Documentation
20 B6 = B3*B5 G6 = G3*G5
21 B9 = C3/B3 G9 = H3/G3
22 B12 = 16*B11^2*(B9/(B9-1))^2*((1+B7)/B7)^2 G12 = 16*1.5^2*(G9/(G9-1))^2*((1+G7)/G7)^2
23 B15 = B12*B14 G15 = G14*G12
B17 = (16*B11^2*B14/6.5)* G17 = (16*G11^2*G14/6.5)*
24 (B9/(B9-1))^2*(1+B7)^3/B7^2 (G9/(G9-1))^2*(1+G7)^3/G7^2