23-C.

(a) Find the retention factors for octane and nonane in Figure 23-7. When you measure distances,
estimate them to the nearest 0.1mm.

0 1.0 5.0 8.6

Figure 23-7) Schematic gas chromatogram showing measurement of retention times.

t r −t m
→ For each peak in the chromatogram, the capacity factor, k , is defined as k = .
tm
5.0−1.0
Octane : k =¿ =4.0
1.0
8.6−1.0
Nonae : k =¿ = 7.6
1.0

(b) Find the ratio

Time octane spends∈stationary phase t m 1.0

→ = = = 0.25
Total time octane spends on column tr 4.0

(c) Find the relative retention for octane and nonane.

t r 2 8.6
→ Relative retention (α ) = = = 2.15
t r 1 4.0

(d) Find the partition coefficient for octane by assuming that the volume of the stationary phase
equals half the volume of the mobile phase.

Vs
→ Retention factor (k) ¿ K ∙
Vm
Vm
Partition coefficient (K) = ∙ k = 2 × 4.0=8.0
Vs
23-D. A gas chromatogram of a mixture of toluene and ethyl acetate is shown here.

(a) Use the width of each peak (measured at the base) to calculate the number of theoretical
plates in the column. Estimate all lengths to the nearest 0.1 mm.
2
5.55t r
→ N=¿ 2
w 1/ 2
2
5.55×(2.0)
Ethyl acetate : N=¿ = 2220 plates
(0.1)2
2
5.55×(6.4 )
Toluene : N=¿ = 1420 plates
(0.4 )2

(b) Using the width of the toluene peak at its base, calculate the width expected at half-height.
Compare the measured and calculated values. When the thickness of the pen trace is
significant relative to the length being measured, it is important to take the pen width into
account. You can measure from the edge of one line to the corresponding edge of the other
line, as shown here.

→ The width of the toluene peak at its base (w) is 1.0cm, so we can expect the width of half-
height (w1/2) is 0.5cm. The actual width of half-height is 0.4cm.

23-5. Why is the extraction of a metal ion into an organic solvent with 8-hydroxyquinoline more
complete at higher pH?

→ 8-Hydroxyquinoline ligand can be represented as a weak acid, HL, which loses one proton
when it binds to a metal ion through the atoms shown in bold type.
 −¿ ( aq ) ¿

HL ( aq ) ⇌ H +¿ (aq) +L ¿

n +¿ ( aq ) ⇌ M Ln (aq )¿

n L−¿ (aq )+M ¿

Each of these ligands can react with many different metal ions, but some selectivity is achieved
by controlling the pH.
+ ¿¿
n +¿⇌ M L n+nH ¿
n HL+ M

As the pH increases, the forward reaction proceeds according to Le Chatelier's principle, so

the fraction of metal in the form M L n extracted in the organic solvent increases.

23-11. Consider the extraction of M n+¿ ¿ from aqueous solution into organic solution by reaction
with protonated ligand, HL:
+ ¿(aq) ¿

M n+¿ (aq )+nHL ( org) ⇌ M L (org )+n H

n ¿

K extraction= [ M Ln ] org ¿ ¿ ¿
Rewrite Equation 23-13 in terms of Kextraction and express Kextraction in terms of the constants in
Equation 23-13. Give a physical reason why each constant increases or decreases Kextraction.

[ HL ]naq [ M Ln ]org
→ K extraction=¿ × × ¿¿ ¿
[ HL ] org [ M Ln ]aq
n

n
KM ∙ β ∙ K a
= [ M L n ] org ¿ ¿ ¿ = n
kl
n
D ≈ K extraction × [ HL ] org
¿¿¿
Because there are concentrations of overlapping components, there is a proportional or
inversely proportional relationship depending on the value.

23-14. For the extraction of Cu 2+ by dithizone in CCl4, KL = 1.1×104, KM = 7×104, Ka =3×10-5, β = 5

×1022 and n = 2.
(a) Calculate the distribution coefficient for extraction of 0.1 μm Cu2+ into CCl4 by 0.1 mM
dithizone at pH 1.0 and at pH 4.0.
n
K M ∙ β ∙ K na [ HL ]org
→ Distribution coefficient(D) = ∙
K nL ¿¿¿

[ HL]org =[ HL ]aq ∙ K L , ¿
2 2
7 ×104 ∙ 5 ×1022 ∙ ( 3 ×10−5 ) ( 0.1 ×10−3 ×1.1 ×10 4 ) 4
When the pH is 1, D=¿ 2
× −1 2
¿ 2.6 ×10
( 1.1 ×10 4 ) ( 10 )
 −5 2 2
7 ×10 ∙5 ×10 ∙ ( 3× 10 ) ( 0.1×10−3 × 1.1× 104 )
4 22
10
When the pH is 4, D= 2
× −4 2
¿ 2.6 ×10
( 1.1× 104 ) ( 10 )

(b) If 100 mL of 0.1 μm aqueous Cu2+are extracted once with 10 mL of 0.1 mM dithizone at pH 1.0,
what fraction of Cu2+ remains in the aqueous phase?
n
n V1
→ The fraction of Cu2+ is q ¿ ( )
V 1+ K V 2

n = 1, using D in place of K

100 −4
q=¿ 4 ¿ 3.84 × 10
100+2.6 ×10 × 10

23-20.

(a) A chromatography column with a length of 10.3 cm and inner diameter of 4.61 mm is packed
with a stationary phase that occupies 61.0% of the volume. If the volume flow rate is 1.13
mL/min, find the linear flow rate in cm/min.

→ The linear velocity tells how many centimeters are traveled in 1 min by the solvent.

the volume flow rate 1.13 mL /min

= 2
Linear velocity = the volume of mobile phase∈1 cm of column π r × 1 cm× (1−0.61 )
❑
1.13 mL /min
¿
( )
2
0.461cm ¿ 17.36 cm/min
3.14 × ×1 cm ×0.39
2

(b) How long does it take for solvent (which is the same as unretained solute) to pass through
the column?

→ The length of column ÷ linear velocity = 10.3 cm÷ 17.36 cm/min ¿ 0.592 min

(c) Find the retention time for a solute with a retention factor of 10.0
2
π r ×10.3 cm ×0.39
→ tm for mobile phase to pass through the column = ¿ 0.593
1.13 mL /min
t r −t m
Retention factor (k) =
tm

∴ retention time ( t r )=k ∙ t m +t m=10.0× 0.593+0.593=6.52 min

23-28. Which of the following columns will provide :

Column 1 : N = 1000; k2 = 1.2; α = 1.16; resolution = 0.6

Column 2 : N = 5000; k2 = 3.9; α = 1.06; resolution = 0.8

Column 3 : N = 500; k2 = 4.7; α = 1.31; resolution = 1.1

Column 4 : N = 2000; k2 = 2.4; α = 1.24; resolution = 1.5

(a) Highest number of plates?

→ The number of plates is N. ∴ The answer is column 2.

(b) Greatest retention?

→ The larger the retention factor, the greater the retention time. ∴ The answer is column 3.

(c) Highest relative retention?

→ The relative retention is α . ∴ The answer is column 3.

(d) Best separation?

→ The higher the resolution, the better the degree of separation. ∴ The answer is column 4.

23-31. Isotopic compounds (isotopologues) are separated in Figure 23-15 by repeated passage
through a pair of columns. Each cycle in the figure represents one pass through length
L=25cm containing N theoretical plates. The relative retention ( α ) is 1.03 and the retention
factor for L-phenylalanine is k2=1.62.
Figure 23-15) Separation of 0.5 mM L-phenylalanine and 0.5 mM L-phenylalanine-D5 by repeated passes through a pair
of Hypersil C8 liquid chromatography columns eluted with 10:90 acetonitrile:water containing 25 mM and
0.1% trifluoroacetic acid in the water. [From K. Lan and J. W. Jorgensen,“Pressure-Induced Retention
Variations in Reversed-Phase Alternate-Pumping Recycle Chromatography,” Anal. Chem. 1998, 70, 2773.]

(a) The observed resolution after 10 cycles is 1.60. Calculate the number of theoretical plates, N,
in column length L. The mixture has passed through length 10L in 10 cycles.

→ Resolution (R) =
4 α ( )
√ N ∙ ( α −1 ) ∙ k 2
1+k 2

α
√ N=¿ R × 4 × ( α −1 ) × k
2
2
( )
1+k
= 1.60 × 4 ×
1.03
(1.03−1)
×
(1+1.62)
1.62
= 355.37

∴ N =( 355.37 )2=12.62× 104

(b) Find the plate height in μm.

4
L 25 cm 1 ×10 μm
→ H=¿ = × = 1.98 μm
N 12.62× 10
4
1 cm

(c) Predict the resolution expected after just two cycles. The observed value is 0.71.
2
→ The number of passes is proportional to the ( resolution ) .
2 2
10 : (1.60)2 = 2 : R2 → 2 × ( 1.60 ) =10 ∙ R

√
2
2× ( 1.60 )
∴ R= =0.715
10
23-32. Chromatograms of compounds A and B were obtained at the same flow rate with two
columns of equal length. The value fo tm is 1.3 min in both cases.
(a) Which column has more theoretical plates?
2
16 t r
→ N=¿ 2
, Column 1 and 2 have same value of tr in both A and B.
w
So we only need to check value of w which is the width at base. Column 2 is wider than 1.

As the w value is small, the N value is large. ∴ The answer is column 1.

(b) Which column has a larger plate height?

L
→ H=¿ , L is the same in both column 1 and 2. N is smaller in column 2.
N
∴ The answer is column 2.

(c) Which column gives higher resolution?

→ The resolution is proportional to theoretical plates. ∴ The answer is column 1.

(d) Which column gives a greater relative retention?

tr 2
→ relative retention (α ) = , ∴ relative retention is same in column A and B.
tr 1

(e) Which compound has a higher retention factor?

t r −t m
→ Retention factor (k) = , ∴ The compound B is higher than A.
tm

(f) Which compound has a greater partition coefficient?

→ Partition coefficient is proportional to retention factor.

∴ The compound B is greater than A.

(g) What is the numerical value of the retention factor of peak A?

8 min−1, 30 min
→ k a=¿ ¿ 5.15
1.30 min

(h) What is the numerical value of the retention factor of peak B?

10 min−1 , 30 min
→ k b=¿ = 6.69
1.30 min

(i) What is the numerical value of the relative retention?

k b 6.69
→ α =¿ = = 1.29
k a 5.15

23-49. Two compounds with partition coefficients of 15 and 18 are to be separated on a column
with Vm/Vs=3.0, tm=1.0 min. Calculate the number of theoretical plates needed to produce
a resolution of 1.5.

Vs
→ Retention factor (k) ¿ K ∙
Vm

If the retention factor of the component with a partition coefficient of 15 is k a and the retention
factor of the component with a partition coefficient of 18 is kb,

kb 6
k a=15 ÷ 3.0=5 , k b =18 ÷3.0=6 . And α =¿ = = 1.2.
ka 5

Resolution (R) =
4 α ( )
√ N ∙ ( α −1 ) ∙ k 2
1+k 2

The resolution should be at least 1.5, so if you substitute kb in the k2 place,

( )
2
1.2 7 3
∴ N = 1.5 ×4 × × =1.76 ×10
(1.2−1) 6

23-51. Consider the peaks for pentafluorobenzene and benzene in the gas chromatogram shown
here. The elution time for unretained solute is 1.06 min. The open tubular column is 30.0 m in
length and 0.530 mm in diameter, with a layer of stationary phase 3.0 μm thick on the inner
wall.
(a) Find the adjusted retention times and retention factors for both compounds.

' t r −t m
→ The adjusted retention times (t r ¿=t r −t m , Retention factor (k )=
tm

' 12.98−1.06
Pentafluorobenzene : t r 1=12.98−1.06=11.92 , k1= = 11.25
1.06

' 13.20−1.06
Benzene : t r 2=¿ 13.20 - 1.06=12.14, k2 = =11.45
1.06

(b) Find the relative retention, α .

t r 2 13.20
→ relative retention (α ) = = = 1.017
t r 1 12.98

(c) Measuring on w1/2 the chromatogram, find the number of plates, N 1 and N2, and the plate
height for these two compounds.
 2
5.55t r L
→ N=¿ 2 , H=¿
w 1/ 2
N
2
Measuring the area, w 1/ 2 is about 0.12 in both pentafluorobenzene and benzene.

2
5.55×(12.98) 30.0 m
Pentafluorobenzene : N 1=¿ = 60813 plates, H 1=¿ = 4.9×10-4m
(0.124)2
60813
2
5.55×(13.20) 30.0 m
Benzene : N 2=¿ = 66049 plates, H 2=¿ = 4.5×10-4m
(0.121)2
66049

(d) Measuring the width, w, at the baseline on the chromatogram, find the number of plates for
these two compounds.
2
16 t r
→ N=¿ 2
w
Measuring the area, w is about 0.22 of pentafluorobenzene and about 0.24 of benzene.
2
16 ×(12.98)
Pentafluorobenzene : N 1=¿ = 55696 plates
(0.22)2
2
16 ×(13.20)
Benzene : N 2=¿ = 48400 plates
(0.24)2

(e) Use your answer to (d) to find the resolution between the two peaks.

∆ t r 13.20−12.98
→ Resolution (R) = = = 0.96
w av 0.23

(f) Using the number of plates N= √ N 1 N 2, with values from (d), calculate what the resolution
should be and compare your answer with the measured resolution in (e).

√√N
→ Resolution (R) =
4
N 2 ( α −1 )
1
∙
α
∙
k2
( )
1+k 2

=
√ √55696 × 48400 × (1.017−1) × 11.45
4 1.017 (1+11.45)
= 0.88

The measured resolution in (f) is smaller than in (e).