24-1.

(a) What are the relative advantages and disadvantages of packed and open tubular columns in
gas chromatography?

→ Open tubular columns offer higher resolution, shorter analysis time, and greater sensitivity than
packed columns, but have less sample capacity.

Compared with open tubular columns, packed columns provide greater sample capacity but
give broader peaks, longer retention times, and less resolution. Despite their inferior resolution,
packed columns are used for preparative separations, which require a great deal of stationary
phase, or to separate gases that are poorly retained.

(b) Explain the difference between wall-coated and porous-layer open tubular columns.

→ Wall-coated open tubular column (WCOT): liquid stationary phase on inside wall of column

Porous-layer open tubular column (PLOT): solid stationary phase on inside wall of column

(c) What is the advantage of bonding (covalently attaching) the stationary phase to the column
wall or cross-linking the stationary phase to itself?

→ They reduce the tendency of stationary phase to bleed from the column at high temperature.

24-19.

(a) Use Trouton’s rule, s rule, ∆ H vap ≈ ( 88 J mo l K −1 ) ∙ T bp, to estimate the enthalpy of
−1

vaporization of octane (b.p. 126℃ ).

→ ∆ H vap ≈ ( 88 J mo l K −1 ) × ( 126+273.15 K ) ≈ 35125.2 J mo l−1 ≈ 35.13 k J mo l−1

−1

(b) Use the form of the Clausius-Clapeyron equation below to estimate the vapor pressure of
octane at the column temperature in Figure 24-9 (70℃ ).

P1 ∆ H vap 1 1
ln ( ¿ )=−( )( − )¿
P2 R T1 T2

→ The boiling point of a substance is the temperature at which the vapor pressure of a liquid
equals the pressure surrounding the liquid and the liquid changes into a vapor.

∴ The vapor pressure at b.p. = P2 = 1bar

P1 35125.2 J mo l
−1
1 1
ln ( )=−( )( − )¿ ¿ -1.73
¯
1¿ 8.314 J /mol ∙ K 70+273.15 K 126+ 273.15 K

∴ P 1=e−1.73 ¯¿ 0.18 ¯¿
(c) Calculate the vapor pressure for hexane (b.p. 69℃ ) at 70℃ .

→ ∆ H vap ≈ ( 88 J mo l K −1 ) × ( 69+273.15 K ) ≈ 30109.2 J mo l−1

−1

P1 30109.2 J mo l
−1
1 1
ln ( )=−( )( − )¿ ¿ 0.031
1¯
¿ 8.314 J /mol ∙ K 70+273.15 K 69+ 273.15 K
∴ P1=e0.031 ¯¿ 1.03 ¯¿

(d) What is the relationship between solute vapor pressure and retention?

→ The elution time increases as the solute can exist in a gaseous state. Therefore, the higher the
vapor pressure, the shorter the retention time.

(e) Why is the technique called “gas chromatography” if retained analytes are only partially
vaporized?

→ In gas chromatography, gaseous analyte is transported through the column by a gaseous

mobile phase, called the carrier gas.

24-20. Retention time depends on temperature, T, according to the equation log t r=¿
'
( Ta ) +b ,

where a and b are constants for a specific compound on a specific column. A compound is eluted
'
from a gas chromatography column at an adjusted retention time t r=15.0 min when the column
' '
temperature is 373K. At 363K, t r=20.0 min . Find the parameters a and b and predict t r at 353K.

→ log (15.0 min ⁡)=¿ ( 373a K ) +b ( 373a K ) +b ⋯

⟹ 1.18 = (1)

log (20.0 min ⁡)=( ) ( 363 K )

a a
+b ⟹ 1.30 = +b ⋯ (2)
363 K

−0.12 ( )−¿ (
363 K )
a a
(1) – (2) ⟹ = ∴ a=1624.8
373 K

Substituting the value of a into (1) equation, b=−3.17

∴ log t 'r =¿ ( 1624.8

353 K )
– 3,17 = 1.43

∴ t 'r =27.09 min

24-22. This problem reviews concepts from Chapter 23 using Figure 24-7.
Figure 24-7) Permanent gas analysis obtained with a 30m × 0.53nm column coated with a 50- μm-thick porous layer of
MXT-MSieve 5A operated at 30℃; H2 carrier gas with microthermal conductivity detection.

(a) Calculate the number of theoretical plates ( N in Equation 23-30) and the plate height ( H ) for
CO.
2 2
16 t r 16 ×17.05
→ N=¿ 2
= 2 = 3844 plates
w 1.1
L 30 m
H=¿ = = 0.78 cm
N 3844

(b) Find the resolution (Equation 23-23) between argon and oxygen.

∆ tr 2.2−1.1
→ Resolution (R) = = = 1.0
w av 0.1

24-23. This problem reviews concepts from Chapter 23 using Figure 24-15.
Figure 24-15) Resolution of 22 18-carbon fatty acid methyl esters with 1, 2, or 3 double bonds. Peaks 1, 2, 3, 4, 11, 12, 13,
15, 16, 17, 18, 19, 20, and 21 are all trans fats (see Figure 5-3). A Supelco 1L 100 ionic liquid (structure shown on page
637) wall-coated open tubular column (100m × 0.25mm with 0.20- μm-thick film, β =310) was operated at 150℃ with H 2

carrier gas at a linear flow rate of 25 cm/s and flame ionization detection.

(a) Calculate the retention factor for peak 11 given t m=6.7 min .

t r −t m
→ Retention factor (k) =
tm
49.5 min−6.7 min
k =¿ = 6.4
6.7 min

(b) Calculate the number of theoretical plates ( N in Equation 23-31) and the plate height (H ) for
peak 11.
2 2
16 t r 16 ×49.5
→ N=¿ 2
= 2 = 39204 plates
w 1
L 100 m
H=¿ = = 0.26 cm
N 39204

(c) Find the resolution (Equation 23-23) between peaks 16 and 17.

∆ t r 64.0−62.9
→ Resolution (R) = = = 1.38
w av 0.8

24-24.
(a) Why is it illogical to use a thin stationary phase (0.2 μm) in a wide-bore (0.53-mm) open
tubular column?

→ Thin stationary phase gives rapid mass transfer in stationary phase. Wide bore column gives
slow mass transfer in mobile phase. At high temperatures, the stationary phase decomposes
and the decomposition products slowly bleed. These decomposition products increase the
background signal, thereby reducing the signal-to-noise ratio and contaminating the detector.
To reduce disturbance by column bleeding, use as thin a stationary phase and narrow and short
columns as possible within the range of obtaining the desired separation.

(b) Consider a narrow-bore (0.25 mm diameter), thin-film (0.10 μm) column with 5000 plates per
meter. Consider also a wide-bore (0.53 mm diameter), thick-film (5.0 μm) column with 1500
plates per meter. The density of stationary phase is approximately 1,0g/mL. What mass of
stationary phase is in each column in a length equivalent to one theoretical plate? How many
nanograms of analyte can be injected into each column if the mass of analyte is not to
exceed 1.0% of the mass of stationary phase in one theoretical plate?

mass
→ density = ⟹ mass = volume ×density
volume
As a narrow-bore (0.25 mm diameter),

( )
2 2
0.25 mm 0.25 mm
Vs = πL× [( )− −0.0001 mm ]
2 2
−5 2 −2 3
¿ 3.14 × 1000 mm× 2.50 ×10 m m =7.85× 10 mm
Mass(stationary phase) in a meter tube
3
1 mL 1cm
= (7.85 ×10−2 m m 3)× ( 1.0 g ∙ m L−1 ) × 3 × 3 = 7.85×10 g = 7.85×10 ng
-5 4

1c m 1000 mm
Mass in 1 theoretical plate = (7.85×104 ng) / (5000 plates) = 15.7 ng/plate

Injection limit = (15.7 ng/plate)×(0.01) = 0.16 ng

As a wide-bore (0.53 mm diameter),

( )
2 2
0.53 mm 0.53 mm
Vs = πL× [( )− −0.005 mm ]
2 2
−4 2 3
¿ 3.14 × 1000 mm× 2.65 ×10 mm =8.3 m m
Mass(stationary phase) in a meter tube
3
1 mL 1cm
= (8.3 m m )× ( 1.0 g ∙m L ) ×
3 −1
3 × 3 = 8.3×10 g = 8.3×10 ng
-3 6

1c m 1000 mm
Mass in 1 theoretical plate = (8.3×106 ng) / (1500plates) = 5.5×103 ng/plate
 Injection limit = (5.5×103 ng/plate)×(0.01) = 55 ng

24-25. The graph shows van Deemter curves for n -nonane at 70℃ in the 3.0-m-long
microfabricated column in Box 24-2 with a 1-to-2 μm-thick stationary phase.

(a) Why would air be chosen as the carrier gas? What is the danger of using air as carrier gas?

→ Typically, carrier gas is supplied to a high-pressure tank but air does not need a gas tank.

Impurities (like O2 gas) in the carrier gas damage the stationary phase.

(b) Measure the optimum velocity and plate height for air and for H 2 carrier gases.

→ Air : about 10cm/s, 0.04cm

H2 : about 20cm/s, 0,05cm

(c) How many plates are there in the 3-m-long column for each carrier gas at optimum flow rate?

L L
→ H=¿ ⟹ N=¿
N H
3m
Air : N=¿ ¿ 7500 plates
0.04 cm
3m
H2 : N=¿ ¿ 6000 plates
0.05 cm
(d) How long does unretained gas take to travel through the column at optimum velocity for
each carrier gas?

3m
→ time(t) =
optimum velocity
3m
Air : t = = 30s
10 cm/s
 3m
H2 : : t = = 15s
20 cm/s

(e) If stationary phase is sufficiently thin with respect to column diameter, which of the two mass
transfer terms (23-40 of 23-41) becomes negligible? Why?
2 2
1+ 6 k +11k r
→ 23-40) C m=¿ 2
∙
24 (k +1) Dm
2
2k d
23-41) C s=¿ 2
∙
3(k +1) D s

Decreasing stationary phase thickness, d, reduces plate height and increases efficiency because
solute can diffuse faster from the farthest depths of the stationary phase into the mobile
phase. Therefore, Cs(23-41) becomes negligible.

(f) Why is the loss of column efficiency at high flow rates less severe for H 2 than for air carrier
gas?

→ H2 gives better resolution (smaller plate height) than air at high flow rate because solutes
diffuse more rapidly through H2.

24-35. Theoretical performance in gas chromatography. As the inside radius of an open tubular
column is decreased, the maximum possible column efficiency increases and sample capacity
decreases. For a thin stationary phase that equilibrates rapidly with analyte, the minimum
theoretical plate height is given by

H min
r
=
√
1+ 6 k +11k 2
3 (1+ k )
2

where r is the inside radius of the column and k is the retention factor.

(a) Find the limit of the square-root term as k → 0(unretained solute) and as k → ∞ (infinitely
retained solute).

→ As k → ∞ (infinitely retained solute), lim

k→∞ √ 1+6 k +11k 2
3(1+ k )
2
√
=¿
11
3

(b) If the column radius is 0.10 mm, find Hmin for the two cases in part (a).
 √
H min H min 11
→ As k → ∞ (infinitely retained solute), = = ∴ H min =0.19 mm
r 0.10 mm 3

√
H min H min 1 ∴ H =0.058 mm
As k → 0(unretained solute), = = min
r 0.10 mm 3

(c) What is the maximum number of theoretical plates in a 50-m-long column with a 0.10-mm
radius if k =5.0?

→
H min
r
=
√1+ 6 k +11k 2
3 (1+ k )
2

H min
0.1 mm
=
√
1+6 (5.0)+11(5.0)2
3(1+5.0)2
¿1.68 ∴ H min =0.17 mm

L 50 m
N max =¿ = = 2.94×105
H min 0.17 mm

(d) The phase ratio is defined as the volume of the mobile phase divided by volume of the
stationary phase ( β=V m /V s ¿ . Derive the relationship between β and the thickness of the
stationary phase in a wall-coated column (df) and the inside radius of the column (r ).

r
→ β=¿
2 df

In the inner wall-coated column, the phase ratio and thickness of the stationary phases is
inversely proportional.

(e) Find k if K=1000, df = 0.20 μm, and r = 0.10mm.

r 0.10 mm
→ β=¿ = = 250
2 df 2× 0.2 μm
K 1000
k =¿ = =4
β 250