Chapter 23 – Introduction to Analytical Separations 1

Multiple-Choice

23-1 Solvent Extraction

1. is the physical transfer of solute from one phase to another.

A) Partitioning
B) Extraction
C) Activated transport
D) Sieving
E) Miscibility

Answer: B
Easy

Solution
A) Partitioning is a way of working out math problems that involve large numbers by splitting
them into smaller units so they’re easier to work with.
C) Activated transport is the movement of molecules across a cell membrane from a region of
lower concentration to a region of higher concentration—against the concentration gradient.
D) Sieving is a simple technique for separating particles of different sizes. is a simple technique
for separating particles of different sizes.
E) Miscibility is the property of two substances to mix in all proportions (that is, to fully
dissolve in each other at any concentration), forming a homogeneous solution.

2. A solute is to be extracted using 150 mL of solvent. Of the options below, which will
extract the maximum amount of solute?

A) extract with 30 mL five times

B) extract with 37.5 mL four times
C) extract with 75 mL twice
D) extract once with the entire volume
E) extract with 50 mL three times

Answer: A
Intermediate

Solution
The more you divide to extract several times, the greater the amount of solute can be extracted.
n
n V1
After n extractions, each with volume V2, the fraction remaining in phase 1 is q ¿ ( ).
V 1+ K V 2

3. The partition coefficient is modified when the pH of the aqueous phase is adjusted or
when a chelating agent is added. The partition coefficient is renamed the distribution coefficient.
What is the impact on the extraction of a weak acid into an organic solvent as the pH of the
aqueous phase increases?
Chapter 23 – Introduction to Analytical Separations 2

A) As the pH increases the value of D decreases and the percentage weak acid left in the
aqueous phase decreases.
B) As the pH increases the value of D increases and the percentage weak acid left in the
aqueous phase increases.
C) As the pH increases, the value of D decreases and the percentage weak acid left in the
aqueous phase decreases.
D) As the pH increases the value of D increases and the percentage weak acid left in the
aqueous phase decreases.
E) As the pH increases the value of D decreases and the percentage weak acid left in the
aqueous phase increases.

Answer: E
Hard

Solution
total concentration∈ phase 2
D=
total concentration∈ phase 1

Suppose that acid HA(with dissociation constant Ka) is partitioned between aqueous phase 1 and
organic phase 2 with partition coefficient K for HA. Assuming that A - is not soluble in the
organic phase, show that the distribution coefficient is given by
Disstribution of acid between two phase : D=K ∙ ¿ ¿
Where α HA is the fraction of weak acid in the form HA in the aqueous phase.

As the pH increases, the concentration of hydrogen ions decreases. Since the multiplication
numerator is smaller than the addition denominator, the total D value decreases. Because the
partition coefficient(D) become smaller, it can be seen that the weak acid is not extracted with
the organic solvent and remains in an aqueous solution.

23-2 What Is Chromatography?

4. Which form of chromatography is INCORRECTLY defined?

A) adsorption chromatography – solute is adsorbed into solid particles

B) partition chromatography – solute equilibrates between the stationary liquid and the
mobile phase
C) ion-exchange chromatography – solute ions of the opposite charge are attracted to the
stationary phase
D) molecular exclusion chromatography – solute is separated based on size
E) affinity chromatography – solute binds to a molecule specific for the solute

Answer: A
Intermediate

Solution
Chapter 23 – Introduction to Analytical Separations 3

A) adsorption chromatography – solute is adsorbed into solid particles

⤷ on the surface

5. Which statements are NOT true regarding chromatography?

I The stationary phase is typically a liquid bonded to the inside surface of a capillary or the
surface of solid packed in the column.
II The mobile phase entering the column is the eluate.
III Mobile phase is the solvent (gas or liquid) that moves through the column.
IV Eluent is the process of passing mobile phase though a column.
V Columns are either open tubular or packed.

A) I and V
B) II and IV
C) I, II, and III
D) III and V
E) I, IV, and V

Answer: B
Intermediate

Solution
II The mobile phase entering the column is the eluate.
⤷ stationary
IV Eluent is the process of passing mobile phase though a column.
⤷ stationary

23-3 A Plumber’s View of Chromatography

6. is a plot of detector response versus retention time.

A) Spectrum
B) Electrophoretogram
C) Chromatogram
D) Chromospectrum
E) Elution response

Answer: C
Easy

Solution
A) Spectrum is components when visible, ultraviolet, and infrared light are decomposed by a
spectroscope
B) Electrophoretogram is a record that consists of the separated components of a mixture (as of
proteins) produced by electrophoresis in a supporting medium (such as filter paper).
D) Chromospectrum is a non-existent word.
Chapter 23 – Introduction to Analytical Separations 4

E) Elution response is a non-existent word.

7. Which is NOT true for solute retention?

A) Retention time, tr, is the elapsed time between injecting the sample to the arrival of a
sample component at the detector minus the dwell time between the end of the column
and the detector.
B) Adjusted retention time is tr’ = tr – tm, where tr is the retention time and tm is the time for
mobile phase or unretained solutes to pass through the column.
t 'r 2
'
C) The relative retention,  = t r 1 , is the ratio for the adjusted retention time for two
components of the sample, where tr2’ > tr1’ so that  > 1.
t r −t m
D) The retention factor, k = t m , is the time, tr, required to elute a component minus the
time, tm, for mobile phase to pass through the column divided by tm.
K2
E) The relative retention, , also equals K 1 , where K2 and K1 are the partition coefficients
for components 2 and 1.

Answer: A
Intermediate

Solution
Retention time, tr, for each component is the time that elapses between injection of the mixture
onto the column and the arrival of that component at the detector.

8. The relative retention between two solutes, 1 and 2, is  = 1.35. If the adjusted retention
time for solute 2 is 293 s, what is adjusted retention time for solute 1?

A) 396 s
B) 217 s
C) 189 s
D) 241 s
E) 344 s

Answer: B
Intermediate

Solution
For two components 1 and 2, the relative retention,  ( also called separation factor), is the ratio
'
tr2
of their adjusted retention times: α = ' where t 'r 2 ¿ t 'r 1, so  > 1.
tr1
Chapter 23 – Introduction to Analytical Separations 5

'
' t 293
As  = 1.35 and t is 293 s, t = r 2 =
r2
'
r1 =217.03 s.
α 1.35
9. Which is NOT true when scaling up preparative chromatography?

A) Keep column length constant.

B) Cross-sectional area of a column is inversely proportional to the mass of analyte.
C) Maintain constant linear velocity.
D) Sample volume applied to column is proportional to mass of analyte.
E) If you change column length, mass of sample can be increased in proportion to total
length.

Answer: B
Intermediate

Solution
B) Cross-sectional area of a column is inversely proportional to the mass of analyte.

23-4 Efficiency of Separation

Δt r ΔV r 0 . 589 Δt r
= =
10. w
The resolution between two peaks is defined as resolution = av w av w 1/2av .
Which variable is INCORRECTLY defined?

A) tr is the retention time.

B) Vr is the retention volume.
C) wav is the average peak width measured at the base of each peak.
D) w1/2av is the average peak width measured at the base of each peak, divided by 2.
E) resolution is the separation between two adjacent peaks.

Answer: D
Intermediate

Solution
w1/2av is the width at half-height of Gaussian peaks. The width at half-height is usually used
because it is easiest to measure.

11. The longer an analyte remains on the column, the broader the peak becomes. Peaks widen
with time on column due to :

A) effusion.
B) diffusion.
C) adsorption.
D) absorption.
E) viscosity.
Chapter 23 – Introduction to Analytical Separations 6

Answer: B
Easy

Solution
A band of solute broadens as it moves through a chromatography column. One main cause of
band spreading is diffusion, which is the net transport of a solute from a region of high
concentration to a region of low concentration caused by the random movement of molecules.

12. Which is true for plate height?

I The smaller the plate height, the narrower the peaks.

II The larger the plate height, the better separation between peaks.
III Plate height can be calculated from the column length, L, and the number of theoretical
plates, N.
IV For fixed number of theoretical plates, N, the longer a solute is on column, the wider the
peak will become.

A) I, II, and IV
B) II and IV
C) I, III, and IV
D) II only
E) IV only

Answer: C
Intermediate

Solution
II The larger the plate height, the better separation between peaks
⤷ smaller

23-5 Why Brands Spread

13. The van Deemter equation describes plate height in terms of constants A, B, C, and the
linear velocity, ux. Which statement is NOT true for the van Deemter equation?

B
H≈ A+ + Cu x
ux
A) A takes into account multiple pathways through the column. The value of A is column
specific and independent of linear flow.
B) B takes into account longitudinal diffusion of the analyte in the mobile phase. The value
of B is column specific and the impact of B on the plate height is inversely proportional
to the linear velocity.
C) C takes into account equilibrium time between the stationary and mobile phase. The
value of C is column specific and the impact of C on plate height is proportional to the
linear velocity.
Chapter 23 – Introduction to Analytical Separations 7

D) To minimize plate height, the optimal flow rate is the minima for the plot of
B/u x + Cu x
versus flow rate.
E) Linear velocity is the flow rate of the mobile phase.

Answer: D
Intermediate

Solution
D) To minimize plate height, the optimal flow rate is the minima for the plot of
B/u x + Cu x
B
versus flow rate. A+ +C u x
ux

14. Which comparison of open tubular columns to packed columns is INCORRECT?

A) Open tubular columns have higher resolutions than packed columns.

B) Open tubular columns have increased linear velocity or a longer column or both.
C) Packed columns have decreased sensitivity.
D) Packed columns have longer analysis times.
E) Packed columns have a lower sample capacity.

Answer: E
Intermediate

Solution
E) Packed columns have a lower sample capacity.
⤷ Open tubular

2
15. The observed variance, σ obs , for a peak is the sum of the variances from all contributing
2
factors. Which of the following is not a contributing factor to σ obs ?

A) σ 2column

B) σ 2detector

C) σ 2injection

D) σ 2tubing

E) σ 2source

Answer: E
Intermediate

Solution
Chapter 23 – Introduction to Analytical Separations 8

A band of solute invariably spreads as it travels through a chromatography column and emerges
at the detector with a standard deviation σ . Each individual mechanism contributing to
broadening produces a standard deviation σ i. The observed variance (σ 2obs) is the sum of
variances from all contributing mechanism : σ 2obs =σ 21 +σ 22+ σ 23 +∙∙ ∙=∑ σ 2i
The observed variance is σ 2obs =σ 2column + σ 2injection + σ 2detector +σ 2tubing
Calculated

23-1 Solvent Extraction

16. Calculate the weak acid, HA, concentration that remains in the aqueous phase when 50.0
mL of 0.184 M HA at pH = 4.75 is extracted with 50 mL of toluene three times. The partition
coefficient for the extraction is 5.17, favoring toluene. The Ka for HA is 8.0 x 10−4.

Answer: 72.5% remains or 0.133 M HA remains in the aqueous phase.

Hard
Calculate the distribution coefficient, D, from [H+], Ka and K, substitute into the extraction
equation and solve for q3. Multiply q3 by the original concentration to calculate concentration
remaining HA.

Solution
D=K ∙ ¿ ¿
Using D in place of K, the fraction concentration remaining in the aqueous phase is

( )
3
50
=0.726 → 72.6% left in aqueous phase
3
q=
50+ 0.1124 × 50
0.184 M ×0.726=0.133 M remins in the aqueous phase

17. Suppose that the partition coefficient for an amine, B, is K = 3.0 and the acid dissociation
constant for BH+ is Ka = 1.0 x 10−9. If 50.0 mL of 0.010 M aqueous amine is extracted with
100.0 mL of solvent two times, what percentage amine remains in aqueous solution if the pH of
the aqueous phase is 9.00?

Answer: 32.7%
Hard
Calculate the distribution coefficient, D, from [H+], Ka and K, substitute into the extraction
equation and solve for q2. Multiply q2 by 100 to get percentage.

Solution
K ∙ Ka
D=
K a +¿ ¿
Using D in place of K, the fraction concentration remaining in the aqueous phase is

( )
2
50
=0.0625 → 6.25%
2
q ¿
50+ 1.5× 100
I think the above answer is wrong.

23-4 Efficiency of Separation

Chapter 23 – Introduction to Analytical Separations 9

18. For two separated solutes the  = 1.10 and the k2 = 4.38. How many theoretical plates are
required to achieve a resolution of 1.5?

Answer: 6572 theoretical plates are required.

Intermediate
Plug the value of , k2, and resolution value into the Purnell equation, solving for N.

Solution

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

1.5= √
4 ( )( )
N 1.10−1
1.10
4.38
1+ 4.38

( )( )
√ N=1.5 × 4 ×
1.10
1.10−1
1+ 4.38
4.38
∴ N =6572.1
∴ 6572 theoretical plates are required.

19. Calculate the resolution for two chromatographic peaks that elute at tr1 = 1770 s and tr2 =
1800 s with base peak widths of w1 = 51 s and w2 = 57 s.

Answer: 1.11
Intermediate
Calculate tr and wav and plug into equation 23-23.

Solution
∆ tr
Resolution=
w av
1800−1770 30
R= = =1.11
(
1 51+57
2 2 )27

20. Calculate the number of theoretical plates and plate height for a peak with a retention
time of 1295 seconds, a width at the baseline of 27 seconds and elutes from a 15 m column.

Answer: 36807 plates, 0.408 mm

Intermediate
Calculate the number of plates, N, from the retention time and the baseline width, equation 23-
30. Then, divide the number of plates into the length of the column to get plate height.

Solution
2
16 t r 16 ×1295 2
N= 2 = 2
=36807.13 → 36807 plates
w 27
Chapter 23 – Introduction to Analytical Separations 10

L 15 m
H= = =0.408 mm
N 36807.13