CHEM2202 Chemical Instrumentation

Exercise 2.
Separation and Chromatography
Due date:
October 3, 2014 (Sunday)
1.

The partition coefficient for the weak acid HA is 7.4 and the dissociation constant K a' for the acid
in water is 110-6. What fraction of the acid will be extracted at pH 3 and pH 8? Assume a single
extraction with equal volumes of organic and aqueous phases.
Hint:
The dissociation reaction of the weak acid HA can be expressed as:

HA H + + A
Only the neutral form (HA) can be extracted into the organic phase.
The equilibrium concentrations of different species of the acid are:

K a' =

[H + ][ A ]
[HA]
+

Rearranging the above equation gives the relation of the fraction of HA and the concentration of H :

fHA =

[HA]
1
= '

[HA] + [ A ] K a /[H + ] + 1

For the extraction equilibrium with equal volume of aqueous and organic phases:

HA,aq =

1
1
=
1 + D(Vorg / Vaq ) 1 + D

since D =

HA,aq =

2.

[HA]org
[HA]total ,aq

1
=
1 + K p' fHA

[HA]org
[HA]aq / fHA

1+

= K p' fHA ,

1
K p'
(1 + K a' /[H + ])

A 2.00 L sample of water contains a chemical X. X is very soluble in ether; the formal partition
constant K p' = 500. X is pre-concentrated in ether by shaking the sample with 10.0 mL of ether.
The final concentration of X in the ether extract is 2.0010-3 M. (a) What is the concentration of
X in the original water sample? (b) What fraction of X would remain in the 2.00 L water sample
if the water sample is extracted with five fresh portion of ether, each of volume of 2.00 mL?

3.

A liquid chromatographic column has the following properties:

Length of packing
24.7 cm
VM
1.37 mL
VS
0.165 mL
A summary of the chromatogram of a mixture of species A, B, and C is given below:
Retention time, min.
Base width (W), min
Nonretained
3.1
-A
5.4
0.41
B
13.3
1.07
C
14.1
1.16
Calculate
(a)
The number of plates for each peak.
(b)
The mean and the standard deviation of N.
(c)
The plate height for the column.
(d)
The capacity factor of species B.
(e)
The partition coefficient of species B.
(f)
The resolution for peaks B and C.
(g)
The number of theoretical plates necessary to separate B and C with a resolution of 1.5.
(h)
The length of column necessary for the separation in (g).
(i)
The time required to elute B and C using the new column in (h).