Laboratory Report

Short Laboratory Report

SIC2022 Basic Analytical Chemistry

Experiment No: 5
Title: Separation of Chloride and Bromide by Ion Exchange
Chromatography
Name: Sharvani A/P Karthigesu
Matric number: U2103660/1
Name of Partners: 1. Low Ru Yi
2. Nur Eillia Shuhada Binti Ab Rahman
Date: 15/11/2022
Title

Separation of Chloride and Bromide by Ion Exchange Chromatography

Objective

i. To demonstrate the chromatographic separation of chloride ion and

bromide ion from known amount of chloride and bromide salt.
ii. To quantitatively determine the percentage of chloride ions and bromide
ions recovered from the chromatographic seperation column.

Results and Discussion

➢ Mass of NaCl : 0.1003 g

➢ Mass of KBr : 0.2070 g

Preparation of Column

20g of resin was washed with distilled water followed by HNO3 and then packed in
the column as shown in figure 1.

Figure 1: Column packed with resin slurry

The column was washed with HNO3 until the washing was free from chloride ions.
Silver nitrate test was done on the eluent collected and no precipitate was formed
which indicates that all the chloride ion have been washed off. It is shown in figure 2.
 Figure 2: Eluent of HNO3 forming no precipitation

Then, sodium nitrate solution was passed through the column. The effluent collected
was used to determine the blank.

Blank Determination

10cm3 of the effluent (0.30 mol dm-3 sodium nitrate) with added 2 drops of potassium
chromate as an indicator was titrated against standard silver nitrate solution that has
been diluted ten times. Table 1 shows the volume of diluted siver nitrate used for blank
titration.

Table 1: Volume of diluted silver nitrate used for blank titration

Titration 1 2
Initial burette reading/ mL 14.12 17.40
Final burette reading/ mL 16.00 19.40
Volume of diluted silver nitrate
1.88 2.00
added/ mL

Average Volume of diluted silver nitrate added = 1.94mL

1
Volume of standard silver nitrate used: 10 × 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑑𝑖𝑙𝑢𝑡𝑒𝑑 𝑠𝑖𝑙𝑣𝑒𝑟 𝑛𝑖𝑡𝑟𝑎𝑡𝑒 𝑢𝑠𝑒𝑑

= 0.194 mL
Therefore, for blank, we can see that 0.194ml of standard silver nitrate is required to
form silver chromate, Ag2CrO4. The end-point is determined when the colour of analyte
changes from yellow to red brown which indicates the formation of silver chromate.

Determination of chloride and bromide

After the solution of sodium chloride and potassium bromide added to the
column, 10ml of the effluent was titrated against standard silver nitrate solution with
potassium chromate as the indicator. A white precipitate is also formed together with
the colour change to red brown at the end point which indicates the formation of silver
halide. Table 2 shows the volume of standard silver nitrate used for titration against
10ml of effluent for the separation of chloride and bromide.

Table 2: Volume of standard silver nitrate used for titration against 10ml of effluent
for the separation of chloride and bromide.
Number
Volume of
of moles
Volume Initial Final standard Volume oh Concentrat
of burette burette silver of halide halide ion of
effluent reading reading nitrate reacted/ exist halide
/mL /mL /mL used/mL mL / mmol / mmol L-1
10 2.60 4.20 1.60 1.41 0.0703 7.03
20 4.20 8.40 4.20 4.01 0.2003 20.03
30 9.59 14.30 4.71 4.52 0.2258 22.58
40 14.40 22.50 8.10 7.91 0.3953 39.53
50 22.50 32.10 9.60 9.41 0.4703 47.03
60 32.10 39.20 7.10 6.91 0.3453 34.53
70 0.90 4.50 3.60 3.41 0.1703 17.03
80 4.50 8.40 3.90 3.71 0.1853 18.53
90 8.60 13.55 4.95 4.76 0.2378 23.78
100 14.20 19.45 5.25 5.06 0.2528 25.28
110 19.45 24.75 5.30 5.11 0.2553 25.53
 120 19.88 23.95 4.07 3.88 0.1938 19.38
130 23.95 26.90 2.95 2.76 0.1378 13.78
140 28.90 30.20 1.30 1.11 0.0553 5.53
150 30.20 31.10 0.90 0.71 0.0353 3.53
160 31.10 31.60 0.50 0.31 0.0153 1.53

Calculation for the concentration of halides ion in each fraction:

The concentration of the chloride ions and bromide ions can be determined
respectively from the concentration of AgCI and AgBr represented by the following
equations:

Ag+ (aq) + Cl- (aq) → AgCl (s)

Ag+ (aq) + Br- (aq) → AgBr (s)

From the titration result obtained,

Volume of halide reacted =

Volume of standard silver nitrate used(ml) – Volume of standard silver nitrate used for blank(0.194ml

The concentration of halide can be calculated using the formula:

𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒 𝑜𝑓 ℎ𝑎𝑙𝑖𝑑𝑒(𝑚𝑚𝑜𝑙)

Concentration of halide (mmol L-1) = 10𝑚𝑙 × 10−3

Where,

Number of mole of halide (mmol) =

𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑡𝑑. 𝑠𝑖𝑙𝑣𝑒𝑟 𝑛𝑖𝑡𝑟𝑎𝑡𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛(mmol L − 1) ×

𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 ℎ𝑎𝑙𝑖𝑑𝑒 𝑟𝑒𝑎𝑐𝑡𝑒𝑑(𝐿)

From the results obtained in table 2, we can plot a graph as shown in figure 3 below.
 Graph of concentration of halide against volume of
effluent Chloride ion
Bromide ion
concentration of halide/ mmol L-1 50.00
45.00
40.00
35.00
30.00
25.00
20.00
15.00
10.00
5.00
0.00
0 20 40 60 80 100 120 140 160 180
Volume of effluent/mL

Figure 3: Graph of concentration of halide against volume of effluent.

The percentage of halide ion recovered is calculated as shown below:-

𝑆𝑢𝑚 𝑜𝑓 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒 𝑜𝑓 ℎ𝑎𝑙𝑖𝑑𝑒 𝑐𝑜𝑙𝑙𝑒𝑐𝑡𝑒𝑑

Percentage of halide ion recovered= × 100%
𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒 𝑜𝑓 ℎ𝑎𝑙𝑖𝑑𝑒

For chloride,

The number of mole of chloride collected from each effluent is shown in table 3.

Table 3: Number of mole of chloride collected from each 10ml of effluent

Volume of effluent/mL Number of moles of chloride exist/

mmol
10 0.0703
20 0.2003
30 0.2258
40 0.3953
50 0.4703
60 0.3453
70 0.1703

The number of moles for first two readings are omitted as the flow rate was being
adjusted for the first 20 seconds. Therefore, the flow rate was unstable and the
number of moles of chloride exist is considered insignificant.
For effluent of volume 30ml to 70ml, the sum of number of moles of chloride
collected is 1.6070 mmol.

𝑚𝑎𝑠𝑠 𝑁𝑎𝐶𝑙 (𝑔)

The initial number of mole of chloride = 𝑅𝑀𝑀 𝑜𝑓 𝑁𝑎𝐶𝑙 (𝑔 𝑚𝑜𝑙−1)

0.1003𝑔
= 58.443 𝑔 𝑚𝑜𝑙−1

= 0.001716 mol

= 1.716 mmol

Thus,

1.607 𝑚𝑚𝑜𝑙
Percentage of Cl- ions recovered = x 100%
1.716 𝑚𝑚𝑜𝑙

= 93.65%

For bromide,

The number of mole of bromide collected from each effluent is shown in table 4.

Table 4: Number of mole of bromide collected from each 10ml effluent

Volume of effluent/mL Number of moles of bromide exist/

mmol
80 0.1853
90 0.2378
100 0.2528
110 0.2553
120 0.1938
130 0.1378
140 0.0553
130 0.0353
140 0.0153
150 0.1853
160 0.2378
For effluent of volume 80ml to 160ml, the sum of number of moles of bromide
collected is 1.3687 mmol.

𝑚𝑎𝑠𝑠 𝐾𝐵𝑟 (𝑔)

The initial number of mole of chloride = 𝑅𝑀𝑀 𝑜𝑓 𝐾𝐵𝑟 (𝑔 𝑚𝑜𝑙−1 )

0.2070𝑔
= 119.002 𝑔 𝑚𝑜𝑙−1

= 0.001739 mol

= 1.739 mmol

Thus,

1.369 𝑚𝑚𝑜𝑙
Percentage of Br- ions recovered = x 100%
1.739 𝑚𝑚𝑜𝑙

= 78.72%

The anion exchange resin are generally in the chloride form, but is converted into the
nitrate form by washing with sodium nitrate solution represented by the following
equation:
𝐑𝐞𝐬𝐢𝐧 − 𝐂𝐈 + 𝐍𝐎𝟑− ⟶ 𝐑𝐞𝐬𝐢𝐧 − 𝐍𝐎𝟑 + 𝐂𝐈 −

Concentrated nitrate ion will shift the equilibrium to the right while the chloride ion will
be replaced and eluted from the column. This is due to the concentration difference
between the nitrate ions and chloride ions. Separation is possible as bromide ion is
adsorbed stronger than the chloride ion because the equilibrium constant for Bromide
ion is higher than that of chloride ion. This causes the chloride ion to be eluted through
the column faster than bromide ions.

The ions were not 100% recovered from the column because a few errors occurred
while conducting this experiment. First of all, the flow rate of the column was not
maintained at 1cm3 per minute throughout the whole elution period. It was being
adjusted for the first 20 seconds and towards the end of the elution, the flow rate was
slightly increased due to time constraint. This could have been the reason why only
78.72% bromide ion was recovered as complete separation was not attained. Next,
sodium nitrate solution was poured a little quickly into the column which disrupted the
surface of column which was packed uniformly. The end point of the titration was also
overshoot at some points which could have caused inaccuracy in the results.
Therefore, a few precautions shall be taken when conducting this experiment. We
should always maintain the flow rate at 1cm3 per minute. The resin column should also
be packed uniformly with no air bubbles in the resin bed. The column should not be
left to dry. Next, while adding any solution into the column, a dropper should be used
or the solution should be poured in slowly to prevent the resin bed from being
disrupted. To avoid, overshooting, we should put a white paper below the conical flask
to observe the colour changes more clearly. The 10cm3 of effluent collected should be
titrated one by one and should not be mixed up.

Conclusions

The chromatographic separation of chloride ion and bromide ion from known amount
of chloride and bromide salt is successfully demonstrated. It is shown by the two
peaks observed on the graph of concentration of halide against volume of effluent.
The percentage of chloride ions recovered was 93.65% and the percentage of
bromide ion recovered was 78.72%.

Question and Answer

1. What is the role of chromatography in chemical analysis?

Chemical analysis refers to the determination of the physical properties or
chemical composition of samples of matter. The chemical composition of
matter can be known through various separating techniques (Braun, 2022).
Chromatography enables separation of mixtures for qualitative or
quantitative analysis. The separation is done based on characteristics such
as size and shape, total charge, hydrophobic groups present on the surface,
and binding capacity of the sample to be determined with the stationary phase
(Coskun, 2016). It is done through the movement of sample through a stationary
phase with the aid of a mobile phase.

2. Name the stationary phase and mobile phase used in this experiment.
Stationary phase: The resin-nitrate slurry
Mobile phase: Sodium nitrate solution

3. What is the meaning of ion-exchange in this study?

 In this study, the chemical group attached to the resin is negatively charged
NO3-. When NaCl and KBr is passed through the column, the cations(K+ and
Na+) acts as counter ions that will exchange its anions (Cl- and Br-) with the NO3-
attached to the resin (Ahern & Rajagopal, 2021). The exchange in the binding
between ions to separate chloride ions and bromide ion refers to the ion-
exchange in this study.

References

Braun, R. Denton (2022, August 1). chemical analysis. Encyclopaedia Britannica.

https://www.britannica.com/science/chemical-analysis

Coskun O. (2016). Separation techniques: Chromatography. Northern clinics of

Istanbul, 3(2), 156–160. https://doi.org/10.14744/nci.2016.32757

Ahern, K., & Rajagopal, I. (2021, December 26). 3.4.3. Ion Exchange
Chromatography. Chemistry LibreTexts. Retrieved November 21, 2022, from
https://chem.libretexts.org/Courses/University_of_Arkansas_Little_Rock/CHEM
_4320_5320%3A_Biochemistry_1/03%3A_Methods_of_Protein_Purification_a
nd_Characterization/3.4%3A_Chromatography/3.4.3._Ion_Exchange_Chromat
ography

Department of Chemistry, Faculty of Science, University of Malaya. (n.d.). Basic

Analytical Chemistry Second-Year Laboratory Manual. Retrieved from
https://kimia.um.edu.my/