Equilibria in aqueous solutions

pH-Titration: analysis of an alkali mixture

Objective

The purpose of this experiment is to determine the % composition of each basic

substance in a mixture by potentiometric titration.

Background

The qualitative and quantitative determination of constituents in a solution containing

sodium carbonate, sodium hydrogen carbonate and sodium hydroxide alone or mixed are a prime
example of the application of neutralization titrations. No more than two of these three
constituents can coexist because of reaction with the third. Thus, a mixture of sodium hydroxide
and sodium hydrogen carbonate will result in the formation of sodium carbonate until one of
these two is exhausted. So, only a combination of sodium hydroxide and sodium carbonate or a
mixture of sodium carbonate and sodium hydrogen carbonate can exist. The titration of such
mixtures will yield two end points. The composition of the solution can be derived from the
ratio of the volumes necessary to reach the end points.
Let’s say a solution contained one or more of the following species Na2CO3, NaHCO3
and NaOH. A 50-mL portion required 22.1 mL of .100 N HCl to reach the first end point when
titrated to a phenolphthalein end point. A second sample was titrated with bromocresol green as
the indicator, the solution being boiled near the second equivalence point in order to remove
CO2.] A total of 48.4 ml of HCl was required to reach the second end point Here exactly 48.4
mL of the HCl was used. What was the formal composition of the sample?
Had the sample contained only NaOH, no appreciable volume of acid would have been
required for titration from the first to second end point [the phenolphthalein to the bromocresol
green endpoint.] (That is, Vep1 = Vep2) On the other hand if only sodium hydrogen carbonate had
been present the solution would have been acidic to the first end point [the phenolphthalein end
point from the outset] (Vep1 = 0 ml) If only sodium carbonate had been present, the volume of
acid to reach the first end point [phenolphthalein end point] would have been exactly half of the
volume for the second end point [bromocresol green end point.] Since a total of 48.4 ml was
required for the second end point [bromocresol green end point], and the first end point
[phenolphthalein end point] was less than half this amount, the mixture must have contained
sodium carbonate and sodium hydrogen carbonate.

# moles of CO32- = (0.0221 L)(0.100 M) = 0.00221 moles

(1st end point) – (2nd end point) = (0.0484 - 0.0221) = 0.0263 L

# moles CO32- and HCO31- = (0.0263 l)(0.100 M) = 0.00263 moles

# moles HCO31- = 0.00263 - 0.00221 = 0.00042 moles

From this data we can calculate the initial concentration of each of the species.
 [Na2CO3] = 0.00221 moles/ 0.05000 L = 0.0442 M

[NaHCO3] = 0.00042 moles/ 0.05000 L = 0.0084 M

We are going to adopt a similar method for the analysis of the mixture of two alkalis.
One contains NaOH + Na2CO3 and the other contains Na2CO3 + NaHCO3. We use ca calibrated
pH probe to determine the endpoints. This process will give an accurate endpoint compared to
visual indicators. Shown below are the sample derivative plots for two types of mixtures to be
analyzed.

Derivative plot for NaO H + Na 2 CO 3 m ixture

3
d[pH] / dV

2 <--Na 2 CO 3 -->
<-------------------NaO H + Na 2 CO 3 ---------------->
1

0
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00
avg. volum e(m L) of acid added

D e r iv a tiv e p lo t fo r N a 2 C O 3 + N a H C O 3 m ix tu r e

4
d[pH] / dV

3
2 m o le s o f m o le s o f
< -- --- N a 2 C O 3 --- --> < --- ---- --- N a 2 C O 3 + N a H C O 3 --- ---- ---- --- >
1
0
0 5 10 15 20 25
a v e ra g e v o lu m e ( m L ) o f th e a c id a d d e d

Equipment
pH electrode connected to LabWORKS interfaced with a computer, thermometer, ice,
buret or a drop counter, pipet, volumetric flasks
Chemicals
Solutions of HCl (~0.1 M), NaOH (~0.1 M), buffer solution, distilled degassed water

Procedure

Standardization of NaOH

Fill the rinsed burette with NaOH solution provided. Make sure that the air trapped near
the stopcock is released before beginning the titration. Also, remove the funnel from the burette
top if used for filling the solution. Accurately weigh about 0.3 – 0.4 g of potassium acid
phthalate (KHP, MW 204.23 g/mol), transfer it to a 125 mL Erlenmeyer flask, and completely
dissolve it with the use of about 50 mL of distilled water. Add 1-2 drops of phenolphthalein
indicator, titrate it against faint pink endpoint, washing down the sides of the interior of the flask
with distilled water intermittently. Determine the molarity of NaOH with the use of 1:1
stoichiometry between KHP and NaOH. Determine the average molarity of NaOH from three
trials.

Standardization of HCl

Pipette out three different samples (say 10.00, 11.00 and 12.00 mL) of HCl solution in
three cleaned and labeled 125-mL Erlenmeyer flasks with the use of a clean rinsed pipette.
Dilute the solution to about 75 mL with distilled water. Add 10 drops of Bromothymol blue
indicator to each. Titrate the solution against the standardized NaOH to a persistent light blue
color washing down the sides of the interior of the flask with distilled water intermittently.
Determine the molarity of HCl with the use of 1:1 stoichiometry between HCl and NaOH and the
previously determined molarity of NaOH. Determine the average molarity of HCl from three
trials.

Sample Preparation
Weigh accurately about 1 gram of dry sample in a dry 50-mL beaker and dissolve the
sample in distilled water. Transfer this solution to a 250-mL volumetric flask and dilute it to the
mark with boiled and cooled water. Mix thoroughly and seal tightly.

Calibration of the pH electrode

Remove the electrode from the storage solution, rinse it with distilled water and blot the
water with tissue paper taking special precaution not to damage the electrode tip (made of special
soft glass). Dip this in a buffer solution of designated pH. In the “LABSER” menu of “Calibrate
instruments”, select “pH1” (make sure the electrode is connected to the input 1) and follow
instructions. Once calibrated, rinse the electrode with distilled water and blot it dry.

Titration of the sample solution

Pipette out 25.00 mL of the mixed alkali solution in a clean 250-mL Erlenmeyer flask
and add about 100 mL of distilled water to this solution. Insert the pH probe and be sure that the
tip of the probe is completely immersed in the solution. Invoke the experiment designed for
recording the pH-volume data in a spreadsheet format. Record the initial volume on the burette
and enter it in the spreadsheet. Add the HCl drop wise while monitoring the pH. Add enough
HCl to create a pH change of 0.3 units. Note, initially this will require quite a bit of HCl. As the
solution mixture approaches the end point the amount of HCl added to create this change would
get much smaller. Very close to the end point you may find that addition of a drop may cause a
pH change greater than 0.3. Continue adding HCl until you detect two regions where there were
large changes in the pH will small additions of acid. Continue this till you reach the pH of
around 2.5.

Sample pH versus volume of HCl and dpH/dV versus volume are shown below. Before
moving on to a different sample, make sure that you have attained a good set of data. Show the
plot to your instructor or TA to ensure that the data is of good quality. Anomalous data can result
from many errors possible especially if the solution not thoroughly mixed, or HCl was dropped
on the side of the electrode.
Data
De r ivative plot
14.00
12.00 3
10.00 2.5

d[pH] / dV
8.00 2
1.5
6.00
1
4.00
0.5
2.00 0
0.00 0.00 10.00 20.00 30.00 40.00
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 avg. volum e

Standardization of NaOH

Trial 1 Trial 2 Trial 3

Mass of KHP
Initial Buret reading
Final Buret reading
Volume of NaOH added (mL)
Moles of KHP
Molarity of NaOH
Average molarity of NaOH

Standardization of HCl

Trial 1 Trial 2 Trial 3

Volume of HCl
Initial Buret reading
Final Buret reading
Volume of NaOH added (mL)
Moles of NaOH
Molarity of HCl
Average molarity of HCl ±
Sample spreadsheet:

Sample # 1.048 grams of the sample is dissolved in 250 mL, 25.00 mL titrated against
0.0998 M HCl

Initial Buret Volume (mL) pH Difference Difference Average Derivative

Reading added in vol (dV) in pH (dPH) of V1& V2 dpH/dV

7.41 0.00 12.1303 0.22 0 0.11 0

7.63 0.22 12.1303 0.78 0.0335 0.61 0.0429
8.41 1.00 12.0968 0.83 0.0348 1.42 0.0419
9.24 1.83 12.0620 1.15 0.0335 2.41 0.0291
10.39 2.98 12.0285 0.79 0.0334 3.38 0.0423
11.18 3.77 11.9951 1.23 0.0516 4.39 0.0420
12.41 5.00 11.9435 1.76 0.0837 5.88 0.0476
14.17 6.76 11.8598 0.89 0.0670 7.21 0.0753
15.06 7.65 11.7928 1.16 0.0682 8.23 0.0588
16.22 8.81 11.7246 0.76 0.0657 9.19 0.0864
16.98 9.57 11.6589 1.11 0.0863 10.13 0.0777

Results

Enter the pH and volume data into a spreadsheet and plot the titration curve and the
derivative plot. From the derivative plot locate the volume of the two end points. Using these
volumes, the concentration of the acid and the sample sizes, calculate the composition of the
sample. Submit your result along with the data, plots and a sample calculation.

Analyze the possible sources of errors, these include, errors in sample mass, molarity of
NaOH, molarity of HCl, burette reading during the pH titration, pH reading during the titration.

The mass of each alkali calculated by respective end points should add up to the sample
mass. (Considering that you used only 25 mL of 250 mL solution, i.e. if the sample weighed is
1.00 grams, only 1/10th of it is used for titration) This also serves as an internal check for the
accuracy of your work.