ANALYSIS OF CARBONATE MIXTURES

AIM

The main objective of this experiment is to determine the constituents in a solution containing
Na2CO3, NaHCO3 and NaOH alone or in a mixture by using titrimetry.

INTRODUCTION

Qualitative and quantitative determinations of the constituents in a solution containing Na2CO3,

NaHCO3 and NaOH alone or in a mixture provide an interesting example for neutralization
titrations. It is obvious that no more than two of these constituents can be present in a solution
together since the reaction between some of them eliminates the third one. Mixing of NaOH with
NaHCO3 results in the formation of Na2CO3 until one or the other (or both) of the original reactants
is used up.

NaOH + NaHCO3 → Na2 CO3 + H2 O

Analysis of such mixtures requires the use of two indicators in their titrations with standard acid
solutions. An indicator with a transition range in the pH range of 8 to 10, such as phenolphthalein,
is used for detecting the first end point; an acid range indicator such as bromocresol green is
used for the second end point. Titration can be done

A) In one sample, using both indicators by successive addition of acid solution after each
color change.
B) Using two samples containing exactly the same amount of mixture solution and applying
two indicators separately.

The composition of the solution can be obtained using the volumes of acid used for reaching the
each end point as shown in calculation part (Figure 1 and Table 1).

Table 1. Volume relationship in the analysis of carbonate and carbonate mixtures in the
titration of one sample.
Relationship between volume of acid needed
Composition to reach the phenolphthalein end point, (Vph)
and bromocresol green end point, (Vbcg)
a) NaOH Vphth>0, Vbcg=0
b) Na2CO3 Vphth = Vbcg
c) NaHCO3 Vphth=0 Vbcg>0
d) NaOH and Na2CO3 Vphth > Vbcg
e) Na2CO3 and NaHCO3 Vphth< Vbcg

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Figure 1. Titration curves for the analysis of mixtures containing sodium hydroxide, carbonate,
and hydrogen carbonate mixtures.
(a) NaOH, (b) Na2CO3, (c) NaHCO3 , (d) NaOH and Na2CO3, (e) Na2CO3 and NaHCO3

Here titration using one sample will be discussed.

REAGENTS AND APPARATUS

 Unknown NaOH, Na2CO3, NaHCO3 solutions (2 replicates for each student)

 Bromocresolgreen, phenolphthalein indicators (ready)
 Buret
 2 Erlenmeyer flasks of 250 mL
 100 mL graduated cylinder
 Wash bottle

PROCEDURE

A. Titration of Solutions with Known Composition but Unknown Quantity

In this experiment, 5 unknown solutions (2 replicates from each one) will be given to each student.
The list of unknown solutions is as follows:

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 Composition
1 NaOH alone
2 Na2CO3 alone
3 NaHCO3 alone
4 NaOH and Na2CO3
5 Na2CO3 and NaHCO3

Obtain two replicate solution with known composition but unknown quantity from your assistant
and to each unknown solution, the following procedure will be applied:
1) Add 100.0 mL distilled water using a graduated cylinder and 5-6 drops of phenolphthalein.
2) Titrate the solution with the standard HCl solution (standardized in the previous neutralization
titration experiment) until the pink color of indicator disappears. This corresponds
phenolphthalein end point (Vphth).
3) Then, add 4-5 drops of bromocresol green (blue) and carry the titration with the standard HCl
solution until a permanent green color appears. The volume of HCl used starting from the
first end point (see Fig. 1) gives the amount of HCl consumed to reach the bromocresol green
end point (Vbcg).
 After the observation of permanent green color, the sample solution is heated. By this
way buffering effect of HCO3- may be prevented and end point may be seen more easily.
If there is CO2 in the solution, the indicator should change from green color to blue as
CO2 is driven off during heating. When you see blue color, titrate this solution with 0.1 M
HCl till green color is observed and this additional amount of HCl has to be added to Vbcg
to determine end point.

B. Titration of a Solution with an Unknown Composition and Unknown Quantity

1) Obtain two replicate unknown solution from your assistant:
2) Apply the same procedure that is given in Section A for unknown solutions.
3) Record the volumes of standard HCl solution which are used to obtain phenolphthalein, Vphth,
and bromocresol green end points, Vbcg.
4) First determine the composition of the unknown solution using the relations given in Table 1
and then calculate the mass of the component(s) in your unknown solution for quantitative
determinations.

CALCULATIONS

Calculations for Titrations of NaOH, Carbonate and Carbonate Mixtures

Once the composition of the unknown solution is found then the mass of components in the
unknown solutions can be calculated as follows;

i. NaOH, NaHCO3, Na2CO3 alone

Mass of NaOH in mg = Vphth x MHCl x fwNaOH
Mass of NaHCO3 in mg = Vbcg x MHCl x fwNaHCO3

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 Vbcg + Vphth
Mass of Na2 CO3 in 𝑚𝑔∗ = ( ) x MHCl x fwNa2 CO3
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*For the analysis of Na2CO3 since Vphth and Vbcg are expected to be equal, the average of these
values can be used in calculations.

ii. For the mixture of NaOH and Na2CO3

Mass of NaOH in mg = (Vphth − Vbcg ) x MHCl x fwNaOH
Mass of Na2 CO3 in 𝑚𝑔∗ = (Vphth − Vbcg ) x MHCl x fwNaOH

mg NaOH = (Vphth-Vbcg) x MHCl x fw NaOH

mg Na2CO3 = Vbcg x MHCl x fw Na2CO3

iii. For the mixture of Na2CO3 and NaHCO3

mg Na2CO3 = Vphth x MHCl x fw Na2CO3
mg NaHCO3 = (Vbcg – Vphth) x MHCl x fw NaHCO3

where:
fw: formula weight in mg/mmol

PRE-LAB STUDIES

Read Applications of Neutralization Titrations from the textbook.

1) Draw a titration curve for a polyprotic acid (any diprotic acid you can choose) with a strong
base. Define all regions on the graph by writing related titration reactions.
2) Explain why NaOH, NaHCO3 and Na2CO3 cannot exist together and examine each case by
writing related reactions.

POST-LAB STUDIES

1) It is stated in Table 1 for the titration of NaHCO3 Vphth = 0; however, we consumed some small
amount of HCl to observe the color change. State reason(s) for that event.
2) Answer the following questions:
a) Why do we heat the solution after observing the bromocresol green end point? Write the
related reaction(s).
b) What does the color change from green to blue indicate?
c) If no color change is observed after heating, what does that indicate?
d) If additional acid is not required after boiling, what does that indicate? In this case, what is the
next step in the titration?
3) How did you decide the composition of your unknown? Sketch the titration curve
corresponding to your unknown composition.

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4) In the titration of NaOH and Na2CO3 mixture, three end points are expected; but there are two
end points observed corresponding to phenolphthalein and bromocresol green indicator.
Explain why?
5) The indicator Thymol Blue changes color (Blue to Yellow) over the same pH range as
Phenolphthalein. Why is Phenolphthalein a better choice of indicator than Thymol Blue?

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Name surname: Section: Date:

DATA SHEET
ANALYSIS OF CARBONATE MIXTURES
Experimental Results:

Concentration of HCl (standardized in neutralization titration experiment), M=

Uknown Replicate Volume of HCl (mL), Vphth Volume of HCl (mL), Vbcg
composition Number phenolphthalein end point bromocresol green end point
NaOH 1
2
Na2CO3 1
2
Na2HCO3 1
2
NaOH+ Na2CO3 1
2
Na2CO3+ Na2HCO3 1
2
Unknown 1
2

Unknown Composition: …………………………………………………..

True Values:

Concentration, M
NaOH
Na2CO3
NaHCO3

Uknown
Volume, mL
composition
NaOH
Na2CO3
Na2HCO3
NaOH+ Na2CO3
Na2CO3+ Na2HCO3
Unknown

Unknown Composition: …………………………………………………..

TA`s Name and Signature: