Titration of Sodium Carbonate

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 Carbonate Chemistry
CO2 in atmosphere and dissolved in water
Major global buffering system
Industrial sources
limestone: CaCO3(s) + heat CaO(s) + CO2(g)
trona (Na2CO3) deposits

Air/Water Equilibrium

CO2 (aq) H2CO3 (aq)

2 HO
CO2 ( g)

Ionization in Water

H 2CO3 H HCO3 K a1 106.34

HCO3 H CO32 K a 2 1010.36
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 Titration of Na2CO3 with HCl
Step 1: Na2CO3 + HCl NaHCO3 + NaCl

Step 2: NaHCO3 + HCl H2CO3 + NaCl

Overall: Na2CO3 + 2HCl H2CO3 + 2NaCl

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At Ve1:
nNa2CO3 nHCl Ve1M HCl
10

Phenolphthalein
8
pH
6
At Ve2:
BCG
4 1 mol Na2CO3
nNa2CO3 nHCl
2 2 mol HCl
Ve1 Ve2 1 mol Na2CO3
0 Ve 2 M HCl
0 1 2 3
2 mol HCl
Equivalents of HCl added
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 Derivative Plots
Derivative plots can be used for accurate location of the equivalence point

Raw data Spreadsheet

First and Second
Derivative Plots
Click on Derivative
Plots tab

Raw data: pH vs V
1st derivative: d(pH)/dV
2nd derivative
2nd derivative: d2(pH)/(dV)2
Determination of Carbonate in a Sample
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A 1.2040-g sample containing sodium 10

carbonate and inert material was

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dissolved in water and titrated to the

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bromcresol green end point, requiring
4
32.50 mL of 0.1020 M HCl.
2

0
Calculate the % Na2CO3 in the sample. 0 1 2 3

For the BCG endpoint, the reaction is

Na2CO3 + 2HCl H2CO3 + 2NaCl

1 Na2 CO3
nNa2CO3 nHCl
2 HCl

M HCl mLHCl
1 0.105989 g
100
% Na2CO3
Wt Na2CO3
100 2 mmol
Wt sample 1.2040 g

% Na2CO3 = 14.59% 7
Effects of Carbonate Equilibria on
Titration of Carbonate

Shift in Phenolphthalein Endpoint

Boiling to Enhance Second Endpoint

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 Effect of Absorbed CO2 on Titration of Na2CO3 with HCl
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Ve1 Ve2 Ve1 decreases
10

8
Before Ve2 is not affected
pH

Use Ve2 for calculations

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2
1 Na2CO3
nNa2CO3 nHCl
2 HCl
0
0 10 20 30

Volume of HCl added, mL

1
M HCl Ve 2
14

12 2

10
After
8 CO2(g) + H2O(l) + CO32(aq) 2HCO3(aq)
pH

0
0 10 20 30 10
Volume of HCl added, mL
Boiling to Enhance Visual Endpoint in Titration of Na2CO3
with HCl
Na2CO3 + 2HCl H2CO3 + 2NaCl

NaHCO3

NaHCO3 Boiling removes H2CO3 as

+ gaseous CO2
H2CO3
H2CO3(aq) CO2(g) + H2O

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 Summary: Titration of Sodium Carbonate
Titration of Na2CO3 with strong acid yields two equivalence points

At phenolphthalein end point

Na2CO3 NaHCO3

At bromcresol green (or methyl red) end point

All carbonate is converted to H2CO3

pH of carbonate solutions may be unstable due to exchange of CO2

with atmosphere.

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