CSUS - CH31 [Titrating Soda Ash (Na2CO3) with HCl] Instructor: J.T.

, 1

Note 01: A primary standard should essentially available in pure form , stable
towards light and heat and react in a stoichiometric proportion.

Note 02:
• HCl is not primary standards and need to be standardized.
• Why HCl is not a primary standard?
• Answer: because HCl is a gas which is dissolved in water to form the
solution the concentration expressed is very approximate.

I. Find the molarity of concentrated HCl:

M =
(d )(W % )(1000)
(M .W .)
Where: d: density (g/mL)
W%: mass percent (g solute / g solvent)
MW: Molar mass (molar weight) (g/mol)

M HCl =
(1.18)(0.38)(1000) = 12.30 mol / L
(36.46)
II. Make one liter of 0.1 M HCl:
Vc ⋅ M c = Vd ⋅ M d
III. To find exact concentration of HCl, dry (~ 140 °C) about 2 g of pure Na2CO3
as a primary standard reagent.
Note 03:
• How many grams of Na2CO3 Standard must be used?
• Answer: Suppose we want to use about 35.0 mL of 0.10 M of HCl from buret
for titration.
Na2CO3 + 2 HCl → 2 NaCl + H2CO3

0.035 L (HCl ) × mol (HCl )

0.10 mol
= 3.5 × 10− 3
L

1 mol Na 2 CO3 2 mol (HCl )

=
X 0.0035

X = 0.00175 mole of Na2CO3

Mass of Na2CO3 = (0.00175 mol) × (106.0 g/mol) = 0.1855 gram

∴ 0.1855 gram of Na2CO3 consumes 35.0 mL of 0.1 M, HCl
CSUS - CH31 [Titrating Soda Ash (Na2CO3) with HCl] Instructor: J.T., 2

Titration Sodium Carbonate with Hydrochloric acid:

pH

11

10
pH = pKa1 = 10.33

9
ΔpH I
8 pH ≅ 8.3
7

6 pH = pKa2 = 6.35

5
ΔV
ΔpH II
4 pH ≅ 4.05
3

10 20 V HCl
[H ][HCO ] = K
+ −
3
= 4.46 ×10 −7
[H 2 CO3 ] a1

[H ][CO ] = K
+ =
= 4.69 ×10 −11
[HCO ]
3
− a2
3
For the reign(I):
Δ pH 10.25 − 6.37
Na2CO3 + HCl → NaCl + NaHCO3 ≈ = 0.97
ΔV 4

For the reign (II):

Δ pH 6.37 − 2
NaHCO3 + HCl → NaCl + H2CO3 ≈ = 1.75
ΔV 2 .5

Δ pH
Larger means easer to see color change due change in pH.
ΔV

Since the second equivalence point is sharper and provides more accuracy.
CSUS - CH31 [Titrating Soda Ash (Na2CO3) with HCl] Instructor: J.T., 3

There are 3 ways to improve accuracy & precision of titration:

• Match titration solution to reference solution *.
Note 04: (Reference solution should have same pH, Indicator
Concentration and ionic strength)
• Heat solution (H2CO3→ CO2 + H2O)
• Back titration

* We are using the match titration solution.

Note 05: Methyl orange as indicator: there is a gradual smooth change from one
color to the other, taking place over a range of pH.

indicator pKind pH range

methyl orange 3.7 3.1 - 4.4

Make your reference solution:

a) Calculation pH (Where: n ≡ mole)

H2CO3 ' H+ + HCO3-

i-x x x

Where, i = [H2CO3]0 = (nH2CO3) / Vtotal

Vtotal = 60 mL (Na2CO3) + 35 mL (HCl) = 95 mL

(nH2CO3)= (n Na2CO3) = 1/2 (n HCl )

= 1/2 [0.1 (mmol/mL) × 35 mL] = 1.75 mmol

Note 06: 0.0001 mol/mL = 0.1 mmol/mL

i = (1.75 mmol) / (95 mL) = 0.0184 M

X2 /(i - x) = Ka1 ; Ka1= 4.45 × 10-7

[H+] = X = 9.05 × 10-5 ; pH = 4.04

b) Calculate for Sodium acetate-acetic acid buffer solutions solution with

pH = 4.04:
Note 07: pKa for acetic acid is 4.757
CSUS - CH31 [Titrating Soda Ash (Na2CO3) with HCl] Instructor: J.T., 4

pH = pKa + log
[A ]
−

[HA]

4.04 = 4.757 + log ([A-] / [HA])

[A ] = 0.1934
−

[HA]

c) Calculate the ionic strength:

1
μ= ∑
2 i
Ci ⋅ Z i2

Na2CO3 + 2 HCl → 2NaCl + H2CO3

Note 08: The only formed salt at equivalent point is sodium chloride.
[NaCl] = (nNaCl)/ Vtotal = nHCl / V total = 3.5 (mmol) / 95 (mL)

[NaCl] = 0.0368 M

μ=
1
2
[( ) (
0.0368 × 12 + 0.0368 × 12 )] = 0.0368

μ NaCl [ ]
= μ NaA = 0.0368 = A − = [NaCH 3COO ]

[A ] = 0.1934
−

[HA]
0.0368
= 0.1934
[HA]
[HA] = [CH3COOH] = 0.1903

d) Make 500 mL buffer solution from stock solutions:

M . V = M' . V'
(See the concentration labels of sodium acetate and acetic acid)
e) Make your reference solution with 95 mL buffer solution and same number
of drops methyl orange indicator.