Estimation of Na2CO3 and NaOH in a mixture using standard ~ (N/20) HCl solution

Theory: The existence of two equivalence points on the titration of Na 2CO3 is due to the
fact that the neutralisation of Na 2CO3 solution by a strong acid like HCl occurs in two
steps:

Na2CO3 + HCl = NaHCO3 + NaCl [pH at equivalence point = 8.3]

NaHCO3 + HCl = NaCl + CO2 + H2O [pH at equivalence point = 3-4]

So at the half neutralisation point (pH = 8.3) phenolphthalein (pH range = 8.3-10) will
show its colour change from pink to colourless. Thus at this stage using phenolphthalein
as indicator, only half of the Na2CO3 and full amount of NaOH will be neutralised.

If the mixture is titrated using methyl orange as indicator (pH range = 3.1-4.4)
complete neutralisation will occur i.e. the titre value corresponds to full amount of
NaOH and Na2CO3.

½ Mole of Na2CO3 ≡ 1 Mole of NaOH ≡ 1equivalent

1000 mL 1 (N) HCl solution ≡ 53 g Na2CO3 ≡ 40 g NaOH

Chemicals required:
(a) Standard ~ (N/20) Na2CO3 solution
(b) Standard ~ (N/20) HCl solution
(c) Phenolphthalein indicator (0.5 % solution in 1:1 alcohol)
(d) Methyl orange indicator (0.05 % in water)
(e) Supplied mixture containing Na2CO3 and NaOH mixture

Procedure:
A) Preparation of 250 mL standard ~ (N/20) Na2CO3 solution
Required weight of Na2CO3 = 0.6625 g
Table-I
Initial weight Final weight Weight taken Strength (S1)=
(bottle+Na2CO3) (bottle+ Na2CO3) (w1-w2 )g w1-w2 /0.6625(N/20)
(w1g) (w2g)

Strength of Na2CO3 solution = S1(N)

B) Standardisation of HCl by standard ~ (N/10) Na2CO3 solution
25 mL of standard Na2CO3 solution is pipetted out in a 250 mL conical flask, 2
drops of methyl orange indicator is added, diluted with distilled water to 100 mL and
then titrated with continuous stirring with a glass rod or shaking the conical flask by
adding HCl solution from a burette drop by drop until the yellow colour just changes to
pale red. Burette reading is noted. This experiment is repeated until two concordant
reading are obtained.

Dr. Shyamapada Shit, Associate Professor in Chemistry, WBES.

 Table-II
No. of Vol. of Na2CO3 Burette reading (mL) Mean volume Strength of
obs. solution taken Initial Final Difference [V2 mL(say)] Na2CO3
(V1 mL) solution (S1)
1. 25
2. 25
3. 25

C) i) 25 mL of the supplied solution is pipetted out into a 250 mL conical flask, 2 drops of
phenolphthalein indicator is added, diluted to 100mL with distilled water. The solution is
then treated with (N/20) HCl by adding drop wise from a burette with constant shaking (or
stirring) until the pink colour just disappeared. Burette reading is noted (say V 3 mL),
corresponded to the half amount of Na2CO3 and the full amount of NaOH.
ii) To the above titrated solution two drops of methyl indicator is added. The solution turned
light yellow. Titration is continued with HCl running from the burette until yellow colour of
the solution changed to pale red. Titration is repeated trice to get concordant reading (say
the volume is V4 mL), corresponded to the half amount of Na2CO3.
Table-III
No. Vol. of Na2CO3 Burette reading (mL) Strength of
of + NaOH For first end point For second end point HCl
obs. mixture
solution taken Titre Average Titre Average
(V1 mL) value value
1. 25 V3 V4 S2(N)
2. 25 (say) (say)
3. 25
Calculation:
1. Strength of HCl = V1 x S1/V2 = S2 (N)
2. Half amount of Na2CO3 + full amount of NaOH in 25 mL mixture ≡ V3 ml of S2(N) HCl.
Half amount of Na2CO3 ≡ V4 ml of S2(N) HCl.
Thus, full amount of Na2CO3 in 25 mL mixture ≡ 2V4 ml of S2(N) HCl.
Again, full amount of NaOH in 25 mL mixture ≡ (V3-V4) ml of S2(N) HCl.

1000 mL 1(N) HCl ≡ 53 g Na2CO3

∴ 2V4 ml of S2(N) HCl ≡ 53 x2V4 xS2/1000 g Na2CO3
Now, 25 mL mixture solution contains = 53 x2V4 xS2/1000 g Na2CO3
1 L mixture solution contains = 53 x2V4 xS2 x 40 /1000 g Na2CO3 = P g/L (say) of Na2CO3.

Similarly, 1000 mL 1(N) HCl ≡ 40 g NaOH

∴ (V3-V4) ml of S2(N) HCl.≡ 40 x (V3-V4) xS2/1000 g NaOH
Now, 25 mL mixture solution contains = 40 x (V3-V4) xS2/1000 g NaOH
1 L mixture solution contains = 40 x (V3-V4) xS2 x 40 /1000 g NaOH = Q g/L (say) of NaOH.
__________________________________________________________________________

NOTE: [Stock supplied mixture is prepared by mixing 15 mL 1(N) NaOH and 35 mL of 1

(N) ~ (N/20) Na2CO3 and diluting the solution up to 1L by adding distilled water]

Dr. Shyamapada Shit, Associate Professor in Chemistry, WBES.