Acidimetric Analysis

Acidimetric Analysis
direct or residual
titrimetric analysis of a
base using an accurate
Titrant: acid volume of an acid

Analyte: base
Acidimetric analysis
Direct or residual titrimetric analysis of a base using an accurate volume of an acid
• Direct Titration
- Conducted by introducing a standard acid solution gradually from a burette
into a solution of the base being assayed

• Residual titration
- the basic sample is treated with an amount of standard acid known to be in
excess of a chemically equivalent amount, and the excess acid is subsequently
titrated with a standard base
Substances analyzed by acidimetry
• Organic substances Indicators
urea, sodium salicylate, • Methyl orange
diphenhydramine, emetine
• Methyl red
hydrochloride, meprobamate,
paramethadione, pyrazinamide • Methylene blue

• Inorganic substances • Bromocresol purple

sodium bicarbonate, milk of
magnesia, ammonium chloride,
calcium hydroxide, lithium
carbonate, zinc oxide
Double indicator titration

Made use in volumetric work to

determine the proportion of the
components of certain mixtures by
observing two end points in a
single titration
Compatible components in a mixture
• Generally, a mixture of either polyacidic base or polybasic acid
- Carbonates (CO32-), Bicarbonates (HCO3-), & Hydroxides (OH-)
- Phosphates (PO33-), dihydrogen phosphates (H2PO3-), and hydrogen
phosphates (HPO32-)
 determination of total alkalinity and sodium carbonate content
of sodium hydroxide

PP end point

MO end point
determination of total alkalinity and sodium carbonate content
of sodium hydroxide

Total Alkalinity
The total volume of an acid used in the titration to
neutralize a base calculated as sodium hydroxide
(NaOH)

mL x N x meq wt of NaOH x 100

%=
sample wt

mL x N x 0.0400 x 100
%=
sample wt
determination of total alkalinity and sodium carbonate content
of sodium hydroxide

Let’s establish
the following
✓ the volume of acid
consumed to reach the
PP endpoint is for NaOH
& Na2CO3
✓ the volume of acid
needed to neutralize
NaHCO3 to an MO
endpoint is equal to what
is needed to neutralize
Na2CO3 to a PP endpoint
determination of total alkalinity and sodium carbonate content
of sodium hydroxide

Let the following be

Vpp = total volume of acid
consumed to reach PP
endpoint
Vmo = total volume of acid
consumed to reach MO
endpoint
Vmo = VNaHCO3
Therefore, total volume to
neutralize Na2CO3

Vmo x 2
determination of total alkalinity and sodium carbonate content
of sodium hydroxide

Sodium Carbonate Content

(Vmo x 2) x N x meq wt of Na2 CO3 x 100
%=
sample wt

mL x N x 0.053 x 100
%=
sample wt
A 965.4-mg sample of sodium hydroxide required 20.80 mL of 1 N sulfuric
acid in titration to a phenolphthalein endpoint, and 21.75 mL of 1 N sulfuric
acid consumed in titration to a methyl orange end point.

Total Alkalinity
mL x N x 0.0400 x 100
%=
sample wt

% = 90.12%
A 965.4-mg sample of sodium hydroxide required 20.80 mL of 1 N sulfuric
acid in titration to a phenolphthalein endpoint, and 21.75 mL of 1 N sulfuric
acid consumed in titration to a methyl orange end point.

PROPORTION OF Na2CO3
Vpp = 20.80 mL; Vmo = 0.95 mL = VNaHCO3
Total volume to neutralize Na2CO3 = 0.95 mL x 2 = 1.90 mL

1.90 x 1 N x 0.053 x 100

%Na2CO3 = = 10.4%
0.9654 g
In titration of a 1.0900-g mixture of sodium carbonate (98.5% Na2CO3) with 0.9050N sulfuric
acid, what volumes would be necessary to produce (a) a phenolphthalein end point, (b) a
methyl orange end point?
✔ Neutralization of CO32- happens in two steps
✔ Each step consumes the same amount of volume, or
✔ The total volume required to neutralize is twice of the volume of any step
✔ Complete neutralization of CO32- happens at the methyl orange end point

𝑁 × 𝑉 × 𝑚𝑒𝑞 𝑤𝑡 × 100
%=
𝑤𝑡 𝑠𝑎𝑚𝑝𝑙𝑒
0.9050 𝑁 × 𝑉 × 0.053 × 100 Vphenolphthalein = 11.19 mL
98.5% =
1.0900
Vmethyl orange = 22.38 mL
98.5 × 1.0900
𝑉=
0.9050 𝑁 × 0.053 × 100
𝑉 = 21.18 𝑚𝐿
In a titration of a mixture of 0.5000 g of pure Na2CO3 and 0.4000 g of pure NaHCO3
with 1.1050 N sulfuric acid, what volume of the acid would be necessary to
(a) to produce a phenolphthalein endpoint and
(b) additionally to produce a methyl orange end point

VPP = VCO3 / 2

VMO = VCO3 / 2 + VHCO3

In a titration of a mixture of 0.5000 g of pure Na2CO3 and 0.4000 g of pure NaHCO3
with 1.1050 N sulfuric acid, what volume of the acid would be necessary to
(a) to produce a phenolphthalein endpoint and
(b) additionally to produce a methyl orange end point

VCO3 VHCO3
𝑤𝑡 𝑤𝑡
𝑁= 𝑁=
𝑉 × 𝑚𝑒𝑞 𝑤𝑡 𝑉 × 𝑚𝑒𝑞 𝑤𝑡 Vpp = VCO3 / 2
0.5000 𝑔 0.4000 𝑔
1.1050 𝑁 = 1.1050 𝑁 = Vpp = 8.54 / 2 = 4.27 mL
𝑉 × 0.053 𝑉 × 0.084
0.5000 𝑔 0.4000 𝑔
𝑉= 𝑉=
1.1050 𝑁 × 0.053 1.1050 𝑁 × 0.084
Vmo = VCO3 / 2 + VHCO3
𝑣𝑐𝑜3 = 8.54 𝑚𝐿 𝑉𝐻𝐶𝑂3 = 4.31 𝑚𝐿
Vmo = 4.27 + 4.31 = 8.58 mL
Calculate the proportion of (a) KOH, (b) K2CO3, (c) the total alkalinity in terms of KOH , in a
solution of potassium hydroxide, 25.00 mL of which required 26.00 mL of 0.8650 N sulfuric acid
in titration to a phenolphthalein end point and 31.15 mL of the same acid in titration to a methyl
orange end point

VPP = VCO3 / 2 + VOH

26.00 mL = VCO3 / 2 + VOH

VMO = VCO3 / 2
31.15 mL – 26.00 mL = VCO3 / 2
5.15 mL = VCO3 / 2
Calculate the Na2CO3 and NaHCO3 content of a 1.2500-g sample requiring 13.80 mL of 0.5250
N hydrochloric acid on titration to a phenolphthalein end point and an additional 16.30 mL on
further titration to a methyl orange end point.

VPP = VCO3 / 2
13.80 mL = VCO3 / 2

VMO = VCO3 / 2 + VHCO3

16.30 mL = VCO3 / 2 + VHCO3
 Nitrogen determination Kjeldahl method

The Kjeldahl method of nitrogen

Analytical chemistry is a method for
the quantitative determination
of nitrogen in chemical
substances developed by Johan
Kjeldahl in 1883.
analysis is the worldwide standard for
calculating the protein content in a
wide variety of materials ranging
from human and animal food,
fertilizer, wastewater and fossil
fuels.
 If the nitrogen of a compound is in the
trivalent state, an equivalent amount of
ammonia can be obtained as ammonium
sulfate by digestion of the sample with
concentrated sulfuric acid.
Principle
what really happens..
• The dried and homogenized material is pretreated with salicylic acid and sulfuric
acid to form the nitro derivatives with nitrite and nitrate.
• In the following step the nitro derivatives are reduced to the aminoform with
thiosulfate.
• After this the digestion in a suitable Kjeldahl tube with sulfuric acid takes place.
• To rise the temperature potassium sulfate is added and titanium dioxide/copper
sulfate is used as a catalyst.
• After adding sodium hydroxide to the digestion solution the produced ammonium
from all nitrogen species is evaporated by water steam distillation as ammonia.
• This is condensed in a conical flask with boric acid solution.
• The amount is titrated against indicator with sulfuric acid
• the sample is first digested in strong sulfuric
acid1 in the presence of a catalyst2, which helps
in the conversion of the amine nitrogen to
ammonium ions
• N  (NH4)2SO4
• Product: Ammonium sulfate; (NH4)2SO4
• To separate ammonia from the digestion
mixture
• (NH4)2SO4 + NaOH 
2NH3 + 2H2O + Na2SO4
• Product: Ammonia; NH3
• if boric acid1 is used as the receiving
solution instead of a standardized mineral
acid, the chemical reaction is
• NH3 + H3BO3  NH4H2BO3
• Product: Ammonium-borate complex
• The nitrogen content is then estimated by titration of the ammonium
borate formed with standard sulfuric or hydrochloric acid, using a
suitable indicator to determine the end-point of the reaction
• H2BO3- + H+ H3BO3
• Product: H3BO3; boric acid
• The concentration of hydrogen ions (in moles) required to reach the
end-point is equivalent to the concentration of nitrogen that was in
the original food
• H2BO3- + H+ H3BO3
• Product: Boric acid; H3BO3
has the advantages that only one standard
solution is necessary for the determination
and that the solution has a long shelf life
Boric acid method (direct titration)
Residual titration
• In back titration (commonly used in macro Kjeldahl), the ammonia is captured by a
carefully measured excess of a standardized acid solution in the receiving flask.
The excess of acid in the receiving solution keeps the pH low, and the indicator
does not change until the solution is "back titrated" with base.
• The ammonia can be distilled into an excess of standard strong acid (HCl or
H2SO4), and the excess determined by back titration with a strong standard base,
since the solution at the equivalence point contains (NH4)2SO4, or NH4Cl
Disadvantages of residual titration
• Ammonia may be collected into a solution of a strong acid (HCl or H 2SO4). The
excess of standard acid is instead usually titrated with a strong base.
• Two standard solutions are then needed:
1) titrant (NaOH solution) and
2) the strong acid in the receiver.
Acidimetric Analysis
End