PHAN111LEC_WEEK 8 Preparation and Standardization of 0.

1 N Silver
Ammonium Thiocynate
6) Standard Solution – Ammonium Thiocyanate
Precipitimetry/Argentometry/Saturation 7) Secondary Standard – 0.1 N Silver Nitrate
Method
• Árgentum = silver ENDPOINT DETERMINATION
• Determination of Halide-ions: bromide, 1. Cessation of precipitation or appearance of
chloride, mercury, fluoride, iodide → when turbidity
combined with silver, mercury or lead, 2. Instrumental Methods
produces precipitate a. When precipitate is being weighed, it
• Sample is titrated with a standard solution of becomes gravimetric method of
a precipitating agent in the presence of a analysis
suitable indicator b. Potentiometric Titration – use of
electrodes (through potentiometer)
Principles to measure the potentials of the
1) Solubility Product Principle solution during the titration process;
• Solubility Product Constant (Ksp) – good for colored substances but a
equilibrium constant of at solid slow, sensitive process for the
dissolving at a solution; represents reading to stabilize
the level of solubility; the more 3. Use of internal indicators
soluble, the higher the Ksp a. Colored Ion/Volhard’s Method by
Jacob Volhard
If Ionic product exceeds the Ksp, precipitation i. For chloride determination
occurs; if Ksp is less than Ksp, no precipitation ii. Ferric Alum or Ammonium
Iron (III) Sulfate (FAS) or
Ex. 𝐹𝑒𝑁𝐻4 (𝑆𝑂4 )2 is used using
Ammonium Thiocyanate VS
𝑁𝑎𝐶𝑙 + 𝐴𝑔𝑁𝑂3 → 𝐴𝑔𝐶𝑙 ↓ + 𝑁𝑎𝑁𝑂3 or 𝑁𝐻4 𝑆𝐶𝑁 as 2nd VS to
produce Ferric Thiocyanate
Analytes which is responsible for the
2) Those which form a very slightly soluble reddish-brown color
substance (precipitate) with the compound endpoint
in the standard solution iii. Residual Titration
• NaCl iv. Nitric Acid is used to prevent
• 𝐾𝐶𝑙3 precipitation of silver as
• Thiamine HCl carbonate or phosphate,
• Mustine Chloride – nitrogen mustard prevent hydrolysis of ferric
solution for anti-cancer therapeutics alum to form ferric oxide
• Carbromal – hypnotic sedative; in v. Acidic medium & NH4SCN
combination with phenobarbital inc. solubility which leads to
titration reading errors;
Standard Solutions solutions include:
3) Substances: 1. Nitrobenzene is used
• 𝐴𝑔𝑁𝑂3 to form a film for AgCl
• 𝑁𝐻4 𝑆𝐶𝑁 to prevent reaction
• 𝐾𝑆𝐶𝑁 with NH4SCN
2. Filtration of the
Preparation and Standardization of 0.1 N Silver precipitate
Nitrate Ex.
4) Standard Solution – Silver Nitrate Sol.
5) Primary Standard: Analytical Grade Sodium 𝑁𝑎𝐶𝑙 + 𝐴𝑔𝑁𝑂3 → 𝐴𝑔𝐶𝑙 ↓ + 𝑁𝑎𝑁𝑂3
Chloride 𝐴𝑔𝑁𝑂3 𝑒𝑥𝑐𝑒𝑠𝑠 + 𝑁𝐻4 𝑆𝐶𝑁 → 𝐴𝑔𝑆𝐶𝑁 + 𝑁𝐻4 𝑁𝑂3
 𝐹𝑒𝑁𝐻4 (𝑆𝑂4 )2 + 3𝑁𝐻4 𝑆𝐶𝑁 or
→ 𝑭𝒆(𝑺𝑪𝑵)𝟑 + 2(𝑁𝐻4 )2 𝑆𝑂4 2𝐶𝑁 − + 𝐴𝑔 → 𝐴𝑔(𝐶𝑁)2 ↓

b. Colored Secondary iii. Denige’s Method

Precipitate/Mohr’s Method by 1. For iodide ions
Friedrich Mohr e. Gay Lussac’s Method
i. Direct Method i. no indicator
ii. Potassium Chromate or ii. based on flocculation
𝐾2 𝐶𝑟𝑂 is used; yellowish, (amalgamation/clumping)
crystalline organic compound iii. not reliable
that yields toxic fumes when
heating, strong oxidation Calculations
agent used in textile dying 8) Gram equivalent weight is obtained by
iii. Endpoint is a reddish dividing the molecular weight by the total
secondary precipitate valence of the precipitating or precipitated
iv. Used to measure fluoride ion
ions 𝑀𝑊
𝑔. 𝑒𝑞. =
v. Neutral medium should be 𝑓
used; if alkaline, it produces 9) Precipitation methods can be divided into
NaOH, if acidic, CrO will direct and residual methods
become a dichromate
Ex. For Direct:

𝑁𝑎𝐶𝑙 + 𝐴𝑔𝑁𝑂3 → 𝐴𝑔𝐶𝑙 ↓ + 𝑁𝑎𝑁𝑂3 (𝑚𝐿) (𝑁) (𝑚𝐸𝑞)

𝐴𝑔𝑁𝑂3 + 𝐾2 𝐶𝑟𝑂 → 𝑨𝒈𝑪𝒓𝑶 ↓ + 𝐾𝑁𝑂3 %= 𝑥 100
𝑤𝑡

c. Colored Adsorption Product/Fajan’s For Residual:

Method by Kazimiers Fajan
i. Dicholorofluorescein is used [(𝑁1 𝑉1 ) − (𝑁2 𝑉2 )] (𝑚𝐸𝑞)
%= 𝑥 100
that adheres to the surface of 𝑤𝑡
AgCl to make it negatively
charged Practice
ii. From greenish yellow 1. A sample of ammonium bromide weighing
fluorescence to the endpoint 0.4128 g was dissolved in water, acidifed
of reddish-pink color with HNO3 and 50 mL of 0.1 N AgNO3
iii. Excess titration solution added. The excess of the latter
iv. Fluorescein TS is a weak acid, required 16.5 mL of 0.05015 N NH4SCN
which means that pH of soln. solution for titration. What is the percentage
should be slightly alkaline to purity of NH4Br in the sample?
keep the indicator in an anion
state 𝑁𝐻4 𝐵𝑟 = 14 (1) + 1 (4) + 80 (1)
Ex. = 98 / 1(1000)
= 0.098 𝑔/𝑚𝐸𝑞
𝑁𝑎𝐶𝑙 + 𝐴𝑔𝑁𝑂3 → 𝐴𝑔𝐶𝑙 ↓ + 𝑁𝑎𝑁𝑂3
𝐴𝑔𝐶𝑙− + 𝐴𝑔𝑁𝑂3 𝑒𝑥𝑐𝑒𝑠𝑠 → 𝑨𝒈𝑭 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑
[(𝑁1 𝑉1 ) − (𝑁2 𝑉2 )] (𝑚𝐸𝑞)
%= 𝑥 100
UNOFFICIAL USP METHODS 𝑤𝑡
%
d. Turbidity/Liebig’s Method [(0.1 𝑁 𝑥 50 𝑚𝐿) − (0.05015 𝑁 𝑥 16.5 𝑚𝐿)] (0.098 𝑔/𝑚𝐸𝑞)
i. For assay of cyanide =
0.4128 𝑔
𝑥 100
ii. Permanent cloudy/murky % = 𝟗𝟗. 𝟎𝟔 % 𝒐𝒇 𝑵𝑯𝟒𝑩𝒓
solution
Ex. 2. What volume of 0.05015 N thiocyanate
solution would be required to titrate the
𝐾𝐶𝑁 + 𝐴𝑔𝑁𝑂3 → 𝐾𝐴𝑔(𝐶𝑁)2 ↓ + 𝐾𝑁𝑂3 excess from 50 mL of 0.1 N AgNO3 that was
 added to a solution of 0.2215 g of NH4Cl
which is 99.5% pure? [(𝑁1 𝑉1 ) − (𝑁2 𝑉2 )] (𝑚𝐸𝑞)
%𝑁𝑎𝐶𝑙 = 𝑥 100
𝑤𝑡
𝑁𝐻4 𝐶𝑙 = 14 (1) + 1 (4) + 35(1) %𝑁𝑎𝐶𝑙 =
[(25 mL x 0.1 N ) − (12 mL x 0.09524 N )] (0.058 𝑔/𝑚𝐸𝑞)
𝑥 100
0.1423 𝑔
= 53 / 1(1000)
%𝑁𝑎𝐶𝑙 = 𝟒𝟓. 𝟕𝟖% 𝒐𝒇 𝑵𝒂𝑪𝒍
= 0.053 𝑔/𝑚𝐸𝑞

[(𝑁1 𝑉1 ) − (𝑁2 𝑉2 )] (𝑚𝐸𝑞)

[(𝑁1 𝑉1 ) − (𝑁2 𝑉2 )] (𝑚𝐸𝑞) %𝑁𝑎𝐵𝑟 = 𝑥 100
%= 𝑥 100 𝑤𝑡
𝑤𝑡 [(25 mL x 0.1 N ) − (12 mL x 0.09524 N )] (0.103 𝑔/𝑚𝐸𝑞)
%𝑁𝑎𝐵𝑟 = 𝑥 100
% [(𝑁1 𝑉1 ) − (𝑁2 𝑉2 )] (𝑚𝐸𝑞) 0.1423 𝑔
= %𝑁𝑎𝐵𝑟 = 𝟗𝟖. 𝟐𝟑% 𝒐𝒇 𝑵𝒂𝑩𝒓
100 𝑤𝑡
% (𝑤𝑡) = [(𝑁1 𝑉1 ) − (𝑁2 𝑉2 )] (𝑚𝐸𝑞)
% (𝑤𝑡) [(𝑁1 𝑉1 ) − (𝑁2 𝑉2 )] (𝑚𝐸𝑞) 4. A 0.2182 g sample of NaCl was assayed by
=
𝑚𝐸𝑞 𝑚𝐸𝑞 the Volhard method using 50.00 mL of
% (𝑤𝑡) 0.0985 N silver nitrate and 11.75 mL of
= (𝑁1 𝑉1 ) − (𝑁2 𝑉2 ) 0.1240N ammonium thiocyanate Calculate
𝑚𝐸𝑞
1 % (𝑤𝑡) 1 the percent NaCl in the sample.
[(𝑁2 𝑉2 )] = [ − (𝑁1 𝑉1 ) +]
𝑁2 𝑚𝐸𝑞 𝑁2
𝑁𝑎𝐶𝑙 = 23 (1) + 35 (1)
% (𝑤𝑡) (𝑁1 𝑉1 )
𝑉2 = − = 58/1(1000)
𝑚𝐸𝑞 𝑥 𝑁2 𝑁2 = 0.058 𝑔/𝑚𝐸𝑞
0.995 (0.2215 g) (0.1 N x 50 mL ) [(𝑁1 𝑉1 ) − (𝑁2 𝑉2 )] (𝑚𝐸𝑞)
𝑉2 = − %𝑁𝑎𝐶𝑙 = 𝑥 100
0.053 𝑔 𝑥 0.05015 N 0.05015 N 𝑤𝑡
𝑉2 = 𝟏𝟔. 𝟕𝟖 𝒎𝑳 𝒐𝒇𝟎. 𝟎𝟓𝟎𝟏𝟓 𝐍 𝐭𝐡𝐢𝐨𝐜𝐲𝐚𝐧𝐚𝐭𝐞 𝐬𝐨𝐥𝐮𝐭𝐢𝐨𝐧 %𝑁𝑎𝐶𝑙 =
[(0.0985 N 𝑥 50.00 mL) − (0.1240N x 11.75 mL)] (0.058 𝑔/𝑚𝐸𝑞)
𝑥 100
0.2182 g

3. A mixture consisting of pure NaCl and pure %𝑁𝑎𝐵𝑟 = 𝟗𝟐. 𝟏𝟖% 𝒐𝒇 𝑵𝒂𝑪𝒍
NaBr weighs 0.2845 g. It was dissolved in 20
mL of purified water in a 100 mL volumetric
flask, 50 mL of 0.1 N AgNO3 and 3 mL of
HNO3 added diluted with purified water to
the mark, stoppered and shaken thoroughly
until the mixture was uniform. This was
filtered and the first 20 mL of the filtrate
was discarded. The next 50 mL of the filtrate
was treated with 2 mL of ferric alum
indicator solution and titrated with 0.09524
N ammonium solution requiring 12 mL of
the latter to reach the endpoint. What is the
percentage of NaBr and NaCl in the sample?

0.2845 𝑔
𝑥 50 𝑚𝐿 = 0.1423 𝑔 𝑜𝑓 𝑁𝑎𝐶𝑙 𝑎𝑛𝑑 𝑁𝑎𝐵𝑟
100 𝑚𝐿
50 𝑚𝐿
𝑥 50 𝑚𝐿 = 25 𝑚𝐿 𝑜𝑓 𝐴𝑔𝑁𝑂3
100 𝑚𝐿

𝑁𝑎𝐶𝑙 = 23 (1) + 35 (1)

= 58/1(1000)
= 0.058 𝑔/𝑚𝐸𝑞

𝑁𝑎𝐵𝑟 = 23 (1) + 80 (1)

= 103/1(1000)
= 0.103 𝑔/𝑚𝐸𝑞
 PHAN111LEC_WEEK 9 • Ligand – electron pair donor or a Lewis base;

HNP is used for calcium-containing compounds

COMPLEXOMETRY/COMPLEXIMETRY Eriochrome Black TS is used for zinc-containing
1. Analysis of metals compounds
2. Determine hardness of water due to calcium
and magnesium salts, calcium compounds, has the ability to bind with the metal ion and
and their preparations, and determination of produce a complex
deficiencies in the body’s minerals o Monodentate/Unidentate
▪ “one-toothed”; donates one
Hardness in water is due to the presence of Ca and pair of electron
Mg salts; soaps cannot foam; can clog pores and ▪ Forms more stable complexes
cause itching and flaking; can cause kidney stones than polydentates
o Polydentate/Multidentate
Temporary Hardness is caused by bicarbonates and ▪ “many toothed”; donates
can be destroyed by boiling
more than one pair
Permanent Hardness is caused by sulfates and ▪ Example: EDTA which is a
chlorides of Ca and Mg and cannot be affected by hexadentate
boiling • metal ion with chelating agents
• Chelating Agents – substance that can form
Total Hardness – represented by combined
several bonds with a metal; multidentate
temporary and permanent hardness and can be
ligand; forms complexes that are insol. in
determined by titration with EDTA
water, but sol. In organic solvents; used to
• Recommended conc. for drinking water
prevent further reaction of the metal ion
o 40-80 ppm Ca content
o 20-30 ppm Mg content without removing it from the solution
o Total hardness of both must be 2-4 o Examples: Dimethylglyoxime and
moles/L Salicylaldoxime
• Sequestering Agents – chelating agents that
Conc. as CaCO3 Indication form water-soluble complexes with metal
0-60 mg/L Soft water ions; used to remove water hardness
60-120 mg/L Moderately hard water o Combines with calcium and
120-180 mg/L Hard water
magnesium ions and other heavy
>180 mg/L Very hard water
metals
3. Formation of a complex substance
Indicators
4. EDTA (Ethylenediaminetetraacetic acid)
reaction with metal ions to form a water- • Qualities of a good indicators are:
o Sharp color change at endpoint
soluble stable complex or a chelate
compound o Specificity of the indicator for the
o Standardized with CACO3 metal ion under the conditions of
o Indicators used: Hydroxynapthol- the analysis
blue TS, Eriochrome Black TS, or o Have a stability constant smaller
than that of the metal-EDTA
Dithiazone TS
complex
Principle and Concepts o Indicator must give up the metal ion
to the titrant EDTA for complexing
• When a metal ion combines with a molecule
o Should not compete with the EDTA
which donate electrons (reducing agents) =
complex
• When a metal ion combines with a molecule
that contains two or more groups that
donate electrons = chelate
 unreactive to other chelating agents or form
a more stable complex with EDTA
Ex.
𝑀𝑛 + 𝑀𝑔𝐸𝐷𝑇𝐴 → 𝑀𝑔 + 𝑀𝑛𝐸𝐷𝑇𝐴

4. Indirect Titration – used for determination

of ions that do not react with EDTA;
protons from disodium EDTA are displaced
by heavy metal and titrated with sodium
alkali
Ex.
Assay of barbiturates using mercuric ion solution

Factors That Increases Selectivity in EDTA

• Use of masking agents and de-masking
agents
EDTA/Ethylenediaminetetraacetic Acid
o Masking - used to indicate the
• Unselective reagent because it can form
determination of a metal in the
complexes with many charged cations
presence of another metal through
• Disodium salt is preferred over the free acid adjusting the pH or with the use of
in preparing standard sol. of EDTA due to: auxiliary complexing agents such as:
o Being more water-soluble TEA, Thioglycols, Potassium cyanide,
o Non-hygroscopic ammonium fluoride, ascorbic acid,
o Very stable
tartrates, and citrates
• Chemical formula: 𝐶10 𝐻14 𝑁2 𝑁𝑎2 𝑂8 • 2𝐻2 𝑂 ▪ Masking by precipitation
• MW: 372.24 g/mEq ▪ Masking by complex
• Standardization: formation
o An accurately weighed sample of o De-masking – masked substances
calcium carbonate is diluted with 50 regains its ability to enter into a
mL of water, sufficient dilute HCl reaction
acid is added to dissolve the
carbonate and then is then diluted to
150 mL. The mixture is titrated with
EDTA. Calculate the M of the
volumetric solution.

TYPES OF COMPLEXOMETRIC TITRATIONS

1. Direct Titration – simplest and most
convenient method similar to acid-base
titrations but is a slow complex formation;
Ex.
Assay of Calcium Chloride

2. Residual Titration – standard EDTA is added

to the metal solution, excess is backtitrated
• pH control – based on differences in
with another standard solution
stability of the chelates formed between the
Ex.
metal ions and the chelating agent as
Determination of Manganese (EDTA, Zinc VS,
stability of metal complex is pH dependent;
Eriochrome Black TS)
most ligands are basic and bind to H+ ions
hence, ↓pH = less stable
3. Replacement Titration/Substitution – metal
• Use of selective metal indicator – should be
to be analyzed displaces quantitatively from
sufficiently rapid to establish end point
the complex; used for metals that are
without undue waiting
 • Classical Separation – separate ion using dissolved in 500 mL of a solvent. Another 50
precipitation, then redissolve into a solution mL portion of the water sample was treated
for determination with K2C2O4 (potassium oxalate) and the
Ex. resulting mixture consumed 10 mL of EDTA.
CaC2O4, nickel dimethylglyoximate, and CUSCN Find the hardness in ppm in terms of
Calcium Carbonate. Interpret your result.
• Solvent Extraction – separation of metal by
adding excess solution to which will be 𝐶𝐴𝐶𝑂3 = 40(1) + 12 (1) + 16 (3)
diluted in water with EDTA, and then will be = 100 𝑔/𝑚𝑜𝑙
determined
Ex. 0.2155 g
𝑥 25 𝑚𝐿 = 0.0108 𝑔 𝑜𝑓 𝐶𝐴𝐶𝑂3
Zinc can be separated from copper and lead by 500 𝑚𝐿
adding excess ammonium thiocyanate solution and
extracting the resulting zinc thiocyanate with 4- 𝑤𝑡
𝑀=
methylpentan-2-one (isobutyl methyl ketone); the 𝑀𝑊 𝑥 𝐿
0.0108 𝑔
extract is diluted with water with EDTA solution 𝑀=
and the zinc content is determined 100 𝑔/𝑚𝑜𝑙 𝑥 0.02065 𝐿
𝑀 = 0.0052 𝑀 𝑜𝑟 𝑚𝑜𝑙/𝐿 𝑜𝑓 𝐸𝐷𝑇𝐴
• Removal of Anions – anions can interfere 0.0052 𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 100 𝑔 1000 𝑚𝑔
with complexometric titrations; they are 𝑚𝑔 𝑜𝑓 𝐶𝐴𝐶𝑂3 (1𝑠𝑡) = 32.50 mL 𝑥
1000 𝑚𝐿
𝑥
1 𝑚𝑜𝑙
𝑥
1𝑔
removed using ion exchange resins = 16.9 𝑚𝑔 𝑜𝑓 𝐶𝐴𝐶𝑂3 𝑖𝑛 𝑤𝑎𝑡𝑒𝑟

Ex. 1𝐿
Used in water filtration 50 𝑚𝐿 𝑥 = 0.050 𝐿
1000 𝑚𝐿

• Kinetic Masking – special case in which 16.9 𝑚𝑔

𝑝𝑝𝑚 =
metal ion does not effectively enter into 0.050 𝐿
complexation because of its kinetic inertness 𝑝𝑝𝑚 = 𝟑𝟑𝟖 𝒎𝒈/𝑳 𝒘𝒉𝒊𝒄𝒉 𝒄𝒐𝒏𝒄𝒍𝒖𝒅𝒆𝒔 𝒕𝒐 𝒂 𝒗𝒆𝒓𝒚 𝒉𝒂𝒓𝒅 𝒘𝒂𝒕𝒆𝒓
(little to no ability to react); masking
kinetically to speed the rate of reaction 0.0052 𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 100 𝑔 1000 𝑚𝑔
𝑚𝑔 𝑜𝑓 𝐶𝐴𝐶𝑂3 (2𝑛𝑑) = 10 mL 𝑥 𝑥 𝑥 = 16.9 ==
1000 𝑚𝐿 1 𝑚𝑜𝑙 1𝑔
Practice = 5.2 𝑚𝑔 𝑜𝑓 𝐶𝐴𝐶𝑂3 𝑖𝑛 𝑤𝑎𝑡𝑒𝑟

1. A 50 mL water sample was determined for 5.2 𝑚𝑔

hardness in terms of CaCO3. It required 40 𝑝𝑝𝑚 =
0.050 𝐿
mL of a 0.01 M EDTA solution for titration. 𝑝𝑝𝑚
Calculate the total hardness in ppm (mg/L). = 𝟏𝟎𝟒 𝒎𝒈/𝑳 𝒘𝒉𝒊𝒄𝒉 𝒄𝒐𝒏𝒄𝒍𝒖𝒅𝒆𝒔 𝒕𝒐 𝒎𝒐𝒅𝒆𝒓𝒂𝒕𝒆𝒍𝒚 𝒉𝒂𝒓𝒅 𝒘𝒂𝒕𝒆𝒓
Interpret your result.
3. A sample of CaCl2 weighing 1.378 g was
𝐶𝐴𝐶𝑂3 = 40(1) + 12 (1) + 16 (3) dissolved in water and diluted to 250 mL. 50
= 100 𝑔/𝑚𝑜𝑙 mL of this solution was titrated with 38.2 mL
of 0.048 M disodium edentate. If each mL of
0.01 𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 100 𝑔 1000 𝑚𝑔 0.05 M disodium acetate is equivalent to
𝑚𝑔 𝑜𝑓 𝐶𝐴𝐶𝑂3 = 40 𝑚𝐿 𝑥 𝑥 𝑥
1000 𝑚𝐿 1 𝑚𝑜𝑙 1𝑔 7.351 mg of 𝐶𝑎𝐶𝑙2 • 2𝐻2 𝑂. What is the
= 40 𝑚𝑔 𝑜𝑓 𝐶𝐴𝐶𝑂3 𝑖𝑛 𝑤𝑎𝑡𝑒𝑟 percentage purity of 𝐶𝑎𝐶𝑙2 • 2𝐻2 𝑂? USP
1𝐿 specs: 99-107%
50 𝑚𝐿 𝑥 = 0.050 𝐿
1000 𝑚𝐿
Formula 1:
40 𝑚𝑔 𝑉 𝑥 𝑁 𝑥 𝑚𝐸𝑞
𝑝𝑝𝑚 = % 𝑝𝑢𝑟𝑖𝑡𝑦 = 𝑥 100
0.050 𝐿
𝑝𝑝𝑚 𝑤𝑡
= 𝟖𝟎𝟎 𝒎𝒈/𝑳 𝒕𝒐𝒕𝒂𝒍 𝒉𝒂𝒓𝒅𝒏𝒆𝒔𝒔, 𝒘𝒉𝒄𝒉 𝒄𝒐𝒏𝒄𝒍𝒖𝒅𝒆𝒔 𝒕𝒐 𝒃𝒆 𝒖𝒏𝒅𝒆𝒓 𝒗𝒆𝒓𝒚 𝒉𝒂𝒓𝒅 𝒘𝒂𝒕𝒆𝒓 Formula 2:
𝐿 𝑜𝑓 𝑡𝑖𝑡𝑟𝑎𝑛𝑡 𝑥 𝑀 𝑥 𝑀𝑊
2. A 50 mL water sample was titrated with % 𝑝𝑢𝑟𝑖𝑡𝑦 = 𝑥 100
𝑤𝑡
32.50 mL of disodium edentate. 20.65 mL Formula 3:
of this EDTA was used to titrate 25 mL of a 𝑡𝑖𝑡𝑒𝑟 𝑥 𝑚𝐿
% 𝑝𝑢𝑟𝑖𝑡𝑦 = 𝑥 100
calcium carbonate solution. A 0.2155 g of 𝑤𝑡
pure calcium carbonate was acidified and
 0.0101 𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 84 𝑔 1000 𝑚𝑔
𝑚𝑔 𝑜𝑓 𝑀𝑔𝐶𝑂3 (2𝑛𝑑) = 3.7 mL 𝑥 𝑥 𝑥
1000 𝑚𝐿 1 𝑚𝑜𝑙 1𝑔
𝐶𝑎𝐶𝑙2 • 2𝐻2 𝑂 = 40 (1) + 35 (2) + 1(4) + 16(2) = 3.1391 𝑚𝑔 𝑜𝑓 𝑀𝑔𝐶𝑂3 𝑖𝑛 𝑤𝑎𝑡𝑒𝑟
= 146 𝑔/𝑚𝑜𝑙
3.1391 𝑚𝑔
1.378 𝑔 𝑝𝑝𝑚 =
𝑥 50 𝑚𝐿 = 0.2756 𝑔 𝑜𝑓 𝐶𝑎𝐶𝑙2 0.020 𝐿
250 𝑚𝐿 𝑝𝑝𝑚 = 𝟏𝟓𝟔 𝒎𝒈/𝑳 𝒘𝒉𝒊𝒄𝒉 𝒄𝒐𝒏𝒄𝒍𝒖𝒅𝒆𝒔 𝒕𝒐 𝒉𝒂𝒓𝒅 𝒘𝒂𝒕𝒆𝒓

0.0382 𝐿 𝑥 0.048 𝑀 𝑥 146 𝑔/𝑚𝑜𝑙 5. Calculate the calcium carbonate content of a

% 𝐶𝑎𝐶𝑙2 • 2𝐻2 𝑂 = 𝑥 100
0.2756 𝑔 sample chalk weighing 0.2545 g and
%𝐶𝑎𝐶𝑙2 • 2𝐻2 𝑂 = 𝟗𝟕. 𝟏𝟒 % 𝒐𝒇 𝑪𝒂𝑪𝒍𝟐 • 𝟐𝑯𝟐 𝑶 consuming 26.67 mL of 0.1150 M EDTA
solution in titration

4. A 20 ml water sample was titrated with 3.50 𝐶𝑎𝐶𝑂3 = 40(1) + 12 (1) + 16 (3)
mL of disodium edentate. 8.56 mL of this = 100 𝑔/𝑚𝑜𝑙
EDTA was used to titrate 15 mL of a calcium
carbonate solution. A 0.145 g of pure
calcium carbonate was acifidied and 1𝐿
dissolved in 250 mL of a solvent. Another 20 26.67 𝑚𝐿 𝑥 = 0.027 𝐿
1000 𝑚𝐿
mL portion of the water sample was treated
with K2C2O4 and the resulting mixture 𝐿 𝑜𝑓 𝑡𝑖𝑡𝑟𝑎𝑛𝑡 𝑥 𝑀 𝑥 𝑀𝑊
% 𝑝𝑢𝑟𝑖𝑡𝑦 = 𝑥 100
consumed 3.7 mL of EDTA. Find the 𝑤𝑡
hardness in ppm in terms of magnesium 0.027 𝐿 𝑥 0.1150 M 𝑥 100 𝑔/𝑚𝑜𝑙
% 𝑝𝑢𝑟𝑖𝑡𝑦 = 𝑥 100
carbonate. Interpret your result. 0.2545 g
0.027 𝐿 𝑥 0.1150 M 𝑥 100 𝑔/𝑚𝑜𝑙
% 𝑝𝑢𝑟𝑖𝑡𝑦 = 𝑥 100
𝐶𝑎𝐶𝑂3 = 40(1) + 12 (1) + 16 (3) 0.2545 g
= 100 𝑔/𝑚𝑜𝑙 % 𝑝𝑢𝑟𝑖𝑡𝑦 = 𝟏𝟐𝟐. 𝟎𝟎 % 𝒐𝒇 𝑪𝒂𝑪𝒍
𝑀𝑔𝐶𝑂3 = 24(1) + 12 (1) + 16 (3)
= 84 𝑔/𝑚𝑜𝑙 6. How many grams of disodium EDTA acetate
or 𝐶10 𝐻14 𝑁2 𝑁𝑎2 𝑂8 • 2𝐻𝑂 is required to
0.145 g prepare 250 mL of a 0.025 M solution?
𝑥 15 𝑚𝐿 = 0.0087 𝑔 𝑜𝑓 𝐶𝐴𝐶𝑂3
250 𝑚𝐿 What would be the titer of this solution in
terms of 𝐶𝑎𝐶𝑙2 • 2𝐻2 𝑂, 𝑀𝑔𝑆𝑂4, 𝑎𝑛𝑑 𝑍𝑛𝐶𝑙2?
1L
8.56 𝑚𝐿 𝑥 = 0.0086 𝐿 𝑜𝑓 𝐸𝐷𝑇𝐴
1000 𝑚𝐿 𝑤𝑡
𝑀=
𝑀𝑊 𝑥 𝐿
𝑀 (𝑀𝑊)(𝐿) = 𝑤𝑡
𝑤𝑡
𝑀=
𝑀𝑊 𝑥 𝐿
0.0087 𝑔 (0.025 M) (371)(0.250 𝐿) = 𝑤𝑡
𝑀=
100 𝑔/𝑚𝑜𝑙 𝑥 0.0086 𝐿 𝟐. 𝟑𝟏𝟖𝟖 𝒈 𝒐𝒇 𝑬𝑫𝑻𝑨 𝒂𝒄𝒆𝒕𝒂𝒕𝒆 = 𝑤𝑡
𝑀 = 0.0101 𝑀 𝑜𝑟 𝑚𝑜𝑙/𝐿 𝑜𝑓 𝐸𝐷𝑇𝐴
𝑡𝑖𝑡𝑒𝑟 = 𝑀 (𝑀𝑊 )(0,001 𝐿)
0.0101 𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 84 𝑔 1000 𝑚𝑔
𝑚𝑔 𝑜𝑓 𝑀𝑔𝐶𝑂3 (1𝑠𝑡) = 3.50 mL 𝑥 𝑥 𝑥 𝑡𝑖𝑡𝑒𝑟 = 0.025 𝑀 (146 𝑔/𝑚𝑜𝑙)(0,001 𝐿)
1000 𝑚𝐿 1 𝑚𝑜𝑙 1𝑔
= 2.9694 𝑚𝑔 𝑜𝑓 𝑀𝑔𝐶𝑂3 𝑖𝑛 𝑤𝑎𝑡𝑒𝑟 𝑡𝑖𝑡𝑒𝑟 = 𝟑. 𝟔𝟓 𝒎𝒈/𝒎𝑳 𝒐𝒇 𝑪𝒂𝑪𝒍𝟐 • 𝟐𝑯𝟐 𝑶

1𝐿 𝑡𝑖𝑡𝑒𝑟 = 0.025 𝑀 (120 𝑔/𝑚𝑜𝑙)(0,001 𝐿)

20 𝑚𝐿 𝑥 = 0.020 𝐿 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑡𝑖𝑡𝑒𝑟 = 𝟑 𝒎𝒈/𝒎𝑳 𝒐𝒇 𝑴𝒈𝑺𝑶𝟒
1000 𝑚𝐿

2.9694 𝑚𝑔 𝑡𝑖𝑡𝑒𝑟 = 0.025 𝑀 (135 𝑔/𝑚𝑜𝑙)(0,001 𝐿)

𝑝𝑝𝑚 = 𝑡𝑖𝑡𝑒𝑟 = 𝟑. 𝟑𝟕𝟓 𝒎𝒈/𝒎𝑳 𝒐𝒇 𝒁𝒏𝑪𝒍𝟐
0.020 𝐿
𝑝𝑝𝑚 = 𝟏𝟒𝟖. 𝟒𝟕 𝒎𝒈/𝑳 𝒘𝒉𝒊𝒄𝒉 𝒄𝒐𝒏𝒄𝒍𝒖𝒅𝒆𝒔 𝒕𝒐 𝒉𝒂𝒓𝒅 𝒘𝒂𝒕𝒆𝒓

7. A 200 mg sample of pure calcium carbonate

was acidified and dissolved in 500 mL of
solution. A 50 mL sample required 25 mL of
an EDTA solution for titration. Find the
molarity of the EDTA solution.

𝐶𝑎𝐶𝑂3 = 40(1) + 12 (1) + 16 (3)

= 100 𝑔/𝑚𝑜𝑙

0.2 g
𝑥 50 𝑚𝐿 = 0.02 𝑔 𝑜𝑓 𝐶𝐴𝐶𝑂3
500 𝑚𝐿
𝑤𝑡
𝑀=
𝑀𝑊 𝑥 𝐿
0.02 𝑔
𝑀=
100 𝑔/𝑚𝑜𝑙 𝑥 0.025 𝐿
𝑀 = 𝟎. 𝟎𝟎𝟖𝟎 𝑴 𝒐𝒇 𝑬𝑫𝑻𝑨 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏
 PHAN111LEC_WEEK 9 𝐹2 + 2𝑒 − = 2𝐹; 𝑜𝑥𝑖𝑑𝑖𝑧𝑖𝑛𝑔 𝑎𝑔𝑒𝑛𝑡

Oxidation-Reduction Titration
• Wherein oxidation states of a certain atoms
change; relies on the oxidation number of
substances
• Electrons are transferred between reactants
• Simplest type is the direct combination of
elements
Ex.
𝑀𝑔0 + 𝑂2 0 = 𝑀𝑔2+ 𝑂 −2

−2
𝑍𝑛0 + 𝐻2 +1 𝑆 −8 𝑂4 = 𝑍𝑛+2 𝑆 −8 𝑂4 −2 + 𝐻2 0
From 𝑍𝑛0 to 𝑍𝑛+2 = reducing agent, underwent
oxidation; 2 electrons loss
From 𝐻2 +1 to 𝐻2 0 = oxidizing agent, underwent
reduction; 2 electrons gained

• Importance:
o Antiseptic effect
o Effects on hair treatment
o Black and white photography
o Breath alcohol analyzer

Principle and Concepts Standard Solutions for REDOX

a. Faraday’s Law – “change of one is equal to • Strong Oxidizing Agents
the gain or loss of 96,500C of electricity for o Potassium Permanganate ; 𝐾𝑀𝑛𝑂4
each formula weight of element or group of o Ceric Sulfate ; 𝐶𝑒𝐻2 𝑂4 𝑆
elements involved.” o Iodine
• Reducing Agent o Bromine
o Loses electrons o Potassium Iodate ; 𝐾𝐼𝑂3
o Causes the reduction (i.e. gain of • Strong Reducing Agents
positive charge) o Oxalic acid ; 𝐶2 𝐻2 𝑂4
o VILEORA = Valence Increase Loses o Ferrous sulfate ; 𝐹𝑒𝑆𝑂4
Electrons Oxidation Reducing Agent o Sodium Thiosulfate ; 𝑁𝑎2 𝑆2 𝑂3
Ex.
𝐹𝑒 +2 = 𝐹𝑒 +3 + 𝑒 IMPORTANT COMBINATIONS:
• Oxidizing Agent Potassium Permanganate and Oxalic Acid
o Gains electrons Ceric Sulfate and Ferrous Sulfate
o Causes the oxidation (i.e. loss of Iodine and Sodium Thiosulfate
positive charge)
o VaDGEORA = Valence Decrease
Gain Electrons Reduction Oxidizing Rules in Oxidation Reaction
Agent 1. Oxidation state of an element in a free state
or combined form is equal to zero
Ex. 2. Oxidation state of H+ in a compound is +1
𝐶𝑒 +4 = 𝐶𝑒 +3 + 𝑒 except in combination with metals which is -
• Half Reactions 1
Ex.
𝐻2 0 + 𝐹2 0 = 2𝐻+1 𝐹 −1 𝑁𝑎 +1 𝐻−1
𝐶𝑎 +2 𝐻2 −1
𝐻2 = 2𝐻 + 2𝑒 − ; 𝑟𝑒𝑑𝑢𝑐𝑖𝑛𝑔 𝑎𝑔𝑒𝑛𝑡 𝐴𝑙 +3 𝐻3 −1
 i. can be standardized easily
3. Oxidation state of oxygen in a compound is - ii. can retain its concentration
2 except in peroxides which is -1 for a long period of time; if
Ex. properly kept, otherwise it
𝐻2 +1 𝑂2 −1 can lose concentration from
purple to brown (useless)
4. Group IA – oxidation state is +1 iii. The reaction of
Group IIA – oxidation state is +2 permanganate in solution is
Halogens – oxidation state is -1 but positive rapid
with oxygen iv. Can serve as an indicator in
Flourine is always -1 titration
Ex. b. Primary standard: Sodium Oxalate;
−1
𝐶𝑙+3 𝑂2 −2 ; "𝑐ℎ𝑙𝑜𝑟𝑖𝑡𝑒" Oxalic acid is most effective chemical
𝐶𝑙𝑂3 ; "𝑐ℎ𝑙𝑜𝑟𝑎𝑡𝑒" substance in removing KMnO4 stains
𝐶𝑙𝑂; "ℎ𝑦𝑝𝑜𝑐ℎ𝑙𝑜𝑟𝑖𝑡𝑒" c. Excess KMnO4 imparts pink color
𝐶𝑙 +7 𝑂4 −2 ; "𝑝𝑒𝑟𝑐ℎ𝑙𝑜𝑟𝑎𝑡𝑒"
5. For monoatomic compounds, the charge is Types of Titration Example Analytes
its oxidation state Direct Hydrogen Peroxide
6. The algebraic sum of the oxidation state of a Indirect Malic acid in Cherry
neutral compound is equal to zero Juice
Ex. Residual Sodium nitrite
𝑁𝑎 +1 𝐶𝑙−1
𝐾 +1 𝐶𝑙−1 d. 2 Types of Residual Titration
𝐾 𝑀𝑛+7 𝑂4 −2
+1 i. Titration in which excess of
𝑁𝑎2 +1 𝐶2 +3 𝑂4 −2 standard KMnO4 is employed
𝐶𝑎 +2 𝐶 +3 𝑂3 −2 to oxidize a substance, and
𝐻2 +1 𝑆 +6 𝑂4 −2 the amount in excess is
determined by the reduction
𝐻2 +1 𝑂2 −1
with:
𝐴𝑔+1 𝑁 +5 𝑂3 −2
1. Standard oxalic acid
𝑀𝑔+2 𝑂−2
2. Excess ferrous
𝑁𝑎2 +2 𝐶 +2 𝑂3 −2
ammonium sulfate
𝐾 +1 𝐻+1 𝐶 +4 𝑂3 −2 and back titrated with
𝑍𝑛+2 𝑆 +6 𝑂4 −2 potassium
7. The oxidation state of a polyatomic ions is permanganate
equal to the ionic charge ii. Titration in which an excess
Ex. of standard oxalic acid
𝐶2+6 𝑂4 −2 ; "𝑐𝑎𝑟𝑏𝑜𝑛 𝑜𝑥𝑎𝑙𝑎𝑡𝑒" solution is added to the
𝐻+1 𝐶 +4 𝑂3 −2 ; "𝑏𝑖𝑐𝑎𝑟𝑏𝑜𝑛𝑎𝑡𝑒" substance and the excess
𝐶𝑟2 +6 𝑂7 −2 ; "𝑑𝑖𝑐ℎ𝑟𝑜𝑚𝑎𝑡𝑒" oxalic acid is titrated with
𝑃 +5 𝑂4 −2 ; "𝑝ℎ𝑜𝑠𝑝ℎ𝑎𝑡𝑒" standard KMnO4.
𝑆 +6 𝑂4 −2 ; "𝑠𝑢𝑙𝑓𝑎𝑡𝑒" B. Cerimetry
𝐶 +4 𝑂3 −2 ; "𝑐𝑎𝑟𝑏𝑜𝑛𝑎𝑡𝑒" a. VS: Ceric Sulfate and Ferrous
−2
𝐶𝑟 +6 𝑂4 −2 ; "𝑐ℎ𝑟𝑜𝑚𝑎𝑡𝑒" Ammonium sulfate (for residual)
b. Indicators: orthophenanthroline-
𝑆2 +2 𝑂3 −2 ; "𝑡ℎ𝑖𝑜𝑠𝑢𝑙𝑓𝑎𝑡𝑒"
ferrrous sulfate; red in reducing
𝑀𝑛 +7 𝑂4 −2 ; "𝑝𝑒𝑟𝑚𝑎𝑛𝑔𝑎𝑛𝑎𝑡𝑒"
agents, pale green or blue in
𝐶6 +1 𝐻5 +1 𝑂7 −2 ; "𝑐𝑖𝑡𝑟𝑎𝑡𝑒"
oxidizing agents
c. Analytes: ferrous sulfate syrup and
TYPES OF REDOX TITRATION tablets, menadione tablets,
A. Permanganometry menadione sodium bisulfite, and
a. Uses KMnO4 VS; characteristics: menadione sodium bisulfate
valuable and powerful oxidizing injection, ferrous carbonate mass and
agent used for the titration of iron pills.
 d. Ceric sulfate is a powerful oxidizing with standard ferrous ammonium sulfate
agent that can be used in titrations with orthophenanthroline T.S. as indicator
of organic substances; should not be
boiled with HCl and should only be C. Iodimetry
conducted only in acid media to a. VS: Iodine as oxidizing agent; iodine
prevent hydrolysis solutions and sodium thiosulfate in
e. Solutions in this type are less neutral or slightly acidic medium
susceptible to decomposition and it b. Direct reaction
can be used in the titration of c. Indicator: In colorless, iodine is
ferrous ion in the presence of sufficient; Freshly prepared Starch
chloride at room temp. solution is most commonly used;
f. Advantages Carbon tetrachloride and chloroform
i. Stable over prolonged may be used
periods of time even on
Free Iodine Solution is used; difficult to prepare
boiling;
because iodine is less soluble in water; ergo it was
ii. React quantitatively with
made with the use of KI
oxalate or arsenic ion
iii. No intermediate products are
𝐾𝐼 + 𝐼2 = 𝐾𝐼3
formed in the reduction of
ceric to cerium d. Analytes: Pharmaceutical solutions
iv. Maybe employed in the of arsenites, trivalent antimony
determination of reducing compounds, thiosulfates, sulfites,
agent in the presence of high mercurous compounds, ascorbic acid,
concentration HCl methenamine. Sodium sulfite,
v. Not too highly calomel, caffeine in APC tablets, and
colored(colorless) to obstruct yellow mercurous iodide
the vision when reading the
meniscus Types of Reaction Example Analytes
Ex. Direct Ascorbic acid,
Antimony potassium
Assay of Ferrous Sulfate Tablets (Direct Titration) tartrate
• 20 tablets are weighed, dissolved in a Residual w/ 𝑁𝑎2 𝑆2 𝑂3 Calomel, antipyrine
mixture of 20 mL diluted sulfuric acid and 80
mL of boiled and cooled water and filtered. D. Iodometry
Orthophenanthroline T.S. is added and a. Titration in which an equivalent
titrated with ceric sulfate. Each mL of 0.1 N amount of iodine from potassium
ceric sulfate is equivalent to 27.8 mg of iodide is liberated using Sodium
𝐹𝑒𝑆𝑂4 • 7𝐻2 𝑂 thiosulfate
b. Indirect reaction
Assay of Potassium Chloride in Ringer’s solution and c. Indicator: iodine is sufficient with a
injection (Residual assay) small amount of carbon tetrachloride
• The principle consists in precipitation of the d. Never carried out in strongly basic
sample with sodium cobaltinitrite in the solution
presence of alcohol forming dipotassium
sodiumcobalnitrite. The precipitate is Types of Reaction Example Analytes
washed with 70% alcohol, centrifuged, Direct CuSO4
decanted, and allow to drain and dried to 80 Residual Phenol, resorcinol, lead
degC. When the dried precipitate is treated oxide
with a measured excess of standard ceric
sulfate solution and 18 N sulfuric acid, REDOX Method with 0.1 N Bromine
heated until the precipitate has disappeared. • A.k.a. Koppesschar’s Solution
The mixture is cooled to room temperature • used in assays of aniline, phenol and
and the excess of ceric sulfate is titrated resorcinol
 • Bromine is liberated when solution is 2.) What volume of 0.1225 N sodium hydroxide
acidified would be required in a titration of a 0.1065
• VS does not contain bromine but rather an g sample of oxalic acid if a 0.1126 g sample
equivalent amount of potassium bromate of the oxalic acid required 24.65 mL of
and excess potassium bromide 0.0965 N potassium permanganate in a
titration?
Redox Reaction with Potassium Iodate
• Potassium iodate is used as oxidizing agent 𝐻2 𝐶2 𝑂4 + 𝑁𝑎𝑂𝐻 → 𝑁𝑎2 𝐶2 𝑂4 + 𝐻2 𝑂
with iodides, arsenites, and other reducing
agents 𝐻2 𝐶2 𝑂4 = 1(2) + 12(2) + 16(4)
• Depends upon the formation of iodine 90
=
monochloride in strong HCl solution 2(1000)
= 0.045 𝑔/𝑚𝑜𝑙
Practice
1.) A 0.2295 g of sodium oxalate (97.8%)
required 35.12 mL of a potassium 𝑤𝑡
𝑁=
permanganate solution in a titration. What 𝑚𝐿 𝑥 𝑚𝐸𝑞
was the normality of the permanganate 𝑁 𝑥 𝑚𝐿 𝑥 𝑚𝐸𝑞 𝑤𝑡
= .
solution? 𝑁 𝑥 𝑚𝐸𝑞 𝑁 𝑥 𝑚𝐸𝑞
𝑤𝑡
𝑚𝐿 =
𝑁𝑎2 𝐶2 𝑂4 + 𝐾𝑀𝑛𝑂4 + 𝐻2 𝑆𝑂4 𝑁 𝑥 𝑚𝐸𝑞
→ 𝑀𝑛𝑆𝑂4 + 𝑁𝑎2 𝑆𝑂4 + 𝐾2 𝑆𝑂4 + 𝐶𝑂2
+ 𝐻2 𝑂
0.1065 g
𝑚𝐿 =
* find the byproduct with similar molecules that 0.1225 N 𝑥 0.045 𝑔/𝑚𝑜𝑙
depicts a change in oxidation; usually find the change 𝑚𝐿 = 𝟏𝟗. 𝟑𝟐 𝒎𝑳 𝒐𝒇 𝑵𝒂𝑶𝑯
in the middle atom

𝑁𝑎2 +1 𝐶2 +2 𝑂4 −2 → 𝐶 +4 𝑂2 −2 3.) What volume of 0.1225 N sodium hydroxide

* Half Reaction Formula: would be required in a titration of a 0.1065
𝐶2 +3 → 𝐶 +4 + 2𝑒 − ; 𝑟𝑒𝑑𝑢𝑐𝑖𝑛𝑔 𝑎𝑔𝑒𝑛𝑡 g sample of sodium oxalate if a 0.1126 g
The factor would be 2 since 2 electrons are lost sample of the sodium oxalate required 24.65
mL of 0.0965 N potassium permanganate in
a titration?
𝑁𝑎2 +1 𝐶2 +2 𝑂4 −2 = 23(2) + 12(2) + 16(4)
134 𝑁𝑎2 +1 𝐶2 +2 𝑂4 −2 → 𝐶 +4 𝑂2 −2
=
2(1000)
= 0.067 𝑔/𝑚𝐸𝑞
𝑁𝑎2 +1 𝐶2 +2 𝑂4 −2 = 23(2) + 12(2) + 16(4)
𝑚𝐿 𝑥 𝑁 𝑥 𝑚𝐸𝑞 134
% 𝑝𝑢𝑟𝑖𝑡𝑦 = 𝑥100 =
𝑤𝑡. 2(1000)
% 𝑝𝑢𝑟𝑖𝑡𝑦 𝑚𝐿 𝑥 𝑁 𝑥 𝑚𝐸𝑞 = 0.067 𝑔/𝑚𝐸𝑞
=
100 𝑤𝑡.
𝑚𝐿 𝑥 𝑁 𝑥 𝑚𝐸𝑞 𝑤𝑡
%𝑝𝑢𝑟𝑖𝑡𝑦 (𝑤𝑡. ) = 𝑁=
𝑚𝐿 𝑥 𝑚𝐸𝑞. 𝑚𝐿 𝑥 𝑚𝐸𝑞
%𝑝𝑢𝑟𝑖𝑡𝑦 (𝑤𝑡. ) 𝑚𝐿 𝑥 𝑁 𝑥 𝑚𝐸𝑞 𝑁 𝑥 𝑚𝐿 𝑥 𝑚𝐸𝑞 𝑤𝑡
= =
𝑚𝐿 𝑥 𝑚𝐸𝑞 𝑚𝐿 𝑥 𝑚𝐸𝑞 𝑁 𝑥 𝑚𝐸𝑞 𝑁 𝑥 𝑚𝐸𝑞
%𝑝𝑢𝑟𝑖𝑡𝑦 (𝑤𝑡. ) 𝑤𝑡
𝑁= 𝑚𝐿 = .
𝑚𝐿 𝑥 𝑚𝐸𝑞 𝑁 𝑥 𝑚𝐸𝑞

0.978 (0.2295 g) 0.1065 g

𝑁= 𝑚𝐿 =
35.12 mL 𝑥 0.067 𝑔/𝑚𝐸𝑞 0.1225 N 𝑥 0.067 𝑔/𝑚𝐸𝑞
𝑁 = 𝟎. 𝟎𝟗𝟓𝟒 𝑵 𝒐𝒇 𝑲𝑴𝒏𝑶𝟒 𝑚𝐿 = 𝟏𝟐. 𝟗𝟖 𝒎𝑳 𝒐𝒇 𝑵𝒂𝑶𝑯
 [(𝑁1 𝑉1 ) − (𝑁2 𝑉2 )] 𝑥 𝑚𝐸𝑞
%= 𝑥100
4.) P. 162 from book: A 2 mL sample of 𝑤𝑡.
hydrogen peroxide solution required 8.5 mL %=
[(0.1𝑁 𝑥 54.58 𝑚𝐿) − (0.0975 𝑁 𝑥 25 𝑚𝐿)] 𝑥 0.0345 𝑔/𝑚𝑜𝑙
𝑥100
0.11 𝑔
of a permanganate solution in titration. If
% = 𝟎. 𝟗𝟒% 𝒐𝒇 𝑵𝒂𝑵𝑶𝟑
each mL of the permanganate solution is
equivalent to 0.007294 g of Fe. What % w/v
6.) Twenty tablets of ferrous sulfate weighed
of hydrogen peroxide was in the sample?
5.985 g and a powdered sample of 0.298 g
was titrated consuming 5.85 mL of 0.1458 N
𝐻2 +1 𝑂2 −1 → 𝑂2 0 ; 𝑂2 + 2𝑒 − of ceric sulfate solution. Each mL of 0.1 N of
ceric sulfate is equivalent to 27.80 mg of
𝐻2 𝑂2 = 1(2) + 16(2)
ferrous sulfate. What is the amount of
34
= ferrous sulfate per tablet? Calculate thel
2(1000) percentage label claim if each tablet is 250
= 0.017 𝑔/𝑚𝐸𝑞
mg.
𝐹𝑒 = 56 5.985 𝑔 𝑥
56 𝑥 = 0.2993 𝑔 𝑜𝑟 299.25 𝑚𝑔
𝐹𝑒 = 20 𝑡𝑎𝑏𝑙𝑒𝑡𝑠 1 𝑡𝑎𝑏𝑙𝑒𝑡
1(1000)
𝐹𝑒 = 0.056 𝑔/𝑚𝐸𝑞 * If substance with a given titer value is similar to the
substance assayed, there is no need to make the
𝑡𝑖𝑡𝑒𝑟 = 𝑁 (𝑚𝐸𝑞) reaction as mEq can already be computed from the
𝑡𝑖𝑡𝑒𝑟 𝑁 (𝑚𝐸𝑞)
= titer formula
𝑚𝐸𝑞 𝑚𝐸𝑞
𝑡𝑖𝑡𝑒𝑟 𝑡𝑖𝑡𝑒𝑟 = 𝑁 (𝑚𝐸𝑞)
𝑁=
𝑚𝐸𝑞 𝑡𝑖𝑡𝑒𝑟 𝑁 (𝑚𝐸𝑞)
=
𝑁 𝑁
0.007294 g 𝑡𝑖𝑡𝑒𝑟
𝑁= 𝑚𝐸𝑞 =
0.056 𝑔/𝑚𝑜𝑙 𝑁
𝑁 = 0.1303 𝑁 𝑜𝑓 𝐾𝑀𝑛𝑂4
0.0278 𝑔
𝑚𝐿 𝑥 𝑁 𝑥 𝑚𝐸𝑞 𝑚𝐸𝑞 =
0.1 N
% 𝑝𝑢𝑟𝑖𝑡𝑦 = 𝑥100 𝑚𝐸𝑞 = 0.278 𝑔/𝑚𝐸𝑞
𝑤𝑡.
8.5 mL 𝑥 0.1303 𝑁 𝑥 0.017 𝑔/𝑚𝑜𝑙
% 𝑝𝑢𝑟𝑖𝑡𝑦 = 𝑥100 𝑚𝐿 𝑥 𝑁 𝑥 𝑚𝐸𝑞
2 mL 𝑚𝑔/𝑡𝑎𝑏 = 𝑥 𝑚𝑔/𝑡𝑎𝑏
% 𝑝𝑢𝑟𝑖𝑡𝑦 = 𝟗𝟒. 𝟏𝟒% 𝒘/𝒗 𝒐𝒇 𝑯𝟐 𝑶𝟐 𝑤𝑡
5.85 mL 𝑥 0.1458 N 𝑥 0.278 𝑔/𝑚𝐸𝑞
𝑚𝑔/𝑡𝑎𝑏 = 𝑥 299.25 𝑚𝑔
5.) p. 169, no. 2: % of sodium nitrite in 0.298 g
/𝑡𝑎𝑏
potassium permanganate 𝑚𝑔
= 𝟐𝟑𝟖. 𝟏𝟏 𝒎𝒈/𝒕𝒂𝒃 𝒐𝒇 𝑭𝒆𝑺𝑶𝟒
𝑡𝑎𝑏
𝑁𝑎 +1 𝑁 +3 02 −2 → 𝐻+1 𝑁 +5 𝑂3 −2

𝑁𝑎𝑁𝑂2 = 23(1) + 14(1) + 16(2) 𝑒𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡𝑎𝑙 𝑣𝑎𝑙𝑢𝑒

69 %𝑙𝑎𝑏𝑒𝑙 = 𝑥100
= 𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑣𝑎𝑙𝑢𝑒
2(1000) 238.11 𝑚𝑔
= 0.0345 𝑔/𝑚𝐸𝑞 %𝑙𝑎𝑏𝑒𝑙 = 𝑥100
250 mg
%𝑙𝑎𝑏𝑒𝑙 = 𝟗𝟓. 𝟐𝟒% 𝒐𝒇 𝑭𝒆𝑺𝑶𝟒
1.100 𝑔
𝑥 10 𝑚𝐿 = 0.11 𝑔
100 𝑚𝐿 7.) Twenty tablets of ascorbic acid weighed
4.2500 g and a powdered sample of 0.3075
𝑇𝑜𝑡𝑎𝑙 𝑚𝐿 𝑜𝑓 𝐾𝑀𝑛𝑂4 = 50 𝑚𝐿 + 4.50 𝑚𝐿 g was titrated consuming 21.5 mL of 0.1085
= 54.58 𝑚𝐿 𝑜𝑓 𝐾𝑀𝑛𝑂4 N iodine solution. Each mL of 0.1 N iodine is
equivalent to 8.80 mg of ascorbic acid. What
is the amount of ascorbic acid per dose of
two tablets?
 5.985 𝑔 𝑥
𝑥 = 0.2125 𝑔 𝑜𝑟 212.5 𝑚𝑔
20 𝑡𝑎𝑏𝑙𝑒𝑡𝑠 1 𝑡𝑎𝑏𝑙𝑒𝑡

𝑡𝑖𝑡𝑒𝑟 𝑁 (𝑚𝐸𝑞)
=
𝑁 𝑁
𝑡𝑖𝑡𝑒𝑟
𝑚𝐸𝑞 =
𝑁

0.0088 𝑔
𝑚𝐸𝑞 =
0.1 N
𝑚𝐸𝑞 = 0.088 𝑔/𝑚𝐸𝑞

𝑚𝐿 𝑥 𝑁 𝑥 𝑚𝐸𝑞
𝑚𝑔/𝑡𝑎𝑏 = 𝑥 𝑚𝑔/𝑡𝑎𝑏
𝑤𝑡
21.5 mL 𝑥 0.1085 N 𝑥 0.088 𝑔/𝑚𝐸𝑞
𝑚𝑔/𝑡𝑎𝑏 = 𝑥 212.5 𝑚𝑔/𝑡𝑎𝑏
0.3075 g
𝑚𝑔/𝑡𝑎𝑏 = 141.86 𝑚𝑔/𝑡𝑎𝑏 𝑜𝑓 𝑎𝑠𝑐𝑜𝑟𝑏𝑖𝑐 𝑎𝑐𝑖𝑑

𝑑𝑜𝑠𝑒 𝑜𝑓 2 𝑡𝑎𝑏𝑠 = 141.86 𝑚𝑔/𝑡𝑎𝑏 (2)

𝑑𝑜𝑠𝑒 𝑜𝑓 2 𝑡𝑎𝑏𝑠 = 𝟐𝟖𝟑. 𝟕𝟐 𝒎𝒈/𝟐 𝒕𝒂𝒃𝒔 𝒐𝒇 𝒂𝒔𝒄𝒐𝒓𝒃𝒊𝒄 𝒂𝒄𝒊𝒅
 PHAN111LEC_WEEK 10 o Filtration and washing of the
precipitate to remove adhering or
absorbed substances
Gravimetric Method o Drying of the precipitate and
• Consists of isolating from the sample the weighing it accurately
constituent to be determined in its pure Ex.
state and weighing accurately
• Isolation may be carried out by: Gravimetric Method by Precipitation Assay of
o Precipitating the sought substance in Sodium Sulfate
an insoluble form (most common) • Five hundred mg sample is dissolved in 150
o Depending on pure metal by mL of distilled water, 12 mL of conc. HCl is
electrolysis (not commonly used in added and heated to boiling. 20 mL of
pharmaceutical analysis) barium chloride (precipitating agent) is
o By converting the substance to a gas poured to the hot solution of the sample.
which is absorbed in a suitable The precipitate formed is allowed to settle
reagent and test for complete precipitation by
adding a few drops of barium chloride
Precipitation solution. Cover the beaker with a watch
• Low solubility; large particles; easily filtered; glass and digest first below boiling for one
pure and stable hour. The supernatant liquid is decanted and
• Laws Applied on Precipitation the precipitate is washed three times with
o Solubility Product Principle warm water. The residue is white. It is then
▪ If the ionic product exceeds cooled and weighed.
the solubility product
constant precipitation will Calculations
occur • Example:
o The Common Ion Effect o Bismuth carbonate is required to
▪ If there is an excess of one yield on ignition not less than 90% of
ion over the other, the 𝐵𝑖2 𝑂3 . The percentage of the latter
solubility of the precipitate may be obtained by simply dividing
will decrease the weight of the residue by the
o Law of Mass Action weight of the sample and multiply by
▪ The rate of reaction is 100.
directly proportional to the • Factor – commonly called as chemical
product of the molecular factor, calculation factor, conversion factor,
concentrations of the equivalent factor, or gravimetric factor;
reacting substance defined as the weight of the constituent
▪ Velocity of reaction depends determined or sought and is equivalent to
on the molecular the unit weight of a given substance
concentrations of the
reactant 𝑀𝑊 𝑜𝑓 𝑠𝑥.
𝐶𝐹 = .
▪ At equilibrium, the products 𝑀𝑊 𝑜𝑓 𝑝𝑝𝑡.
is equal to reactants
• Isolation by precipitation involves: 𝑤𝑡. 𝑜𝑓 𝑝𝑝𝑡 𝑥 𝐶𝐹
%= 𝑥 100
o Weighing of appropriate quantity of 𝑤𝑡. 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒
the sample
o Preparation of tared crucible where Ex.
precipitate is dried and weighed
o Bringing into solution of the The chemical factor of 𝑁𝑎2 𝑆𝑂4 in 𝐵𝑎𝑆𝑂4 :
constituent to be determined,
separating it from substances that 𝑀𝑊 𝑜𝑓 𝑠𝑥.
may interfere in the process 𝐶𝐹 = .
𝑀𝑊 𝑜𝑓 𝑝𝑝𝑡.
o Precipitation of the constituent to be 𝑁𝑎2 𝑆𝑂4 142.52
determined 𝐶𝐹 = = = 𝟎. 𝟔𝟎𝟖𝟔
𝐵𝑎𝑆𝑂4 233.43
 = 233 𝑔/𝑚𝑜𝑙

Practice
1) A 0.3056 g sample of soluble chloride was 𝑀𝑊 𝑜𝑓 𝐴𝑙2 (𝑆𝑂4 )3
𝐶𝐹 = .
analyzed gravimetrically for Cl and 0.7265 g 𝑀𝑊 𝑜𝑓 𝐵𝑎𝑆𝑂4
of AgCl was obtained. Calculate the Cl and
NaCl contents of the sample, expressing * Identical elements between molecules should be equivalent
each in % w/w to each other; therefore, since there are 3 SO4 molecules in
Al2SO4, there should be 3 SO4 molecules as well in BaSO4
__𝐶𝑙 + 𝐴𝑔𝑁𝑂3 → 𝐴𝑔𝐶𝑙 ↓ + __𝑁𝑂3
𝑁𝑎𝐶𝑙 + 𝐴𝑔𝑁𝑂3 → 𝐴𝑔𝐶𝑙 + 𝑁𝑎𝑁𝑂3 𝑀𝑊 𝑜𝑓 𝐴𝑙2 (𝑆𝑂4 )3
𝐶𝐹 = .
𝑀𝑊 𝑜𝑓 3𝐵𝑎𝑆𝑂4
𝐶𝑙 = 35 𝑔/𝑚𝑜𝑙 342 𝑔/𝑚𝑜𝑙
𝐶𝐹 = .
3 𝑥 233 𝑔/𝑚𝑜𝑙
𝑁𝑎𝐶𝑙 = 23 (1) + 35 (1) 𝐶𝐹 = 𝟎. 𝟒𝟖𝟗𝟑
= 58 𝑔/𝑚𝑜𝑙
3) A precipitate of AgCl weighing 0.2432 g was
𝐴𝑔𝐶𝑙 = 108 (1) + 35 (1) obtained from 25 mL sample of HCl
= 143 𝑔/𝑚𝑜𝑙 solution. Calculate (a) HCl content of the
solution w/v, (b) molarity of the solution
𝑀𝑊 𝑜𝑓 𝐶𝑙
𝐶𝐹 = .
𝑀𝑊 𝑜𝑓 𝐴𝑔𝐶𝑙 𝐻𝐶𝑙 + 𝐴𝑔𝑁𝑂3 → 𝐴𝑔𝐶𝑙 + 𝐻𝑁𝑂3
35 𝑔/𝑚𝑜𝑙
𝐶𝐹 = .
143 𝑔/𝑚𝑜𝑙 𝐻𝐶𝑙 = 1(1) + 35(1)
𝐶𝐹 = 0.2448 = 36 𝑔/𝑚𝑜𝑙

𝐴𝑔𝐶𝑙 = 108 (1) + 35 (1)

𝑤𝑡. 𝑜𝑓 𝑝𝑝𝑡 𝑥 𝐶𝐹 = 143 𝑔/𝑚𝑜𝑙
%= 𝑥 100
𝑤𝑡. 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒
0.7265 g 𝑥 0.2448
% 𝐶𝑙 = 𝑥 100 𝑀𝑊 𝑜𝑓 𝐻𝐶𝑙
0.3056 g 𝐶𝐹 = .
% = 𝟓𝟖. 𝟐𝟎% 𝒐𝒇 𝑪𝒍 𝑀𝑊 𝑜𝑓 𝐴𝑔𝐶𝑙
36 𝑔/𝑚𝑜𝑙
𝐶𝐹 = .
143 𝑔/𝑚𝑜𝑙
𝑀𝑊 𝑜𝑓 𝑁𝑎𝐶𝑙 𝐶𝐹 = 0.2517
𝐶𝐹 = .
𝑀𝑊 𝑜𝑓 𝐴𝑔𝐶𝑙
58 𝑔/𝑚𝑜𝑙
𝐶𝐹 = . 𝑤𝑡. 𝑜𝑓 𝑝𝑝𝑡 𝑥 𝐶𝐹
143 𝑔/𝑚𝑜𝑙 %= 𝑥 100
𝐶𝐹 = 0.4056 𝑤𝑡. 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒
0.2432 g 𝑥 0.2517
% 𝐻𝐶𝑙 = 𝑥 100
𝑤𝑡. 𝑜𝑓 𝑝𝑝𝑡 𝑥 𝐶𝐹 25 mL
%= 𝑥 100 0.2432 g 𝑥 0.2517
𝑤𝑡. 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 % 𝐻𝐶𝑙 = 𝑥 100
0.7265 g 𝑥 0.4056 25 mL
% 𝑁𝑎𝐶𝑙 = 𝑥 100 % 𝐻𝐶𝑙 = 𝟎. 𝟐𝟒% 𝒘/𝒗 𝒐𝒇 𝑯𝑪𝒍
0.3056 g
% 𝑁𝑎𝐶𝑙 = 𝟗𝟔. 𝟒𝟐% 𝒐𝒇 𝑵𝒂𝑪𝒍
𝑤𝑡
𝑀=
𝑀𝑊 𝑥 𝐿
2) Find the CF of Aluminum sulfate to which a 0.2432 g
precipitate of Barium sulfate was formed. 𝑀=
143 𝑔/𝑚𝑜𝑙 𝑥 0.025 𝐿
𝑀 = 𝟎. 𝟎𝟔𝟖𝟎 𝑴 𝒐𝒇 𝑯𝑪𝒍
𝐴𝑙2 (𝑆𝑂4 )3 = 27 (2) + 32 (3) + 16 (4 𝑥 3)
= 342 𝑔/𝑚𝑜𝑙 4) An unknown sample of a soluble sulfate
weighing 1.800 g yielded 0.9000 g of
𝐵𝑎𝑆𝑂4 = 137 (1) + 32 (1) + 16(4)
 Barium sulfate. Calculate the percentage of
sulfur in the unknown. If soluble sulfate and 𝑀𝑔𝑆𝑂4 = 23(1) + 32(1) + 16(4)
precipitate is barium sulfate, precipitating = 119 𝑔/𝑚𝑜𝑙
agent must be: SO4 + Ba_ to form BaSO4 +
___ 𝐵𝑎𝑆𝑂4 = 137(1) + 32(1) + 16 (4)
= 233 𝑔/𝑚𝑜𝑙
__𝑆𝑂4 + 𝐵𝑎𝐶𝑙2 → 𝐵𝑎𝑆𝑂4 ↓ + __𝐶𝑙
𝑀𝑊 𝑜𝑓 𝑀𝑔𝑆𝑂4
𝐶𝐹 = .
𝑆 = 32 𝑔/𝑚𝑜𝑙 𝑀𝑊 𝑜𝑓 𝐵𝑎𝑆𝑂4
119 𝑔/𝑚𝑜𝑙
𝐶𝐹 = .
𝐵𝑎𝑆𝑂4 = 137(1) + 32(1) + 16 (4) 233 𝑔/𝑚𝑜𝑙
= 233 𝑔/𝑚𝑜𝑙 𝐶𝐹 = 0.5107

𝑀𝑊 𝑜𝑓 𝑆 𝑤𝑡. 𝑜𝑓 𝑝𝑝𝑡 𝑥 𝐶𝐹
𝐶𝐹 = . %= 𝑥 100
𝑀𝑊 𝑜𝑓 𝐵𝑎𝑆𝑂4 𝑤𝑡. 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒
32 𝑔/𝑚𝑜𝑙 0.9000 g 𝑥 0.5107
𝐶𝐹 = . %= 𝑥 100
233 𝑔/𝑚𝑜𝑙 1.800 g
𝐶𝐹 = 0.1373 % = 𝟐𝟓. 𝟓𝟒% 𝒐𝒇 𝑴𝒈𝑺𝑶𝟒

𝑤𝑡. 𝑜𝑓 𝑝𝑝𝑡 𝑥 𝐶𝐹
%= 𝑥 100
𝑤𝑡. 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝐾2 𝑆𝑂4 + 𝐵𝑎𝐶𝑙2 → 𝐵𝑎𝑆𝑂4 ↓ +𝐾𝐶𝑙2
0.9000 g 𝑥 0.1373
%𝑆= 𝑥 100
1.800 g 𝐾2 𝑆𝑂4 = 39(2) + 32(1) + 16(4)
% 𝑆 = 𝟔. 𝟖𝟕% 𝒐𝒇 𝒔𝒖𝒍𝒇𝒖𝒓 = 174 𝑔/𝑚𝑜𝑙

5) Calculate the mercury bichloride content of 𝐵𝑎𝑆𝑂4 = 137(1) + 32(1) + 16 (4)

the sample if 0.2551 g of which yields = 233 𝑔/𝑚𝑜𝑙
0.1815 g of mercuric sulfide
𝑀𝑊 𝑜𝑓 𝐾2 𝑆𝑂4
𝐶𝐹 = .
𝐻𝑔𝐶𝑙2 = 201(1) + 35(2) 𝑀𝑊 𝑜𝑓 𝐵𝑎𝑆𝑂4
= 271 𝑔/𝑚𝑜𝑙 174 𝑔/𝑚𝑜𝑙
𝐶𝐹 = .
233 𝑔/𝑚𝑜𝑙
𝐻𝑔𝑆 = 201(1) + 32(1) 𝐶𝐹 = 0.7468
= 233 𝑔/𝑚𝑜𝑙
𝑤𝑡. 𝑜𝑓 𝑝𝑝𝑡 𝑥 𝐶𝐹
𝑀𝑊 𝑜𝑓 𝐻𝑔𝐶𝑙2 %= 𝑥 100
𝐶𝐹 = . 𝑤𝑡. 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒
𝑀𝑊 𝑜𝑓 𝐻𝑔𝑆 0.9000 g 𝑥 0.7468
271 𝑔/𝑚𝑜𝑙 %= 𝑥 100
𝐶𝐹 = . 1.800 g
233 𝑔/𝑚𝑜𝑙 % = 𝟑𝟕. 𝟑𝟒% 𝒐𝒇 𝑲𝟐 𝑺𝑶𝟒
𝐶𝐹 = 1.1630

𝐴𝑙2 (𝑆𝑂4 )3 + 𝐵𝑎𝐶𝑙2 → 3𝐵𝑎𝑆𝑂4 ↓ +𝐴𝑙𝐶𝑙2

𝑤𝑡. 𝑜𝑓 𝑝𝑝𝑡 𝑥 𝐶𝐹
%= 𝑥 100
𝑤𝑡. 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝐴𝑙2 (𝑆𝑂4 )3 = 23(2) + 32(3) + 16(4𝑥3)
0.1815 g 𝑥 1.1630 = 334 𝑔/𝑚𝑜𝑙
% 𝐻𝑔𝐶𝑙2 = 𝑥 100
0.2551 g
% 𝐻𝑔𝐶𝑙2 = 𝟖𝟐. 𝟕𝟓% 𝒐𝒇 𝑯𝒈𝑪𝒍𝟐 𝐵𝑎𝑆𝑂4 = 137(1) + 32(1) + 16 (4)
= 233 𝑔/𝑚𝑜𝑙
6) Calculate the equivalent amounts of each
and the percentage purity if the unknown in 𝑀𝑊 𝑜𝑓 𝐴𝑙2 (𝑆𝑂4 )3
𝐶𝐹 = .
prob. 4 were MgSO4, K2SO4, and 𝑀𝑊 𝑜𝑓 3𝐵𝑎𝑆𝑂4
Al2(SO4)3. 334 𝑔/𝑚𝑜𝑙
𝐶𝐹 = .
(3)233 𝑔/𝑚𝑜𝑙
𝑀𝑔𝑆𝑂4 + 𝐵𝑎𝐶𝑙2 → 𝐵𝑎𝑆𝑂4 ↓ +𝑀𝑔𝐶𝑙2 𝐶𝐹 = 0.4778
 𝑤𝑡. 𝑜𝑓 𝑝𝑝𝑡 𝑥 𝐶𝐹
%= 𝑥 100
𝑤𝑡. 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒
0.9000 g 𝑥 0.4778
%= 𝑥 100
1.800 g
% = 𝟐𝟑. 𝟖𝟗% 𝒐𝒇 𝑨𝒍𝟐 (𝑺𝑶𝟒 )𝟑
 PHAN111LEC_WEEK 11 o Thimble – area where the sample is
placed
Extractives 𝑤𝑡. 𝑜𝑓 𝑟𝑒𝑠𝑖𝑑𝑢𝑒
• Product of extraction procedure % 𝑒𝑥𝑡𝑟𝑎𝑐𝑡𝑖𝑣𝑒 = 𝑥100
𝑤𝑡. 𝑜𝑓 𝑠𝑥.
• Amount of extractives, which a drug yields
to a given solvent, is a measure of the 𝑤𝑡. 𝑜𝑓 𝑠𝑥. 𝑖𝑛 𝑡ℎ𝑒 𝑡ℎ𝑖𝑚𝑏𝑙𝑒 𝑎𝑓𝑡𝑒𝑟 𝑑𝑟𝑦𝑖𝑛𝑔
amount of certain constituents or group of % 𝑖𝑛𝑠𝑜𝑙. 𝑟𝑒𝑠𝑖𝑑𝑢𝑒 =
𝑤𝑡. 𝑜𝑓 𝑠𝑥.
𝑥100
related constituents, which the drug
contains
• One solvent is not enough to extract all Alcohol-Soluble Extractives
constituents (like dissolves like) • For resins

𝐴𝑙𝑐. 𝑆𝑜𝑙. 𝐸𝑠𝑡𝑟𝑎𝑐𝑡 = 𝑤𝑡. 𝑜𝑓 𝑚𝑜𝑖𝑠𝑡𝑢𝑟𝑒 𝑓𝑟𝑒𝑒 𝑑𝑟𝑢𝑔 − 𝑤𝑡. 𝑜𝑓 𝑖𝑛𝑠𝑜𝑙. 𝑠𝑥.
Concepts
• Solvent used must not dissolve appreciable
quantities of substances other than those
sought in the extraction Water-Soluble Extractives
• Amount of drug soluble is an index of its • For drugs containing one or more important
purity for official requirements; low polarity constituents soluble in water
index = nonpolar and vice versa • Extraction is performed by maceration and
• % extract (solvent-soluble residue) residue after drying to constant weight
• % insoluble residue – contains fibers and
𝑊𝑎𝑡𝑒𝑟 𝑆𝑜𝑙. 𝐸𝑠𝑡𝑟𝑎𝑐𝑡 = 𝑤𝑡. 𝑜𝑓 𝑟𝑒𝑠𝑖𝑑𝑢𝑒 𝑎𝑓𝑡𝑒𝑟 𝑑𝑟𝑦𝑖𝑛𝑔
cellulose, etc.

Properties of a Good Solvent Other Solvents

• Low toxicity • Hexane – for fats and fixed oils through
o Methanol is previously used as a continuous extraction
solvent but is now less used due to • Ether – for resins, fixed oils, coloring matter
its toxicity and crude fiber through continuous
• Ease of evaporation extraction
• Rapid physiologic absorption of the extract
• Preservative action – ethanol is preferred as CRUDE FIBER CONTENT
a solvent than water • Residue consisting chiefly of cellulose that
• Inert – inability to cause a complex remains undissolved after successive
treatment with boiling acid and alkali
EXTRACTION METHODS • Important for food and animal feed Q.C. as it
• Maceration – letting the substance sit in a determines the presence of adulterants
suitable solvent for a long period of time which are also the crude fiber or the plant
• Percolation - filtration wastes
• Digestion – gentle heat applied; for • Samples are exhausted with ether to
thermolabile constituents remove fats and waxes which prevents
• Infusion – maceration through boiling or penetration of the acid and alkali solution
simmering in water into the drug particles
• Decoction – boiling for 15 mins.
• Enfleurage – common in extraction of 𝑤𝑡. 𝑜𝑓 𝑐𝑟𝑢𝑑𝑒 𝑓𝑖𝑏𝑒𝑟
%𝐶𝑟𝑢𝑑𝑒 𝐹𝑖𝑏𝑒𝑟 = 𝑥100
volatile oils; wax as a solvent 𝑤𝑡. 𝑜𝑓 𝑖𝑛𝑠𝑜𝑙 𝑟𝑒𝑠𝑖𝑑𝑢𝑒
• Continuous Extraction or Soxhlet
Extraction – exhaustive extraction 𝑤𝑡. 𝑜𝑓 𝐶𝐹 = 𝑤𝑡. 𝑜𝑓 𝑎𝑠ℎ − 𝑤𝑡. 𝑜𝑓 𝑟𝑒𝑠𝑖𝑑𝑢𝑒

Extraction Procedures
• Soxhlet Apparatus – generally used for Determination of Crude Fiber Content
extraction with volatile solvents wherein 1. Solvent exhausted sample (found in the
small quantities of drug are extracted thimble)
2. Add 200 mL of 1.25% boiling in H2SO4 for • Mercuric Potassium Iodide or Mayer’s
30 minutes Reagent – solution of 1.358 g of mercuric
3. Filter and wash the residue iodide in 60 mL of water with 5 g of KI in a
4. Rinse the residue back into the flask with 10 mL of water and the mixture diluted to
200 mL of boiling NaOH solution adjusted 100 mL. This reagent gives white or slightly
to exactly 1.25%. Again heat the mixture to yellow precipitate with dilute solution of
boiling and continue the boiling for exactly alkaloids
30 minutes
5. Filter through a linen or hardened filter
paper and wash the residue back into the
flask with 200 mL of boiling NaOH solution
adjusted to exactly 1.25%. Again, heat the
mixture to boiling for exactly 30 minutes
6. Under the reflux condenser, wash the
residue with boiling water until the last
washing is neutral, dry it at 110 degC until
of constant weight and note the weight
7. Incinerate the dried residue and weigh the
ash

EXTRACTION OF ALKALOIDS
• Alkaloids – chemical substances which are:
• Nonpolar solvents in solvent-solvent
o obtained from plant, animal or
extraction releases pressure
synthetic sources
o contains organic nitrogen within
Practice Problems
their chemical structure
1) A cocoa sample with a weight of 10.265 g
o usually possess physiological activity
was placed in a tared thimble and exacted
• Alkaloids (R3N) are sparingly soluble in
with either for 5 hours using continuous
water but readily soluble in most organic
extraction method. The ff. are the data
solvents immiscible in water ((ether,
collected.
chloroform (CHCL3), and carbon
tetrachloride (CCl4))
• Alkaloidal Salts (R3+NHCL-) are readily
soluble in water and sparingly soluble in
immiscible solvents
• Alkaloids form highly insoluble precipitates
with a considerable number of reagents with
the salts of some heavy metals such as
mercury, gold, and platinum

Alkaloidal Test Solutions 𝑤𝑡. 𝑜𝑓 𝐶𝐹 = 𝑤𝑡. 𝑜𝑓 𝑎𝑠ℎ − 𝑤𝑡. 𝑜𝑓 𝑟𝑒𝑠𝑖𝑑𝑢𝑒

• Mercuric Iodide TS or Valser’s Reagent – 𝑤𝑡. 𝑜𝑓 𝐶𝐹 = 2.1872 𝑔 − 1.9016 𝑔
prepared by slowly adding 10% solution of 𝑤𝑡. 𝑜𝑓 𝐶𝐹 = 0.2856 𝑔
potassium iodide to red mercuric iodide until
𝑤𝑡. 𝑜𝑓 𝑖𝑛𝑠𝑜𝑙. 𝑟𝑒𝑠𝑖𝑑𝑢𝑒 = 𝑤𝑡. 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝑎𝑛𝑑 𝑡ℎ𝑖𝑚𝑏𝑙𝑒 𝑎𝑓𝑡𝑒𝑟 𝑒𝑥𝑡𝑟𝑎𝑐𝑡𝑖𝑜𝑛
almost all the red mercuric iodide is − 𝑤𝑡. 𝑜𝑓 𝑡𝑎𝑟𝑒𝑑 𝑡ℎ𝑖𝑚𝑏𝑙𝑒
dissolved. The excess mercuric iodide is then 𝑤𝑡. 𝑜𝑓 𝑖𝑛𝑠𝑜𝑙. 𝑟𝑒𝑠𝑖𝑑𝑢𝑒 = 5.0092 𝑔 − 0.9285 𝑔
removed by filtration. This reagent forms a 𝑤𝑡. 𝑜𝑓 𝑖𝑛𝑠𝑜𝑙. 𝑟𝑒𝑠𝑖𝑑𝑢𝑒 = 4.0807 𝑔
white precipitate
• Iodine TS or Wagner’s Reagent – contains
iodine and potassium iodide dissolved in 𝑤𝑡. 𝑜𝑓 𝑐𝑟𝑢𝑑𝑒 𝑓𝑖𝑏𝑒𝑟
%𝐶𝑟𝑢𝑑𝑒 𝐹𝑖𝑏𝑒𝑟 = 𝑥100
distilled water. A 0.1 N Iodine solution may 𝑤𝑡. 𝑜𝑓 𝑖𝑛𝑠𝑜𝑙 𝑟𝑒𝑠𝑖𝑑𝑢𝑒
be employed; this yields a reddish or red- 0.2856 𝑔
%𝐶𝑟𝑢𝑑𝑒 𝐹𝑖𝑏𝑒𝑟 = 𝑥100
brown precipitate 4.0807 𝑔
%𝐶𝑟𝑢𝑑𝑒 𝐹𝑖𝑏𝑒𝑟 = 𝟔. 𝟗𝟗𝟗𝟖%; 𝒚𝒆𝒔 𝒊𝒕 𝒄𝒐𝒏𝒇𝒐𝒓𝒎𝒔
 [(20 mL x 0.1200 N ) − (12.10 mL x 0.1100 N)](0.2102 𝑔/𝑚𝐸𝑞)
%𝑅3 𝑁 = 𝑥100
0.3120 g
𝑤𝑡. 𝑜𝑓 𝑟𝑒𝑠𝑖𝑑𝑢𝑒
% 𝑒𝑥𝑡𝑟𝑎𝑐𝑡𝑖𝑣𝑒 = 𝑥100 %𝑅3 𝑁 = 𝟕𝟐. 𝟎𝟐% 𝒘/𝒘 𝒐𝒇 𝒂𝒎𝒊𝒏𝒐𝒑𝒉𝒚𝒍𝒍𝒊𝒏𝒆
𝑤𝑡. 𝑜𝑓 𝑠𝑥.
41.9875 𝑔 − 38.9966 𝑔
% 𝑒𝑥𝑡𝑟𝑎𝑐𝑡𝑖𝑣𝑒 = 𝑥100
10.265 g 4) 20 tablets of codeine sulfate (3/4 grain) is
% 𝑒𝑥𝑡𝑟𝑎𝑐𝑡𝑖𝑣𝑒 = 𝟐𝟗. 𝟏𝟒%; 𝒏𝒐 𝒊𝒕 𝒅𝒐𝒆𝒔 𝒏𝒐𝒕 𝒄𝒐𝒏𝒇𝒐𝒓𝒎 weighing 1.66 gram. An aliquot portion
weighing 0.5589 g was extracted with
2) Determine % w/w of alkaloids in belladonna chloroform and the extract was evaporated
leaf if 15.00 mL of 0.0210 N H2SO4 was and dried at 100 degC for 2 hours leaving a
added to the extracted alkaloids, and 7.30 residue which weighed 0.305 g. Compute
mL of 0.0198 N NaOH for the residual for the percentage labeled amount.
titration. The weight of the powder of a. Average wt. of tab = 1.66 g/20
belladonna leaf was 1.021 g. Each mL of tablets
0.02 N sulfuric acid is equivalent to 5.788 b. Labeled amount = ¾ grain = 1 gr. =
mg of hyoscyamine 65 mg
c. % purity/assay = wt. of residue/wt.
𝑡𝑖𝑡𝑒𝑟 = 𝑁(𝑚𝐸𝑞) of sample x 100
𝑡𝑖𝑡𝑒𝑟 𝑁(𝑚𝐸𝑞)
=
𝑁 𝑁 𝑤𝑡. 𝑝𝑒𝑟 𝑡𝑎𝑏 = 1.66 𝑔/20 𝑡𝑎𝑏𝑙𝑒𝑡𝑠
𝑡𝑖𝑡𝑒𝑟
= 𝑚𝐸𝑞 = 0.083 𝑔/𝑡𝑎𝑏 𝑜𝑟 83 𝑚𝑔/𝑡𝑎𝑏
𝑁
3 65 𝑚𝑔
5.788 mg 𝑔𝑟𝑎𝑖𝑛 𝑥 = 48.75 𝑚𝑔
= 𝑚𝐸𝑞 4 1 𝑔𝑟
0.02 N
289.4 𝑚𝑔/𝑚𝐸𝑞 𝑜𝑟 0.2894 𝑔/𝑚𝐸𝑞 = 𝑚𝐸𝑞
𝑤𝑡. 𝑜𝑓 𝑟𝑒𝑠𝑖𝑑𝑢𝑒
%𝑎𝑠𝑠𝑎𝑦 = 𝑥100
𝑤𝑡. 𝑜𝑓 𝑠𝑥
[(𝑉1 𝑁2 ) − (𝑉2 𝑁2 )](𝑚𝐸𝑞) 0.305 g
%𝑅3 𝑁 = 𝑥100 %𝑎𝑠𝑠𝑎𝑦 = 𝑥100
𝑤𝑡. 0.5589 g
%𝑅3 𝑁 =
[(15.00 mL x 0.0210 N ) − (7.30 mL x 0.0198 N )](0.2894 𝑔/𝑚𝐸𝑞)
𝑥100 %𝑎𝑠𝑠𝑎𝑦 = 54.57%
1.021 g
%𝑅3 𝑁 = 𝟒. 𝟖𝟑% 𝒘/𝒘 𝒂𝒍𝒌𝒂𝒍𝒐𝒊𝒅𝒔
𝑤𝑡. 𝑜𝑓 𝑟𝑒𝑠𝑖𝑑𝑢𝑒
3) Calculate the % w/w aminophylline if 𝑙𝑎𝑏𝑒𝑙𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡 = 𝑥 𝑎𝑣𝑒. 𝑤𝑡.
𝑤𝑡. 𝑜𝑓 𝑠𝑥
0.3120 g sample, assayed following the
0.305 𝑔
procedure given, required 12.10 mL of 𝑙𝑎𝑏𝑒𝑙𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡(𝑚𝑔) = 𝑥 83 𝑚𝑔/𝑡𝑎𝑏
0.1100N NH4SCN to bring about the 0.5589 𝑔
endpoint in the residual titration of silver 𝑙𝑎𝑏𝑒𝑙𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡(𝑚𝑔) = 45.29 𝑚𝑔/𝑡𝑎𝑏
nitrate. Exactly 20 mL of 0.1200 N AgNO3
𝑎𝑐𝑡𝑢𝑎𝑙 𝑤𝑡.
was taken initially. The titer value for 1 mL %𝑙𝑎𝑏𝑒𝑙𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡 = 𝑥100
of 0.1 N AgNO3 is 21.02 mg aminophylline 𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑤𝑡.
45.29 𝑚𝑔/𝑡𝑎𝑏
%𝑙𝑎𝑏𝑒𝑙𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡 = 𝑥100
𝑡𝑖𝑡𝑒𝑟 = 𝑁(𝑚𝐸𝑞) 48.75 𝑚𝑔
𝑡𝑖𝑡𝑒𝑟 𝑁(𝑚𝐸𝑞) %𝑙𝑎𝑏𝑒𝑙𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡
= = 𝟗𝟐. 𝟗𝟎% 𝒐𝒇 𝒄𝒐𝒅𝒆𝒊𝒏𝒆 𝒔𝒖𝒍𝒇𝒂𝒕𝒆/𝒕𝒂𝒃
𝑁 𝑁
𝑡𝑖𝑡𝑒𝑟
= 𝑚𝐸𝑞
𝑁
5) The weight of 20 tablets of morphine sulfate
21.02 mg (150 mg) is 3.075 g. If 0.3075 g was used in
= 𝑚𝐸𝑞 the assay and it required 10.3 mL of 0.023 N
0.1 N
210.2 𝑚𝑔/𝑚𝐸𝑞 𝑜𝑟 0.2102 𝑔/𝑚𝐸𝑞 = 𝑚𝐸𝑞 NaOH to back titrate, 25 mL of 0.021 N
H2SO4. Calculate the percent labeled
amount of morphine sulfate. Each mL of 1 N
[(𝑉1 𝑁2 ) − (𝑉2 𝑁2 )](𝑚𝐸𝑞) H2SO4 is equivalent to 758.83 mg of
%𝑅3 𝑁 = 𝑥100
𝑤𝑡. morphine sulfate.
 𝑤𝑡. 𝑝𝑒𝑟 𝑡𝑎𝑏 = 3.075 g/20 𝑡𝑎𝑏𝑙𝑒𝑡𝑠
= 0.15375 𝑔/𝑡𝑎𝑏 𝑜𝑟 153.75 𝑚𝑔/𝑡𝑎𝑏

𝑡𝑖𝑡𝑒𝑟 = 𝑁(𝑚𝐸𝑞)
𝑡𝑖𝑡𝑒𝑟 𝑁(𝑚𝐸𝑞)
=
𝑁 𝑁
𝑡𝑖𝑡𝑒𝑟
= 𝑚𝐸𝑞
𝑁

758.83
= 𝑚𝐸𝑞
1N
758.83 𝑚𝑔/𝑚𝐸𝑞 𝑜𝑟 0.75883 𝑔/𝑚𝐸𝑞 = 𝑚𝐸𝑞

[(𝑉1 𝑁2 ) − (𝑉2 𝑁2 )](𝑚𝐸𝑞)

𝑚𝑔/𝑡𝑎𝑏 = 𝑥100
𝑤𝑡.
(10.3
[(25 mL x 0.021 N) − mL x 0.023 N)](0.75883 𝑔/𝑚𝐸𝑞)
𝑚𝑔/𝑡𝑎𝑏 = 𝑥 153.75 𝑚𝑔/𝑡𝑎𝑏
0.3075 g
%𝑎𝑠𝑠𝑎𝑦 = 109.31 𝑚𝑔/𝑡𝑎𝑏

𝑎𝑐𝑡𝑢𝑎𝑙 𝑤𝑡.
%𝑙𝑎𝑏𝑒𝑙𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡 = 𝑥100
𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑤𝑡.
109.31 𝑚𝑔
%𝑙𝑎𝑏𝑒𝑙𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡 = 𝑥100
150 mg
%𝑙𝑎𝑏𝑒𝑙𝑒𝑑 𝑎𝑚𝑜𝑢𝑛𝑡 = 𝟕𝟐. 𝟖𝟕%
 PHAN111LEC_WEEK 12 % 𝑚𝑜𝑖𝑠𝑡𝑢𝑟𝑒 =
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟
𝑥100
𝑤𝑡. 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒

Water Content
• Moisture Determination – necessary to Titrimetric Method / Karl Fischer Method
specify certain water content limits in drug • Coulometric Method
monographs and ensure uniformity in official • Most chemical compounds are relatively
pharmaceuticals; water can be: stable at room temperature
o Water of crystallization (hydrates) • Substances that release water can affect
o Water in the Absorbed form results
• When crude drugs are sold with guaranteed • For crystalline compounds that contains
assay of active constituent, percent of API water in their molecular weight
must be calculated on the basis of a • Most rapid that requires only a small sample
moisture-free drug due to its influence in the and is specific for water
calculated results • Involves titration of sample in reagent
methanol with Karl Fischer Reagent
Water Content Determination Methods containing:
A. Gravimetric Method – for drugs containing o Sulfur Dioxide – reacts with water;
no constituents other than water, volatile at added second
105 degC; it takes 5 hours to determine the o Iodine – reacts with water; added
moisture content; sample needed must be second; forms sulfurtrioxide
10 grams; Drying Constant Weight – after 5 o Pyridine – prevents reverse reaction;
hours, cool the sample in a dessicator, and added last
then weigh; two consecutive weighs with no o Methanol (anhydrous) – prevents the
more than 0.5 milligrams difference; no pyridine-sulfur complex; added first
moisture left to form hydroiodic acid
B. Gravimetric Method – for drugs containing • Karl Fischer Reagent – concentration such
ether-soluble constituents, volatile at 105 that 1 mL of the reagent is equivalent to
degC approximately 5 mg of water; deteriorates
C. Azeotropic Method/Toluene Distillation – gradually; standardized with sodium tartrate
for vegetable drugs containing 2% or more (𝑁𝑎2 𝐶4 𝐻4 𝑂6 • 2𝐻2 𝑂); endpoint is canary
moisture; azeotrope (mixture of two liquids yellow
which each component doesn’t change)
a. Toluene-solvent in NF
b. Xylene-solvent in USP 0.1566 𝑥 𝑚𝑔 𝑜𝑓 𝑠𝑜𝑑𝑖𝑢𝑚 𝑡𝑎𝑟𝑡𝑟𝑎𝑡𝑒
𝐹=
D. Titrimetric Method/Karl Fischer Method – 𝑚𝐿 𝑜𝑓 𝑟𝑒𝑎𝑔𝑒𝑛𝑡 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑
for crystalline compounds that contains
water of hydration or absorbed water 𝑤ℎ𝑒𝑟𝑒 𝐹 𝑟𝑒𝑓𝑒𝑟𝑠 𝑡𝑜 𝒘𝒂𝒕𝒆𝒓 𝒐𝒇 𝒆𝒒𝒖𝒊𝒗𝒂𝒍𝒆𝒏𝒄𝒆
E. Dew Point Method – for determining water
at very low concentration 2𝐻2 𝑂 36.04
F. Electrolytic Hygrometric – for determining 𝑤𝑡. 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 = =
𝑁𝑎2 𝐶4 𝐻4 𝑂6 • 2𝐻2 𝑂 230.88
extremely low concentration of water = 0.1566

Azeotropic Method / Toluene Distillation • Formula:

• When the water has distilled over, rinse the 𝑤𝑎𝑡𝑒 𝑐𝑜𝑛𝑡𝑒𝑛𝑡 = 𝑆 𝑜𝑟 𝑣𝑜𝑙. 𝑜𝑓 𝑟𝑒𝑎𝑔𝑒𝑛𝑡 𝑥 𝐹
condenser tube with toluene. Continue the
distillation for 5 minutes, remove the heat, 𝑆𝑥𝐹
and allow the receiving tube to cool to room % 𝐻2 𝑂 = 𝑥100
𝑚𝑔. 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒
temp. When the water and toluene have • Karl Fischer Titrators
separated completely, read the volume of
water and calculate the percent of moisture
in the sample
 8.5 mL to reach the canary yellow endpoint,
determine the water content of citric acid.

0.1566 𝑥 𝑚𝑔 𝑜𝑓 𝑠𝑜𝑑𝑖𝑢𝑚 𝑡𝑎𝑟𝑡𝑟𝑎𝑡𝑒

𝐹=
𝑚𝐿 𝑜𝑓 𝑟𝑒𝑎𝑔𝑒𝑛𝑡 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑
0.1566 𝑥 350 𝑚𝑔
𝐹=
8.5 𝑚𝐿
𝐹 = 6.4482 𝑚𝑔/𝑚𝐿

Dew Point Method

𝑆𝑥𝐹
• The amount of water vapor in a system may % 𝐻2 𝑂 = 𝑥100
be determined by noting the temperature at 𝑚𝑔. 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒
which a dew or a mist forms when the 20 𝑚𝐿 𝑥 6.4482 𝑚𝑔/𝑚𝐿
% 𝐻2 𝑂 = 𝑥100
system is suddenly cooled under adiabatic 4800 𝑚𝑔
expansion following release of compression % 𝐻2 𝑂 = 2.69% 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑐𝑜𝑛𝑡𝑒𝑛𝑡 𝑖𝑛 𝐶𝑖𝑡𝑟𝑖𝑐 𝐴𝑐𝑖𝑑
Electrolytic Hygrometric Method
• Principle: Selective Electrolysis of water 2) Calculate the water content of an antibiotic
• Amount of electric current is a measure of powder using 350 mg sample. The water
water content equivalence factor (F) of the Karl Fischer
reagent is 4.6, and the volume of the
Ash Content Determination reagent used was 9.2 mL. The % of water
• Total Ash – representation of organic content is…
substances; if mataaas yung ash content,
𝑆𝑥𝐹
hindi maganda; may limits ang ash content % 𝐻2 𝑂 = 𝑥100
• Acid Insoluble Ash – part of total ash that is 𝑚𝑔. 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒
insoluble in 2N HCl % 𝐻2 𝑂 = 12.09% 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑐𝑜𝑛𝑡𝑒𝑛𝑡
• Water soluble Ash
• Sulfates Ash 3) From the following data, compute for the %
content and % acid insoluble ash.
a. Wt. of empty crucible = 26.630 g
b. Wt. of crucible drug = 2.030 g
c. Wt. of crucible with ash = 26.970 g
d. Wt. of crucible and acid insoluble ash
= 26.710 g

𝑇𝑜𝑡𝑎𝑙 𝐴𝑠ℎ (%)

𝑤𝑡. 𝑜𝑓 𝑡𝑜𝑡𝑎𝑙 𝑎𝑠ℎ/𝑎𝑐𝑖𝑑 𝑖𝑛𝑠𝑜𝑙𝑢𝑏𝑙𝑒 𝑎𝑠ℎ
= 𝑥 100
𝑤𝑡. 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝑢𝑠𝑒𝑑

Practice
1) Moisture content of citric acid was
determined by the Karl-Fischer Method, and
the following data were obtained. Wt. of
Citric Acid = 4.8 g, Vol. of reagent consumed
= 20 mL. The water equivalence factor of
the reagent was determined by titrating
0.350 g of sodium tartrate, and consumed
 PHAN111LEC_WEEK 13 Preparation of the Sample of Fats and Oils
• For determination, samples should undergo
preliminary treatment if they are turbid due
Analysis of Fats and Fixed Oils and Fatty
to separation of stearin
Substances • Such oils should be made clear by heating
• Constant – value or number of physical and their container on a water bath at 50 degC
chemical property until the turbidity disappears
o Specific gravity • If warming the oil fails to clarify, it should be
o Melting point filtered through a dry filter paper in a funnel
o Congealing point held in a hot water jacket
o Refractive index
o Optical activity Analysis of Fats and Oils
o Acid value, saponification value, • Determine the specific gravity and melting
ester value, iodine value, acetyl point of the sample
value, hydroxyl value, unsaponifiable • Acid Value/Acid Number/Acidity Index
matter, water, and sediment
o Liberation of free acids due to ester
• Purity of fixed oils, fats, waxes, and resins, hydrolysis from the catalytic action
etc. can’t be ascertained by the usual of light and heat, by bacterial action,
methods based on gravimetric and or by chemical treatment
volumetric processes o High Acid Value DOES NOT indicate
rancidity but hydrolytic
Concepts decomposition during their
• Fats – compounds consisting of fatty acids preparation, purification, or storage
combined with glycerol via ester linkages o Number of milligrams of potassium
• Fixed Oils – mixture of relatively high hydroxide required to neutralize the
quantities of liquid glycerides (glyceryl free acids in 1 g of sample
oleate) o Expressed as the number of
• Fats – contains large amounts of solid milliliters of 0.1 N NaOH required to
glycerides (glyceryl stearate) neutralize the free acids in 10 grams
o Butyric – 4C of sample
o Caproic – 6C
o Caprylic – 8C Acid Value Determination
o Capric – 10C • Unless otherwise directed, dissolve about
o Palmitic – 16C 10.0 g of the substance, accurately weighed,
o Stearic – saturated; 18C in 50 mL of a mixture of equal volumes of
o Oleic – unsaturated; 18C alcohol and ether in a flask
• If the test specimen does not dissolve in the
cold solvent, connect the flask with a
suitable condenser and warm slowly, with
frequent shaking, until the specimen
dissolves
• Add 1 mL of HPH TS, and titrate with 0.1N
KOH VS or 0.1N NaOH VS until solution
• Waxes – esters of high MW monohydric remains faintly pink after shaking for 30
alcohols and high MW fatty acids seconds
• Balsams – contains benzoic or amino acids
or their esters (56.11 𝑚𝑔/𝑚𝐸𝑞)(𝑚𝐿)(𝑁)
• Resins – natural or induced solid or semi- 𝐴𝑉 =
𝑤𝑡. 𝑜𝑓 𝑠𝑥
solid exudates from plants characterized by
being insoluble in water, soluble in alcohol 𝑚𝐿 𝑜𝑓 0.1𝑁 𝑁𝑎𝑂𝐻
and ether, crystallizable and softening or 𝐴𝑉 = 𝑥2
𝑤𝑡. 𝑜𝑓 𝑠𝑥
melting at a moderate heat
 Wherein 2 is based on the amount indicated in
specification

Ester Value
• A.k.a. Ester Number
Saponification Value • Defined as number of KOH in mg required
• A.k.a. Koettsdorfer Number or to saponify esters in 1 g of substance
Saponification Number • Substances that do not contain free acids
• Defined as the number of KOH in mg have equal EV and SV
required to neutralize the free fatty acids • Substances that have fatty acids have EV =
and saponify the esters in 1 g of sample AV – SV
• Helps detect the presence of glycerides • Important in the analysis of beeswax, which
which contain less than 16 or more than 18 indicates the presence of adulterants like
carbon atoms due to the fact that SV is paraffin which consists of high MW that
inversely proportional to the average of the would abnormally increase AV and lowers
MW of fatty acids found in the sample EV
• High SV = low MW fatty acids
𝑚𝐿 (𝑁)(𝑚𝐸𝑞)
Ex. 𝐸𝑉 = 𝑥 1000
𝑤𝑡. 𝑜𝑓 𝑠𝑥.
Saponification Value of Cottonseed Oil
o Place 1.5-2 g of sample accurately 𝐸𝑉 = 𝑆𝑉 (𝑤/𝑜 𝑓𝑎𝑡𝑡𝑦 𝑎𝑐𝑖𝑑𝑠)
weighed in a 250 mL flask
o Add to it exactly 25 mL of alcoholic 𝐸𝑉 = 𝐴𝑉 − 𝑆𝑉 (𝑤/ 𝑓𝑎𝑡𝑡𝑦 𝑎𝑐𝑖𝑑𝑠)
0.5N KOH (alcohol acts as solvent
for the oil and saponification Unsaponifiable Matter
products which are insol. in water).
• Substances that are not saponified by alkali
Reflux on a water bath for 30
hydroxides but are soluble in ordinary fat
minutes frequently rotating the
solvents
contents until saponification is
• After saponification, a small amount of
complete
residue is left consisting of phytosterol if the
o Add 1 mL of HPH and titrate the
oils or fats are of vegetable origin and
excess KOH with 0.5N HCl. (HCL
cholesterol if they are of animal origin
cannot be substituted with H2SO4
• Determination of this constant will indicate
which will yield K2SO4 that will not
the presence of unsaponifiable adulterants
dissolve in alcoholic solution)
such as petroleum oil added to linseed oil
o Perform a blank test (performed to
eliminate errors from all sources) 𝑤𝑡. 𝑜𝑓 𝑟𝑒𝑠𝑖𝑑𝑢𝑒
% 𝑈𝑛𝑠𝑎𝑝𝑜𝑛𝑖𝑓𝑖𝑎𝑏𝑙𝑒 𝑀𝑎𝑡𝑡𝑒𝑟 = 𝑥100
𝑆𝑉 𝑤𝑡. 𝑜𝑓 𝑠𝑥.
(𝑚𝐿 𝑜𝑓 𝐻𝐶𝑙𝑏𝑙𝑎𝑛𝑘 − 𝑚𝐿 𝑜𝑓 𝐻𝐶𝑙𝑠𝑎𝑚𝑝𝑙𝑒 )(𝑁)(56.11 𝑚𝑔/𝑚𝐸𝑞)
=
𝑤𝑡. 𝑜𝑓 𝑠𝑥.
Ex.
 Determination of Unsaponifiable Matter o Drying >120 - LiCod
o Transfer about 5.0 g of the oil or fat, o Semi-Drying 100-120 - CotSe
accurately weighed, to a 250 mL o Non-Drying <100 – OlAf
conical flask, add 50 mL of an • Methods of Determination for IV
alcoholic KOH and heat the flask on o Method I or Hanus Method – uses
a steam bath under a suitable iodobromide in 𝐶𝐻𝐶𝑙3
condenser to maintain reflux for 1 o Method II or Wijs Method – uses
hour, swirling frequently iodochloride in 𝐶𝐶𝑙4
o Cool to a temperature below 25, and
transfer the contents of the flask to a (𝑚𝐿 𝑜𝑓 𝑏𝑙𝑎𝑛𝑘 − 𝑚𝐿 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒)(𝑁)(𝑚𝐸𝑞)
𝑔 𝐼2 = 𝑥100
separator having a 𝑤𝑡. 𝑜𝑓 𝑠𝑥.
polytetrafluoroethylene stopcock,
rinsing the flask with two 50 mL Ex.
portions of water that are added to
the separator Iodine Value Determination
o Extract with three 100 mL portions o Introduce 200 mg of olive oil
of ether, combining with the ether accurately weighed into a 250 mL
extracts in another separator iodine flask
containing 40 mL of water o Add 20 mL of carbon tetrachloride
o Allow the mixture to separate, and and after the oil has dissolve add 25
discard the lower aqueous phase. mL of iodochloride TS accurately
Wash the ether extract with two measured from a burette
additional 40 mL portions of water, o Stopper the vessel, shake and allow
and discard the lower aqueous it to stand for 30 minutes protected
phase. Wash the ether extract from light
successively with a 40 mL portion of o Then add 20 mL of potassium iodide
KOH solution (3 in 100) and a 40 mL TS and 100 mL of recently boiled
portion of water and cooled water
o Wash the ether extract with 40 mL o Titrate the liberated iodine with 0.1N
portions of water until the last Sodium Thiosulfate. When the iodine
washing is not reddened by the color becomes quite pale, add 1 mL
addition of 2 drops of HPH TS. of Starch TS and continue the
Transfer the ether extract to a tared titration until the blue color is
flask, and rinse the separator with 10 discharged
mL of ether, adding the rinsing to the o Perform a blank test
flask.
o Evaporate the ether on a steam bath, Hydroxyl Value
and add 6 mL of acetone to the • A.k.a. Hydroxyl Number
residue. Remove the acetone in a • Defined as number of mg of KOH
current of air, and dry the residue at equivalent to the hydroxyl content of 1 g of
105 degC until successive weighing substance
differ by not more than 1 mg • Gives indication of the identity and purity of
fatty substances possessing alcoholic
Iodine Value hydroxyl groups
• A.k.a. Iodine Number • Low HV = adulteration with high MW
• Defined as the number of grams of iodine alcohols or with non-alcoholic fatty
absorbed under specified condition by 100 substances (i.e. paraffine, and petroleum oil)
grams of substance
• Quantitative measure of the proportion of Acetyl Value of Fatty Acids
unsaturated fatty acids presents in both free • Expressed as number of mg of KOH
and combined esters that have the property required to neutralize the acetic acid
of absorbing iodine obtained by saponification of 1 g of
• Indicate a pure or a mixture acetylated fatty acids
• Type of Fixed Oils Based on Iodine Value:
• Corresponds closely to the hydroxyl value of
fatty alcohol and the two constants have
much the same significance with respect to
identity and purity of substances
• Determined by acetylating hydroxy fatty 3) Find the SV of cottonseed oil if a 1.532 g
acids sample was refluxed with 25 mL of about
• From the saponification value of acetylated 0.5N alcoholic KOH, required 15.70 mL of
fatty acid and avid value of the original fatty 0.5100N HCl for the residual titration. The
acid, acetyl value is determined blank was run using the same volume of
0.5N of alcoholic KOH and required 26 mL
Other Constants of 0.5100N of HCl to bring about the
• Peroxide Value – no., in mEq of oxygen, of endpoint. Does it fit the USP specs of 190-
peroxides in 1 g of sample 198?
• Anisidine Value – defined as 100 times the
absorbance (at 350 mm) of a solution (𝑚𝐿 𝑜𝑓 𝐻𝐶𝑙𝑏𝑙𝑎𝑛𝑘 − 𝑚𝐿 𝑜𝑓 𝐻𝐶𝑙𝑠𝑎𝑚𝑝𝑙𝑒 )(𝑁)(56.11)
𝑆𝑉 =
resulting form reaction of 1 g of fat in 100 𝑤𝑡. 𝑜𝑓 𝑠𝑥.
mL of solvent (26 mL − 15.70 mL)(0.5100N )(56.11)
𝑆𝑉 =
• Total Oxidation Value – combined PV and 1.532 g
Anisidine Value (2PV + AV) 𝑆𝑉 = 𝟏𝟗𝟐. 𝟑𝟗; 𝒚𝒆𝒔, 𝒊𝒕 𝒄𝒐𝒏𝒇𝒐𝒓𝒎𝒔
• Solidification Temperature of FA –
congealing point
• Fatty Acid Composition 4) A corn oil sample weighs 1.60 g was
saponified with 25 mL of alcoholic KOH and
Practice required 9.0 mL of 0.5N HCl to titrate the
1) Find the acid number of a rosin sample excess KOH. In the blank determination, 20
weighing 1.100 g which required 28 mL of mL of 0.5N HCl was required to titrate the
0.1100 N to bring the endpoint alkali. Calculate the SV? USP specs should
be 187-193
(56.11 𝑚𝑔/𝑚𝐸𝑞)(𝑚𝐿)(𝑁)
𝐴𝑉 =
𝑤𝑡. 𝑜𝑓 𝑠𝑥 (𝑚𝐿 𝑜𝑓 𝐻𝐶𝑙𝑏𝑙𝑎𝑛𝑘 − 𝑚𝐿 𝑜𝑓 𝐻𝐶𝑙𝑠𝑎𝑚𝑝𝑙𝑒 )(𝑁)(56.11)
(56.11 𝑚𝑔/𝑚𝐸𝑞)(28 mL)(0.1100 N) 𝑆𝑉 =
𝑤𝑡. 𝑜𝑓 𝑠𝑥.
𝐴𝑉 = (20 mL − 9.0 mL )(0.5N )(56.11)
1.100 g
𝑆𝑉 =
𝐴𝑉 = 𝟏𝟓𝟕. 𝟏𝟏 𝒎𝒈/𝒈 1.60 g
𝑆𝑉 = 𝟏𝟗𝟐. 𝟖𝟖; 𝒄𝒐𝒏𝒇𝒐𝒓𝒎𝒔
2) If 2 g sample of cod liver oil required 4.5 mL
of 0.02N NaOH in the titration of fatty
acids, would it conform with the 5) Beeswax sample has an acid value of 20.4
specification? AV is not more than 1 mL of and saponification value of 89.8. Determine
0.1N NaOH in 2 grams of sample is required. the ester value of the sample. USP specs
should be between 72-77
(56.11 𝑚𝑔/𝑚𝐸𝑞)(𝑚𝐿)(𝑁)
𝐴𝑉 = 𝐸𝑉 = 𝐴𝑉 − 𝑆𝑉
𝑤𝑡. 𝑜𝑓 𝑠𝑥
(56.11 𝑚𝑔/𝑚𝐸𝑞)(4.5 mL)(0.02) 𝐸𝑉 = 20.4 − 89.8
𝐴𝑉 = 𝐸𝑉 = 𝟔𝟗. 𝟒; 𝐝𝐨𝐞𝐬 𝐧𝐨𝐭 𝐜𝐨𝐧𝐟𝐨𝐫𝐦
2g
𝐴𝑉 = 𝟐. 𝟓𝟐 𝒎𝒈/𝒈; 𝒚𝒆𝒔, 𝒊𝒕 𝒄𝒐𝒏𝒇𝒐𝒓𝒎𝒔
6) A 4.09 g sample was treated with KOH
𝑁1 𝑉1 = 𝑁2 𝑉2 dissolved in alcohol and heated under a
(0.02N )(4.5 mL) (0.1𝑁)𝑉2 reflux condenser. The ether extract was
= evaporated to dryness on a water bath. The
0.1𝑁 0.1𝑁
0.9 𝑚𝐿 = 𝑉2 residue left is 0.053 g. Calculate the %
Unsaponifiable Matter
0.9 𝑚𝐿
𝐴𝑉 = 𝑥2 𝑤𝑡. 𝑜𝑓 𝑟𝑒𝑠𝑖𝑑𝑢𝑒
2g % 𝑈𝑛𝑠𝑎𝑝𝑜𝑛𝑖𝑓𝑖𝑎𝑏𝑙𝑒 𝑀𝑎𝑡𝑡𝑒𝑟 = 𝑥100
𝐴𝑉 = 𝟎. 𝟗 𝒎𝑳 𝑤𝑡. 𝑜𝑓 𝑠𝑥.
 0.053 g
% 𝑈𝑛𝑠𝑎𝑝𝑜𝑛𝑖𝑓𝑖𝑎𝑏𝑙𝑒 𝑀𝑎𝑡𝑡𝑒𝑟 = 𝑥100 0.954 𝑚𝐿
4.09 g
𝐴𝑉 = 𝑥2
% 𝑈𝑛𝑠𝑎𝑝𝑜𝑛𝑖𝑓𝑖𝑎𝑏𝑙𝑒 𝑀𝑎𝑡𝑡𝑒𝑟 = 𝟏. 𝟑𝟎% 2.487 g
𝐴𝑉 = 𝟎. 𝟕𝟔𝟕𝟐 𝒎𝑳 𝒐𝒇 𝟎. 𝟏𝐍 𝐍𝐚𝐎𝐇
7) A 0.1194 g sample was dissolved in 𝐶𝐻𝐶𝑙3 .
Twenty-five mL of ICl was added, stoppered,
and allowed to stand for 30 mins. KI was b. A 0.1294 g sample was dissolve in
added and titrated with 8.9 mL of 0.1024 N 𝐶𝐶𝑙3 . Twenty-five mL of ICl was
Sodium thiosulfate. The blank test added, stoppered and allowed to
consumed 24 mL of the titrant. stand for 30 minutes. KI was added
and titrated with 8.9 mL of 0.0994N
𝐼2 = 127 𝑔/𝑚𝑜𝐿 Sodium thiosulfate. The blank test
= 127/1(1000) consumed 24 mL of the titrant.
𝐼2 = 0.127 𝑔/𝑚𝐸𝑞
𝐼2 = 127 𝑔/𝑚𝑜𝐿
(𝑚𝐿 𝑜𝑓 𝑏𝑙𝑎𝑛𝑘 − 𝑚𝐿 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒)(𝑁)(𝑚𝐸𝑞) = 127/1(1000)
𝑔 𝐼2 = 𝑥100
𝑤𝑡. 𝑜𝑓 𝑠𝑥. 𝐼2 = 0.127 𝑔/𝑚𝐸𝑞
(24 mL − 8.9 mL)(0.1024 N)(0.127 𝑔/𝑚𝐸𝑞)
𝑔 𝐼2 = 𝑥100
0.1194 g
𝑔 𝐼2 = 𝟏𝟔𝟒. 𝟒𝟕% (𝑚𝐿 𝑜𝑓 𝑏𝑙𝑎𝑛𝑘 − 𝑚𝐿 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒)(𝑁)(𝑚𝐸𝑞)
𝑔 𝐼2 = 𝑥100
𝑤𝑡. 𝑜𝑓 𝑠𝑥.
8) Determine the iodine value of a sample of (24 mL − 8.9 mL )(0.0994N)(0.127 𝑔/𝑚𝐸𝑞)
𝑔 𝐼2 = 𝑥100
olive oil weighing 0.2100 g if 24.15 mL and 0.1294 g
12 mL of 0.1100N sodium thiosulfate are 𝑔 𝐼2 = 𝟏𝟒𝟕. 𝟑𝟏%; 𝒚𝒆𝒔, 𝒊𝒕 𝒄𝒐𝒏𝒇𝒐𝒓𝒎𝒔
required for the blank and residual titrations.
Does it conform to USP specs of 79-88? c. A 5.09 g sample was treated with
KOH dissolved in alcohol and heated
𝐼2 = 127 𝑔/𝑚𝑜𝐿 under a reflux condenser. The ether
= 127/1(1000) extract was evaporated to dryness
𝐼2 = 0.127 𝑔/𝑚𝐸𝑞 on a water bath. The residue left is
1.053 g
(𝑚𝐿 𝑜𝑓 𝑏𝑙𝑎𝑛𝑘 − 𝑚𝐿 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒)(𝑁)(𝑚𝐸𝑞)
𝑔 𝐼2 = 𝑥100 𝑤𝑡. 𝑜𝑓 𝑟𝑒𝑠𝑖𝑑𝑢𝑒
𝑤𝑡. 𝑜𝑓 𝑠𝑥.
(24.15 − 12 mL )(0.1100N)(0.127 𝑔/𝑚𝐸𝑞 ) % 𝑈𝑛𝑠𝑎𝑝𝑜𝑛𝑖𝑓𝑖𝑎𝑏𝑙𝑒 𝑀𝑎𝑡𝑡𝑒𝑟 = 𝑥100
𝑤𝑡. 𝑜𝑓 𝑠𝑥.
𝑔 𝐼2 = 𝑥100
0.2100 g 1.053 g
% 𝑈𝑛𝑠𝑎𝑝𝑜𝑛𝑖𝑓𝑖𝑎𝑏𝑙𝑒 𝑀𝑎𝑡𝑡𝑒𝑟 = 𝑥100
𝑔 𝐼2 = 𝟖𝟎. 𝟖𝟑% 𝒐𝒇 𝑰𝟐 ; 𝒚𝒆𝒔 𝒊𝒕 𝒄𝒐𝒏𝒇𝒐𝒓𝒎𝒔 5.09 g
% 𝑈𝑛𝑠𝑎𝑝𝑜𝑛𝑖𝑓𝑖𝑎𝑏𝑙𝑒 𝑀𝑎𝑡𝑡𝑒𝑟
9) A sample of cod liver oil was analyzed: = 𝟐𝟎. 𝟔𝟗%; 𝒏𝒐 𝒊𝒕 𝒅𝒐𝒆𝒔 𝒏𝒐𝒕 𝒄𝒐𝒏𝒇𝒐𝒓𝒎
a. A 2.487 g sample was dissolved in
the mixture of alcohol and ether d. A 1.525 g sample was refluxed with
which was neutralized by 0.053N 25 mL of 0.5N KOH and required
NaOH. The resulting solution was 15.7 mL of 0.51N HCl. Blank
heated under reflux condenser and determination consumed 26 mL of
cooled. It was titrated with 1.8 mL of the same acid solution
0.053N NaOH
𝑆𝑉
(56.11 𝑚𝑔/𝑚𝐸𝑞)(1.8 mL )(0.053N ) (𝑚𝐿 𝑜𝑓 𝐻𝐶𝑙𝑏𝑙𝑎𝑛𝑘 − 𝑚𝐿 𝑜𝑓 𝐻𝐶𝑙𝑠𝑎𝑚𝑝𝑙𝑒 )(𝑁)(56.11 𝑚𝑔/𝑚𝐸𝑞)
𝐴𝑉 = =
2.487 g 𝑤𝑡. 𝑜𝑓 𝑠𝑥.
𝐴𝑉 = 𝟐. 𝟏𝟓𝟐 𝒎𝒈/𝒈; 𝒚𝒆𝒔, 𝒊𝒕 𝒄𝒐𝒏𝒇𝒐𝒓𝒎𝒔 (26 mL − 15.7 mL )(0.51N)(56.11 𝑚𝑔/𝑚𝐸𝑞)
𝑆𝑉 =
1.525 g
𝑁1 𝑉1 = 𝑁2 𝑉2 𝑆𝑉 = 𝟏𝟗𝟑. 𝟐𝟖; 𝒏𝒐, 𝒊𝒕 𝒅𝒐𝒆𝒔 𝒏𝒐𝒕 𝒄𝒐𝒏𝒇𝒐𝒓𝒎
(0.053N )(1.8 mL) (0.1𝑁)𝑉2
= e. Does the sample conform with the
0.1𝑁 0.1𝑁
0.954 𝑚𝐿 = 𝑉2 specs?
 i. AV = NMT 1 mL of 0.1N
NaOH in 2 g of sample
ii. SV = 180-192
iii. IV = 145-180
iv. UM = NMT 1.3%
 PHAN111LEC_WEEK 14 ▪ Propionic
▪ Butyric
▪ Valeric
Analysis of Volatile Oils ▪ Benzoic
• A.k.a. Ethereal Oils or Essential Oils or ▪ Cinnamic
Essences ▪ Hydrocyanic
• Odorous compounds found in plants, o Acids in combination with alcohols
distinct odor, optically active, exposure in air as esters
they oxidize ▪ Linalyl acetate
• Contains ▪ Bornyl acetate
o Hydrocarbons of the isocyclic series ▪ Methyl acetate
such as: o Sulfur compounds
▪ Monoturpenes ( C10H16) ▪ Allyl isothiocyanate
▪ Sesquiturpenes (C15H24) • Purity and quality can be judged to some
• Pinene extent by their appearance, odor, color, etc.
• Camphene but the information gained from the
• Limonene determination of their physical constants
• Bronylene
• Fenchene Physical Content
• Dipentene • Specific Gravity – determined by Westphal
• Sylvestrene Balance or Pycnometer that ranges from
• Phellandrene 0.84 to 1.2
o Alcohols both in free state and in o Oils lighter than water: orange,
combination with acids as esters caraway, coriander, lemon,
▪ Cyclic turpentine, and rosemary oils
▪ Monocylic o Oils heavier than water: anise,
• linalool cinnamon, clove, sassafras oils
• Geraniol • Rotatory Power – measured by Laurent
• Citroneol Half-Shadow Polarimeter
• Terpineol o Presence of adulterants such as
• Borneol alcohol or turpentine oil is
• Menthol determined by its influence in the
• Santalool rotatory power values
o Aldehydes • Refractive Index – most used instrument is
▪ Benzaldehyde the Abbe Refractometer that ranges from
▪ Cinnamic aldehyde 1.46 to 1.61 at 20 degC. The determination
▪ Salicylic aldehyde may serve in the detection of extraneous
▪ Citral matter
▪ Citronellal • Congealing Point – most essential oils
o Ketones solidify only at low temp.; low congealing
▪ Camphor point = has impurities
▪ Carvone • Distilling Range
▪ Fenchone o Fractional Distillation – fractionation
▪ Thujone of the oil determines the possible
▪ Menthone presence of alcohol which distills or
o Phenols boils below 100 degC
▪ Anethol • Solubility – generally, volatile oils are soluble
▪ Eugenol in organic solvents (70-90% alcohol);
▪ Carvacrol turpentine oil, petroleum oil or fatty oils are
▪ Saffrol only slightly soluble and can be seen through
▪ Chavicol its turbidity
o Acids sometimes in the free state in
small quantities like Factors causing Deterioration of Volatile Oils
▪ Acetic
• When exposed to light and air, fragrance is
lost
• Terpene-containing oils produces peroxides,
the presence of which indicated by the
whitening of the cork of their containers
• On long standing, volatile oils thicken,
become resinified or deposit crystalline
compounds
• Tin containers promote deterioration of
odor and development of color; should be
an amber-colored bottle
• Adding 5-10% fixed oils or alcohol can
preserve volatile oils Isolation of Volatile Oil in Spirits
• The assay for volatile oils in spirits is based
Isolation of Volatile Oils on the isolation of the oil from the other
• Isolations of volatile oils from crude drugs or components of the spirit by the use of an
oleoresins occur through Steam Distillation immiscible solvent and measuring the
and the measurement of the volume of oil volume of the liberated oil.
obtained • The contents of the bottle are mixed by
rotating the bottle and treated with more
calcium chloride solution until the oil that
separates is brought to the level of the
graduations on the neck of the flask. The
mixture is centrifuged for 5 minutes at about
1500 revolutions per minute and the volume
of the oil is measured using the calibrations
in the neck of the flask.
• The oil in the spirit is salted out of the
• Condenser is combined with the receiver to solution by the addition of the saturated
avoid as much as possible the loss of volatile calcium chloride solution. The kerosene
oil vaporization and to provide direct dissolves the oil.
reading of the volume of oil • The HCl is added to neutralize any alkali
• Oil is the drug to be assayed is lighter than which would otherwise made the acids and
water, its volume is directly measured in the aldehydes in the oil will be water soluble
receiver which is provided with a lower • The Babcock Bottle is provided with a long
portion graduated to tenths of a millimeter neck calibrated into eight divisions of 0.2
• Oil is heavier than water, the oil is mL each
transferred to a measuring cylinder and the • The percent of oil in the spirit is calculated
water with whatever oil remains is placed in as follows:
a separator
• The oil trap is rinsed with ether, the rinsing If the height of the column of the oil-kerosene mixture
added to the separatory funnel. The ethereal occupies 7.5 divisions, thus, the oil will measure 2.5
layer separated is allowed to stand so that divisions
the ether is evaporated, and any oil left is 7.5 𝑑𝑖𝑣 − 5 𝑑𝑖𝑣. = 2.5 𝑑𝑖𝑣
added to the oil in the measuring cylinder. The 5 divisions represent 1 ml of kerosene added since
The volume of the oil is measured at 25 each division is equal to 0.2 mL + 1 for error
2.5 𝑑𝑖𝑣 𝑥 0.21 𝑚𝐿 = 0.525 𝑚𝐿
degC. If the amount of oil is to be expressed
in weight it is dried with anhydrous sodium The number of divisions is multiplied by 0.21 instead of
sulfate and its specific gravity determined at 0.2 to correct for the error due to the solubility of the
25 degC after measuring its volume. oil-kerosene layer in the aqueous layer and also due to
contraction of volume of the immiscible solvents when
• Clevenger Apparatus – only official USP
mixed.
method used in quality control of volatile
0.525
oils through boiling, condensing, and % 𝑜𝑓 𝑉𝑂 𝑖𝑛 𝑠𝑝𝑖𝑟𝑖𝑡𝑠 = 𝑥 100
decantation 5
 % 𝑜𝑓 𝑉𝑂 𝑖𝑛 𝑠𝑝𝑖𝑟𝑖𝑡𝑠 = 10.5% • 1 mL of 0.5N KOH is equivalent to 0.021 g of
acetyl radical
• 1 – (E x 0.0021) is a correction factor which
Determination of Alcohol Content should be done when the sample of volatile
• Menthol and borneol are the alcohols contains both ester and alcohol
present in peppermint oil and rosemary oil • The value 0.0021 is derived from the ratio of
are found free and combined as esters. The the acetyl radical to that of methyl acetate
alcohol content determination is so valuable
that it alone is sufficient to prove the purity Determination of Aldehyde and Ketone Content
and value of the volatile oil • Bisulfate Method – principle of aldehydes
• Determination consists of conversion of the and ketones forming soluble addition
free alcohol to its acetate ester and products with sodium sulfite with water that
saponification of freshly produces acetate, leaves a certain volume of oil which do not
and original acetate with standard alcoholic contain aldehydes or ketones; measured in
potassium hydroxide acacia flask
• Hydroxylamine Method – for ketones only
Isolation of Alcohol Content • By finding the difference between the
• The acetylized oil is allowed to separate volume of original oil and that of the residual
from the aqueous layer oil, the volume of aldehyde or ketone is
• The water layer is rejected and the oil determined
washed with several portions of Sodium • Limited only for the assay of volatile oils
carbonate TS. It is then diluted with an equal which do not contain constituents other
volume of water until the last washing is than aldehyde and ketones or for samples
already alkaline to HPH TS with very little aldehyde content
• The acetylized oil is dried with anhydrous
sodium sulfate. Transfer 5 mL of the dry 𝑉 𝑜𝑓 𝑠𝑥. −𝑉 𝑜𝑓 𝑟𝑒𝑠𝑖𝑑𝑢𝑒
% 𝑉𝑜𝑙 𝑜𝑖𝑙 = 𝑥100
acetylized oil to a tared 100 mL Erlenmeyer 𝑉 𝑜𝑓 𝑠𝑥.
flask and weigh accurately
• Add 50 mL of 0.5N alcoholic KOH, connect Determination of Phenol Content
the flask with a reflux condenser and boil • Volatile oils that contain phenols, when
the mixture on a water bath for exactly one shaken with solution of KOH diminish in
hour volume because of the steady solubility of
• Allow the mixture to cool and add 10 drops the phenol constituents in alkali leaving the
of HPH TS and titrate the excess alkali with non-phenolic portion of the oil undissolved
0.5N H2SO4. A blank determination is
performed Practice
• The acetylization flask should be heated 1) What would be the percentage in VO in
over an asbestos board to avoid the orange spirit if the number of the divisions
decomposition of oil occupied by the oil-kerosene mixture is 8
• The acetylization flask is provided with an and the volume of kerosene added is 1.2 mL.
air condenser to condense any vapors of the The volume of the sample of orange spirit
volatile oil and the acetic acid that is transferred to the Bobcock bottle is 4.8 mL.
produced Compute for the percentage volatile oil if
the volume of kerosene is equivalent to 5
𝐴 𝑥 7813 divisions.
%𝑡𝑜𝑡𝑎𝑙 𝑒𝑠𝑡𝑒𝑟 = 𝑥[1 − (𝐸 𝑥 0.0021)
𝐵 − (𝐴 𝑥 0.021)
8 𝑑𝑖𝑣 − 5 𝑑𝑖𝑣. = 3 𝑑𝑖𝑣
Where A is the difference between mL of sulfuric acid 3 𝑑𝑖𝑣 𝑥 0.21 𝑚𝐿 = 0.63 𝑚𝐿
in blank and sample, B is the weight of acetylized oil,
and E is the percentage of esters calculated as 0.63 𝑚𝐿
% 𝑜𝑓 𝑉𝑂 𝑖𝑛 𝑠𝑝𝑖𝑟𝑖𝑡𝑠 = 𝑥 100
menthyl acetate; 5
% 𝑜𝑓 𝑉𝑂 𝑖𝑛 𝑠𝑝𝑖𝑟𝑖𝑡𝑠 = 𝟏𝟐. 𝟔%
• 1 mL of 0.5N KOH is equivalent to 0.07813 g
of menthol
 2) Exactly 10 mL of cinnamon oil was
introduced into a cassia flask and into it
added was 50 mL of saturated sodium sulfite
solution, boiled and shaken repeatedly. The
undissolved oil remaining after this
treatment measured 4.3 mL. What is the
percentage of cinnamon aldehyde in the
sample?

𝑉 𝑜𝑓 𝑠𝑥. −𝑉 𝑜𝑓 𝑟𝑒𝑠𝑖𝑑𝑢𝑒
% 𝑉𝑜𝑙 𝑜𝑖𝑙 = 𝑥100
𝑉 𝑜𝑓 𝑠𝑥.
10 mL − 4.3 mL
% 𝑉𝑜𝑙 𝑜𝑖𝑙 = 𝑥100
10 𝑚𝐿
% 𝑉𝑜𝑙 𝑜𝑖𝑙 = 𝟓𝟕% 𝒐𝒇 𝒄𝒊𝒏𝒏𝒂𝒎𝒐𝒏 𝒂𝒍𝒅𝒆𝒉𝒚𝒅𝒆

3) 2 mL of benzaldehyde was treated with 25

mL of hydroxylamine HCl and then titrated
with 23 mL of 0.98N NaOH. In the blank
test, the same amount of hydroxylamine
HCL consumed 15 mL of 0.98N NaOH.
Compute for the percentage benzaldehyde if
1 mL of 1N NaOH is equivalent to 106.1 mg
of benzaldehyde

𝑡𝑖𝑡𝑒𝑟 = 𝑁(𝑚𝐸𝑞)
𝑡𝑖𝑡𝑒𝑟 𝑁(𝑚𝐸𝑞)
=
𝑁 𝑁
𝑡𝑖𝑡𝑒𝑟
= 𝑚𝐸𝑞
𝑁

0.1061 g
𝑚𝐸𝑞 =
1N
𝑚𝐸𝑞 = 0.1061 𝑚𝐸𝑞

= (𝑚𝐿 𝑜𝑓 𝑁𝑎𝑂𝐻𝑠𝑎𝑚𝑝𝑙𝑒 − 𝑚𝐿 𝑜𝑓 𝑁𝑎𝑂𝐻𝑏𝑙𝑎𝑛𝑘 )(𝑁)(0.1061)

%𝑏𝑒𝑛𝑧𝑎𝑙. 𝑥100
𝑤𝑡. 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒
(23 mL − 15 mL)(0.98N)(0.1061)
%𝑏𝑒𝑛𝑧𝑎𝑙. = 𝑥100
2 mL
%𝑏𝑒𝑛𝑧𝑎𝑙. = 𝟒𝟏. 𝟓𝟗%