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# PHARCHM 3 LECTURE

## PRACTICE SET ON REDOX TITRATIONS

1. A solution of Na2S2O3 was standardized by dissolving 0.1210-g of KIO3 in water, adding a large excess of KI
and acidifying with HCl. The liberated I2 required 41.64-mL of the thiosulfate solution to decolorize the
blue iodo-starch complex. Calculate the molarity of the Na2S2O3 solution.
Reactions: IO3-1 + 5I-1 + 6H+1 3I2 + 3H2O
I2 + 2Na2S2O3 Na2S4O6 + 2NaI
Molar Masses: KIO3 = 214.0 Na2S2O3 = 158.1 ANSWER: 0.08147M Na2S2O3

2. Exactly 33.31-mL of a KMnO4 solution were required to titrate a 0.1278-g sample of primary standard
Na2C2O4. What is the molarity of the KMnO4 solution?
5Na2C2O4 + 2KMnO4 + 8H2SO4 K2SO4 + 2MnSO4 + Na2SO4 + 10CO2 + 8H2O
Molar Masses: KMnO4 = 158.0 Na2C2O4 = 134.0 ANSWER: 0.01145M KMnO4

3. Determine the percentage of iron in a sample of limonite from the following data.
Weight of sample 0.5000-g
Volume of KMnO4 added 50.0-mL 1.00-mL KMnO4 0.005317-g Fe
Volume of FeSO4 used for back-titration 6.00-mL 1.00-mL FeSO4 0.00920-g FeO
Molar Masses: Fe = 55.85 FeO = 71.84 ANSWER: 44.6% Fe

4. Calculate the percent purity of copper in an ore in terms of Cu2O from the given data:
Weight of copper ore 1.20-g
Volume of Na2S2O3 used 40.00-mL 1.00-mL Na2S2O3 0.004175-g KBrO3
Molar Masses: KBrO3 = 167.0 Cu2O = 143.1 ANSWER: 35.8% Cu2O

5. A 30.00-L air sample was passed through an absorption tower containing a solution of Cd+2, where H2S was
retained as CdS. The mixture was acidified and treated with 10.00 mL of 0.01070 M I2. After the reaction
S-2 + I2 S (s) + 2 I-
was complete, the excess iodine was titrated with 12.85 mL of 0.01344 M thiosulfate. Calculate the
concentration of H2S in ppm; use 1.20 g/L for the density of the gas stream.
Molar Mass: H2S = 34.082 ANSWER: 19.5 ppm H2S

6. A 5.00-mL sample of brandy was diluted to 1.00-L in a volumetric flask. The ethanol in a 25.00-mL aliquot
of the diluted solution was distilled into 50.00-mL of 0.02000M K2Cr2O7 where oxidation to acetic acid
occurred with heating:
3C2H5OH + 2Cr2O7-2 + 16H+1 4Cr+3 + 3CH3COOH + 11H2O
After cooling, 20.00-mL of 0.1253M Fe+2 was introduced into the flask. The excess Fe+2 was then titrated
with 7.46-mL of the standard K2Cr2O7 to diphenylamine sulfonic acid endpoint. Calculate the weight by
volume percent of C2H5OH in the brandy.
Molar Masses: K2Cr2O7 = 294.2 C2H5OH = 46.07 ANSWER: 40.4% C2H5OH

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7. A 0.2891-g sample of an antibiotic powder was dissolved in HCl and the solution diluted to 100.0-mL. A
20.00-mL aliquot was transferred to a flask, followed by 25.00-mL of 0.01767M KBrO3. An excess of KBr
was added to form Br2 and the flask was stoppered. After 10 minutes, during which time the Br2
brominated sulfanilamide, an excess of KI was added. The liberated I2 was then titrated with 12.92-
mL of 0.1215M Na2S2O3. Calculate the percent NH2C6H4SO2NH2 in the powder.
Reactions: a) BrO3-1 + 5Br-1 + 6H+1 3Br2 + 3H2O
b) NH2C6H4SO2NH2 + 2Br2 NH2C6H2Br2SO2NH2 + 2H+1 + 2Br-1
c) Br2 + 2I-1 2Br-1 + I2 (excess KI)
d) I2 + 2S2O3-2 S4O6-2 + 2I-1
Molar Masses: KBrO3 = 167.0 NH2C6H4SO2NH2 = 172.2 ANSWER: 80.47% NH2C6H4SO2NH2

## PRACTICE SET ON GRAVIMETRIC METHODS

1. Treatment of a 0.4000-g sample of impure potassium chloride with an excess of AgNO3 resulted in the
formation of 0.7332 g of AgCl. Calculate the percentage of KCl in the sample.
Molar Masses: AgCl = 143.32 KCl = 74.55 Answer: 95.35% KCl

2. A 0.3516-g sample of a commercial phosphate detergent was ignited at a red heat to destroy the organic
matter. The residue was then taken up in hot HCl, which converted the P to H3PO4. The phosphate was
precipitated as MgNH4PO46H2O by addition of Mg2+ followed by aqueous NH3. After being filtered and
washed, the precipitate was converted to Mg2P2O7 by ignition at 10000C. This residue weighed 0.2161g.
Calculate the percent P in the sample.
Molar Masses: Mg2P2O7 = 222.57 P = 30.974 Answer: 17.11% P

3. The mercury in a 0.7152-g sample was precipitated with an excess of paraperiodic acid, H5IO6, according
to the following reactions:
5 Hg+2 + 2 H5IO6 Hg5(IO6)2 (s) + 10 H+
The precipitate was filtered, washed free of precipitating agent, dried and found to weigh 0.3408-g.
Calculate the percentage of Hg2Cl2 in the sample.
Molar Masses: Hg5(IO6)2 = 1448.75 Hg2Cl2 = 472.09 Answer: 38.82% Hg2Cl2

## 4. At elevated temperatures, NaHCO3 is converted quantitatively to Na2CO3:

2 NaHCO3 (s) Na2CO3 (s) + CO2 (g) + H2O (g)
Ignition of a 0.3592-g sample containing NaHCO3 and non-volatile impurities yielded a residue weighing
0.2362-g. Calculate the percent purity of the sample.
Molar Masses: NaHCO3 = 84.00 CO2 = 44.00 H2O = 18.00 Answer: 92.79% NaHCO3

A 0.2795-g sample of an organic mixture containing only C6H6Cl6 and C14H9Cl5 was burned in a stream of oxygen
in a quartz tube. The products (CO2, H2O and HCl) were passed through a solution of NaHCO3. After
acidification, the chloride in this solution yielded 0.7161-g of AgCl. Calculate the percent of each halogen
compound in the sample. Answers: 57.82% C6H6Cl6 and 42.18%C14H9Cl5
Molar Masses: AgCl = 143.32 C6H6Cl6 = 290.83 C14H9Cl5 = 354.49

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PRACTICE SET ON SPECIAL METHODS OF ANALYSIS

1. From the following data, compute for the percent total ash, percent acid-insoluble ash and percent
moisture. Does the sample conform with the official requirements?
Weight of empty crucible 52.452-g
Weight of crucible + sample 61.684-g
Weight of crucible + sample after drying to constant weight 60.320-g
Weight of crucible + residue after incineration 53.005-g
Weight of crucible + acid-insoluble residue 52.4858-g

## Compendium specifications: Percent Ash n.m.t. 6.00%

Percent Acid-Insoluble Ash n.m.t. 0.5%
Percent Moisture n.m.t. 15.00%

ANSWERS (Hydrous Basis) : 5.99% Ash / 0.366% Acid-Insoluble Ash / 14.8% Moisture

2. The moisture content of citric acid was determined by the titrimetric method with the following data.
Weight of citric acid 4.8-g
Volume of Karl Fischer reagent 20.0-mL

(Note: The water equivalence factor of the Karl Fischer reagent was determined by titrating 0.350-g of
sodium tartrate with 12.0-mL of the Karl Fischer reagent.) What is the percent moisture of the sample?

3. The moisture content of powdered digitalis leaves sample was determined by the toluene distillation
method with the following data.
Weight of powdered digitalis leaves 48.6450-g
Volume of water collected from the distillate 2.5-mL

## USP Water Limit: 6.0%

a) Calculate the percent moisture in the sample. Does it conform with the USP specifications?
b) What would be the volume of water collected from a 50.0-g digitalis leaves sample, if the percent
moisture in the sample is 6.0%? ANSWER: a) 5.1% moisture ; yes b) 3.0-mL water

4. In the assay of benzoin, 2.3 g of the sample were weighed and extracted in a continuous extraction
apparatus with alcohol. The drug-insoluble residue weighed 650-mg. The moisture content of benzoin is
3.2%. Is the benzoin Siam or Sumatra variety?
(Note: Extractive limit of the Siam variety is 90% and Sumatra variety is 75%.)

5. The ether-insoluble residue of cocoa weighing 1.832 g was treated with acid and alkali respectively, and
the remaining residue was found to be 1.435-g. This residue was incinerated and the residue left after
incineration weighed 980-mg. Does the sample conform with the USP requirement for crude fiber which is
7.0%? ANSWER: No (25% crude fiber)

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6. A sample of cod liver oil was analyzed according to the following procedures and the data were collected:
a. A 2.487-g sample was dissolved in a mixture of alcohol and ether which was neutralized with 0.053N
NaOH. The resulting solution was heated under reflux condenser, cooled and titrated with 1.8-mL of
0.053N NaOH.
b. A 0.1194-g sample was dissolved in CHCl3, 25mL of ICl was added, stoppered and allowed to stand for
30 mins. KI was added and titrated with 8.9-mL of 0.1024N Na2S2O3. In the blank test, 34.0- mL of
Na2S2O3 was consumed.
c. A 4.09-g sample was treated with KOH dissolved in alcohol and heated under reflux condenser. The
alcohol was evaporated off and the residue was dissolved in hot water and then extracted with several
portions of ether. The ether extract was evaporated to dryness on a water bath. The residue weighed
0.0535-g.
d. A 1.525-g sample was refluxed with 25.0-mL of 0.50M KOH and required 15.7mL of 0.51M HCl for
residual titration. The blank test required 26.0-mL of 0.51M HCl to bring about an endpoint.

Does the sample conform with the USP specifications for all the constants determined?
Acid Value = nmt 1.0mL of 0.1N NaOH for a 2.0-g sample
Saponification Value = 180 192
Iodine Value = 145 - 180
Unsaponifiable Matter = nmt 1.3%

## ANSWER: a) Yes (A.V. = 0.77-mL) b) Yes (I.V. = 273)

c) No, because value is slightly over the limits (USM = 1.31%) d) Yes (S.V. = 190)

7. A 9.924-g sample of bergamot oil was refluxed with 25-mL of 0.51N alcoholic KOH and required 18.0-mL
of 0.4865N HCl for back titration. A blank test was performed and required 24.0-mL of 0.4865N HCl for
back titration. Calculate the % of bornyl acetate, if 1.0mL of 0.50N KOH is equivalent to 98.15-mg of
bornyl acetate. ANSWER: 5.8% bornyl acetate

8. Exactly 10.0mL of cinnamon oil was introduced into a cassia flask and to it was added 50.0-mL of saturated
NaHSO3 solution, boiled and shaken repeatedly. The undissolved oil remaining after this treatment
measured 4.3-mL. What is the % of cinnamon aldehyde in the sample?

9. If rosemary oil with 7.2% total esters contain 50.0% total borneol (uncorrected), what changes in the result
would the correction cause?
Molar Masses: Bornyl acetate = 196.2 Acetyl radical = 42.04 ANSWER: 49% total borneol

10. What would be the percentage volatile oil in orange spirit, if the number of divisions occupied by the
oil-kerosene mixture is 8.0 and the volume of kerosene added is 1.2-mL. The volume of the sample of
orange spirit transferred to the babcock bottle is 4.8mL. ANSWER: 8.8% volatile oil

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11. The weight of 25 tabs of morphine phosphate (50.0mg) is 3.075g. If 0.3075g was used in the assay and it
required 10.3-mL of 0.023N NaOH to back-titrate 25.0-mL of 0.021N H2SO4, calculate the % labelled amount
of morphine phosphate. (Note: 1.0-mL of 0.02N H2SO4 is equivalent to 8.488-mg of morphine phosphate.)