(Midterm) Pharmaceutical Analysis 1 Flashcards

1
Q

3 DETERMINATION OF THE END POINT

A
  1. Cessation of precipitation or the appearance of turbidity
  2. Use of internal indicators
  3. Instrumental methods, i.e. potentiometer (by using pH meter) or amperometric
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2
Q

Analyte + titrant →

A

precipitate

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2
Q

The approach assumes that under the
experimental conditions used, the product is
virtually insoluble

A

Precipitation

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3
Q

As with other types of reactions, the formation of a precipitate can be used as the basis of a titration.

A

Precipitation

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3
Q

Just enough titrant has been added to react with all of our analyte.

A

The equivalence point

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4
Q

Three indicator methods applied to
the titration of Cl- with AgNO3

A
  1. Volhard Method
  2. Fajan’s Method
  3. Mohr Method
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4
Q

The point where sufficient titrant has been added to be stoichiometrically equivalent to the amount of analyte.

A

The equivalence point

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4
Q

Now, either the amount of Cl- or Ag+ is in excess.

A

The equivalence point

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5
Q

At this point, [Cl-] = [Ag+]

A

The equivalence point

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5
Q

formation of soluble colored complex at the end point

A

VOLHARD METHOD

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6
Q

Indicator of VOLHARD METHOD

A

Ferric ammonium sulfate TS
[Fe(NH4)(SO4)2]

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7
Q

Adsorption of a colored indicator at the end point.

A

FAJANS METHOD

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7
Q

Indirect method for chloride determination.

A

VOLHARD METHOD

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7
Q

Titrant of VOLHARD METHOD

A

0.1 N AgNO3 VS and 0.1 N NH4SCN VS

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8
Q

Titrant of FAJANS METHOD

A

0.1 N AgNO3 VS

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8
Q

Adsorption Indicators in FAJANS METHOD

A

a. Dichlorofluorescein TS (DCF)
b. Tetrabromofluorescein TS (Eosin Y)
c. Tetrabromophenolphthalein ethyl ester TS (TEE)

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9
Q

It forms a red precipitate of silver
chromate which is seen against the
background of white silver chloride

A

potassium chromate TS (K2CrO4)

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9
Q

Titrant in MOHR METHOD

A

0.1 N AgNO3 VS

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9
Q

Uses potassium chromate TS (K2CrO4

A

MOHR METHOD

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9
Q

Standard Solutions

A
  • 0.1 N AgNO3 VS
  • 0.1 N NH4SCN VS
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10
Q

compounds of silver and mercury that can be
readily converted in to soluble mercury of silver salts, may be estimated by direct titration with standard ammonium thiocyanate solution, using ferric ammonium sulfate as indicator.

A

Direct Titration Method

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10
Q

is based on the complete precipitation of insoluble silver salts from nitric acid solution by the addition of excess standard silver nitrate solution to a soluble salt, and the determination of the amount of silver nitrate solution in excess by residual titration with standard ammonium thiocyanate solution, using ferric ammonium sulfate as the indicator.

A

Residual Titration Method (Volhard
Method)

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10
Q

Substances other than chlorides that produce slightly soluble silver salts are bromides, iodides, cyanides, thiocyanate, sulfides,
phosphates, arsenate, carbonates, etc.

A

Residual Titration Method (Volhard
Method)

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11
Q

the second reagent is used to ________ the excess

A

back titrate

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11
Q

the first reagent is ________ in excess

A

added

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11
Q

when two reagents are listed, the analysis is by ________

A

back titration

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11
Q

direct titration with

A

standard ammonium thiocyanate solution, using ferric ammonium sulfate as indicator

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12
Q

Eosin Y TS

A

Fajans Method

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12
Q

USP Requirement in Assay of Sodium Chloride

A

99% - 100.5%

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13
Q

Can be analyzed using either Fajans Method or Volhard Method.

A

Assay of Sodium Chloride

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14
Q

Indicators in Assay of Sodium Chloride

A
  • FAS TS – Volhard Method
  • Eosin Y TS – Fajans Method
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14
Q

FAS TS

A

Volhard Method

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15
Q

a volumetric procedure for metal determination employing metal-ion indicators in the same manner that pH indicators are used in acid-base titrations.

A

Complexometric/EDTA Titrations

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15
Q

a.k.a EDTA complexometric titration

A

disodium ethylenediaminetetraacetate

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16
Q

With the introduction of the analytical reagent
disodium ethylenediaminetetraacetate, a.k.a
EDTA complexometric titration involved.

A

Complexometric/EDTA Titrations

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17
Q

preferred over the free acid in preparing
the standard solution of EDTA

A

Disodium salt

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18
Q

has a molecular weight of 372.24

A

EDTA (C10H14N2Na2O8 with 2H2O)

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19
Q

are best stored in polyethylene containers or in glass containers previously prepared by boiling the container in an alkaline 2% solution of EDTA to remove any metal ions.

A

Solutions

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19
Q

should be metal-free, therefore glass-distilled
water is preferred.

A

water

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20
Q

Reagent

A

▸ Disodium salt
▸ EDTA (C10H14N2Na2O8 with 2H2O)
▸ glass-distilled water
▸ Solutions

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20
Q

indicator used, end point of blue
color

A

Hydroxynaphthol blue

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21
Q

Preparation and Standardization of
0.05 M EDTA

A

▸ Hydroxynaphthol blue
▸ Hydrochloric acid
▸ Sodium Hydroxide

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22
Q

alkalinizes the solution to a pH of about 13, so that the Ca-EDTA complex would be stable and any magnesium which might be present as a
contaminant would not react.

A

Sodium Hydroxide

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22
Q

solubilizes the calcium carbonate by
converting it to calcium chloride

A

Hydrochloric acid

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23
Q

The formation of a stable, soluble complex
is the driving force in the reaction.

A

Complexometric Titration

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23
Q

For successful titration with EDTA, Kf must
be greater than 8

A

Complexometric Titration

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24
Q

The equilibrium constant for the reaction of
a metal ion with a ligand is called Kf or
stability constant.

A

Complexometric Titration

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25
Q

The formation of a stable, soluble complex
is the ______________

A

driving force in the reaction

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26
Q

For successful titration with EDTA, __________

A

Kf must be greater than 8

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26
Q

The equilibrium constant for the reaction of
a metal ion with a ligand is called ___________

A

Kf or stability constant.

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26
Q

Factors Influencing EDTA Titration

A
  • Activity of the metal ion
  • The pH at which the titration is run
  • Presence of interfering ions
  • Organic solvents
  • NaCl
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27
Q

decreases the stability of the complex

A

NaCl

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27
Q

increases the stability of the complex

A

Organic solvents

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28
Q

are compounds whose color changes
when they bind to a metal ion.

A

Metal ion indicators

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29
Q

_____________ must bind metal less strongly than EDTA does

A

Useful indicators

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30
Q

MgIn(Red) + EDTA(Colorless) →

A

MgEDTA(colorless) + In(blue)

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31
Q

Metal Ion indicators

A

▸ Azo dyes
▸ Phthaleins
▸ Tripheylmethane dyes
▸ Xylenol orange
▸ Hydroxynaphthol blue
▸ Hydrocathechol violet
▸ Eriochrome black TS

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32
Q

the colored forms are red (pK 6.3), blue (pK 11.6), yellow orange

A

Eriochrome black TS

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33
Q

Color of Metal-ion Complex

A

▸ Calmagite
▸ Murexide
▸ Xylenol (zyleenol) orange
▸ Pyrocatecol violet

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34
Q

Calmagite

A

wine red

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35
Q

Murexide

A

yellow (Co +2, Ni, +2, Cu +2); Red (Ca +2)

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36
Q

Xylenol (zyleenol) orange

A

red

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36
Q

Pyrocatecol violet

A

blue

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37
Q

EDTA Titration Techniques

A
  • Direct Titration
  • Residual Titration
  • Displacement Method
  • Indirect Titration
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38
Q

Ca 2+, Mg 2+, Zn 2+

A

Direct Titration

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39
Q

used to indicate the determination of a metal in the presence of another metal.

A

Masking

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39
Q

Can be accomplished by adjusting the solution a pH of the titration medium so that it will be favorable for complexation of the metal being determined and not of the other metal

A

Masking

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39
Q

releases metal ion from masking agent (e.g.
formaldehyde)

A

Demasking Agent

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39
Q

metal ions which are determined by
direct titration with EDTA

A

Ca 2+, Mg 2+, Zn 2+

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40
Q

cyanide complex can be demasked with
formaldehyde

A

Demasking Agent

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41
Q

also serve as a masking agents.

A

Auxiliary Complexing Agent

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42
Q

prevent the precipitation of the metal ion in the absence of EDTA.

A

Auxiliary Complexing Agent

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43
Q

Examples of Auxiliary Complexing Agent

A

ammonia, tartrate, citrate,
triethanolamine

44
Q

applied to the analysis of aluminum and bismuth compounds, since conditions for direct titration may introduce errors because of the precipitation of the metal as hydroxides in alkaline media.

A

Residual/Back Titration

45
Q

forms a highly stable complex and can be
titrated at a pH as low as 1 or 2

A

Bismuth

45
Q

for metals that do not give satisfactory end point.

A

Displacement Method

46
Q

VILEORA

A

Valence Increase, Lose Electron, Oxidation,
Reducing Agent

46
Q

an ion that precipitates with certain metal ions (with EDTA)

A

Indirect Titration

47
Q

VDGEROA

A

Valence Decreases, Gain Electron, Reduction,
Oxidizing Agent

48
Q

a.k.a. ferric alum

A

ferric ammonium sulfate

48
Q

mEq of KMnO4(potassium permanganate)

A

MW/5000

48
Q

Standard Solutions
▸ Oxidizing agent

A

▹ potassium permanganate
▹ potassium dichromate
▹ potassium ferricyanide
▹ ceric sulfate
▹ Iodine
▹ Bromine
▹ ferric ammonium sulfate – a.k.a. ferric alum

49
Q

mEq of K2Cr2O7(potassium dichromate)

A

MW/6000

49
Q

mEq of KBrO3(potassium bromate)

A

MW/6000

50
Q

mEq of Ce(SO4)2 (ceric/cerium(IV) sulfate)

A

MW/1000

51
Q

mEq of Fe(NH4)2(SO4)2∙6H2O

A

MW/1000

51
Q

Reducing Agent

A

▸ ferrous ammonium sulfate
▸ potassium arsenite
▸ titanium chloride
▸ sodium thiosulfate
▸ arsenic trioxide
▸ oxalic acid

51
Q

mEq of H2C2O4∙2H2O

A

MW/2000

51
Q

mEq of As2O3

A

MW/4000

52
Q

mEq of TiCl3

A

MW/1000

53
Q

mEq of Na2S2O3∙5H2O

A

MW/1000

53
Q

Permanganometry

A

Permanganate Methods

54
Q

widely used oxidizing titrant

A

Potassium permanganate

55
Q

Acts as self indicator

A

Potassium permanganate

56
Q

Very strong oxidizing agent

A

Potassium permanganate

57
Q

End point of Potassium permanganate

A

Distinct pink color

57
Q

Solutions of oxidizing agents should never be titrated from Mohr burets, since the oxidizing agent attacks the rubber and the KMnO4 titer decreases

A

Permanganate Methods

57
Q

the best standard to use in the standardization of potassium permanganate

A

Sodium oxalate

58
Q

Chemical Reaction of Potassium permanganate

A

5Na2C2O4 + 2KMnO4 + 8H2SO4 → 2MnSO4 +
5Na2SO4 + K2SO4 + 10CO2 + 8 H2O

59
Q

Direct Titration Method

A

ASSAY OF HYDROGEN PEROXIDE SOLUTION

59
Q

must be added to prevent the
formation of manganese dioxide.

A

Sufficient sulfuric acid

60
Q

Concentration is expressed in %w/v

A

ASSAY OF HYDROGEN PEROXIDE SOLUTION

61
Q

USP Requirement in ASSAY OF HYDROGEN PEROXIDE SOLUTION

A

2.5 – 3.5% w/v of H2O2

62
Q

5H2O2 + 2KMnO4 + 3H2SO4 → 2MnSO4 + 5O2 + K2SO4 + 8 H2O

A

Chemical Reaction of ASSAY OF HYDROGEN PEROXIDE SOLUTION

62
Q

acts as reducing agent but chemically it is an oxidizing agent.

A

H2O2

63
Q

employed to those compounds that can be converted through chemical reactions to and equivalent amount of oxalate, which in turn can then be quantitatively oxidized by permanganate.

A

Indirect Titration Method

64
Q

this is an indirect method of determination, since neither the calcium ion nor the malate ion is measure directly.

A

Assay of Cherry Juice for Malic Acid

65
Q

the malic acid is converted to an equivalent amount of calcium salt, which is converted to insoluble calcium oxalate; the oxalate is then liberated and oxidized with permanganate

A

Assay of Cherry Juice for Malic Acid

65
Q

Titration in which an excess of standard potassium permanganate solution is employed oxidize a substance, and the amount in excess is determined by reduction with
▹ excess standard oxalic acid (reducing agent)
▹ excess ferrous ammonium sulfate (reducing agent) and back titration with more standard potassium permanganate (e.g. assay of sodium nitrite)

A

Residual Titration Method

66
Q

Titration in which an excess of standard oxalic acid solution is added to the substance and the excess oxalic acid is titrated with standard potassium permanganate.

A

Residual Titration Method

67
Q

USP Requirement in Assay of Sodium Nitrite

A

97% - 101% NaNO2

68
Q

Dissolve about 1 g of NaNO2, accurately weighed, in water to make 100 mL. Pipet 10 mL of this solution into a mixture of 50 mL of 0.1 N KMnO4 VS, 100 mL of water, and 5 mL of sulfuric acid. When adding the NaNO2 solution, immerse the tip of the pipet beneath the surface of the permanganate mixture. Warm the liquid to 40◦C, allow it to stand for 5
minutes, and add 25 mL of 0.1N oxalic acid VS. Heat the mixture to about 80◦C, and titrate with 0.1 N KMnO4 VS.

A

Procedure of Assay of Sodium Nitrite

69
Q

10NaNO2 + 4KMnO4 +11H2SO4 → 10HNO3 + 4MnSO4 +2K2SO4 + 5Na2SO4 + 6H2O

A

Chemical Reaction of Assay of Sodium Nitrite

70
Q

Ceric Sulfate Titration Method

A

Cerimetry

71
Q

Advantages of Ceric Sulfate Titration Method

A
  1. More stable that standard permanganate solutions.
  2. React quantitatively with oxalate or arsenite ions.
  3. Cerous ion is colorless and does not obscure the indicator end point.
  4. No intermediate products are formed in the reduction of ceric salts.
  5. High concentrations of chloride ions are not oxidized by ceric salts
72
Q

Indicator of Cerimetry

A

Ferrous phenanthroline (Ferroin)

73
Q

Primary standard of Cerimetry

A

arsenic trioxide

73
Q

Catalyst of Cerimetry

A

osmium tetroxide

73
Q

2Ce(SO4)2 + Na3AsO3 + H2O → Ce2(SO4)3 + Na3AsO4 + H2SO4
As2O3 + 6NaOH → 2Na3AsO3

A

Chemical Reaction of Cerimetry

74
Q

Examples of Cerimetry

A

Assay of Ferrous Sulfate Tablets

75
Q

standardized using U.S.P. ascorbic RS

A

Dichlorophenol-Indophenol

76
Q

used as a standard oxidizing agent in the determination of the ascorbic acid content of
ascorbic acid tablets and injection, as well as of the ascorbic acid content in hexavitamin and decavitamin capsules and tablets.

A

Dichlorophenol-Indophenol

77
Q

direct titration of a reducing analyte with
iodine

A

Iodimetry

77
Q

added before the equivalence point is
reached

A

starch TS

78
Q

indirect analysis of an oxidizing agent

A

Iodometry

79
Q

reduced with excess potassium iodide and an equivalent amount of iodine is produce

A

sample of oxidizing agent

79
Q

titrated with a standard solution
of sodium thiosulfate

A

iodine formed

80
Q

In hot water, starch granules burst and form a
colloidal dispersion of beta-amylose, known as
soluble starch, and should be separated by
decantation from alpha-amylose, known as
amylopectin, which is insoluble.

A

Starch Indicator Solution

80
Q

deteriorates rapidly, therefore it should be
prepared freshly each day.

A

Starch Indicator Solution

80
Q

In hot water, starch granules burst and form a
colloidal dispersion of beta-amylose

A

soluble starch

81
Q

used as preservative in the preparation of starch TS.

A

Mercuric iodide (HgI2)

81
Q

should be separated by decantation from alpha-amylose

A

amylopectin, which is insoluble

82
Q

the indicator of choice for those procedures involving iodine because it forms an intense blue complex with iodine.

A

Starch

82
Q

is not a redox indicator; it responds specifically to the presence of I2, not to a change in redox potential.

A

Starch

82
Q

in Starch- Iodine Complex the active fraction is __________

A

amylose

83
Q

a polymer of the sugar a-d-glucose

A

amylose

84
Q

In the presence of starch, iodine forms I2 chains inside the amylose helix and the color turns __________

A

dark blue

85
Q

(0.1 N Iodine VS) - primary standard slowly soluble cold water and readily dissolves in warm water

A

Arsenic trioxide

86
Q

(0.1 N Iodine VS) - solubilizing agent

A

0.1 N Iodine VS

86
Q

(0.1 N Iodine VS) - not very soluble in water but dissolves readily in the presence of potassium iodide (solubilizing agent) because of the
formation of the triiodide ion

A

Iodine

87
Q

(0.1 N Iodine VS) - indicator

A

Starch TS

88
Q

(0.1 N Iodine VS) - buffering agent to keep the solution neutral

A

Sodium bicarbonate

88
Q

(0.1 N Iodine VS) - indicator used in neutralizing the excess sodium hydroxide with HCl

A

Methyl orange

89
Q

no primary standard used because
_____________ is a very stable salt and
can be obtained in a very pure condition, that
is why it does not need to be standardize.

A

0.05M Potassium Iodate

90
Q

mEq of arsenic trioxide (As2O3)

A

0.04946

91
Q

There is no primary standard used because
_____________ is a very stable salt and
can be obtained in a very pure condition, that
is why it does not need to be standardize.

A

0.05M Potassium Iodate

92
Q

(0.05M Potassium Iodate) - added to make the end point observation feasible.

A

Chloroform or carbon tetrachloride

92
Q

(0.1N Sodium Thiosulfate VS) - primary standard and oxidizing agent

A

Potassium dichromate (K2Cr2O7/6000)

92
Q

oxidizes the iodide ion in the presence of acid to and equivalent amount of iodine

A

0.1N Sodium Thiosulfate VS

93
Q

Carbon dioxide free water a.k.a recently boiled water

A

0.1N Sodium Thiosulfate VS

94
Q

a.k.a recently boiled water

A

Carbon dioxide free water

95
Q

(0.1N Sodium Thiosulfate VS) - acts as a preservative to prevent acid-catalyzed hydrolysis

A

Sodium carbonate

96
Q

(0.1N Sodium Thiosulfate VS) - added to prevent bacterial growth

A

CHCl3

96
Q

(0.1N Potassium Arsenite Solution) - primary standard

A

Arsenic trioxide

97
Q

Neutralized by potassium hydroxide and forms ___________

A

potassium arsenite

97
Q

(0.1N Potassium Arsenite Solution) - used to provide the pH of about 9 which is necessary for accurate results and a rapid reaction with iodine.

A

Potassium bicarbonate

98
Q

Substances that are oxidizing agents which
cannot be determined direct titration with a
standard solution of a reducing agent are _____________

A

assayed indirectly

99
Q

Substances that are oxidizing agents which
cannot be determined direct titration with a
standard solution of a reducing agent are
assayed indirectly

A

Iodometry

100
Q

Examples of Iodometry

A

▹ Assay of Selenium Sulfide
▹ Assay of Sodium Hypochlorite Solution
▹ Assay of Cupric Sulfate

100
Q

USP Requirement in Assay of NaOCl

A

4-6% w/w

101
Q

KI, acetic acid, 0.1N sodium thiosulfate, starch TS

A

Assay of NaOCl

102
Q

Titrant of Assay of Ascorbic Acid

A

0.1 N I2 VS

103
Q

Indicator of Assay of Ascorbic Acid

A

Starch TS

104
Q

For aniline, phenol, and resorcinol, bromine is
employed as an oxidizing agent in place of
iodine, since it is reduced by the readily oxidized organic substances in a reaction that proceeds quantitatively with the production of water- insoluble bromine substitution products such as tribromoaniline, tribromophenol

A

Oxidation-Reduction Method with
0.1N Bromine

104
Q

Titer value (mg) of Assay of Ascorbic Acid

A

8.806 mg

105
Q

USP Requirement of Assay of Ascorbic Acid

A

99-100.5%

106
Q

For _______,_______,_________ , bromine is
employed as an oxidizing agent in place of
iodine, since it is reduced by the readily oxidized organic substances in a reaction that proceeds quantitatively with the production of water- insoluble bromine substitution products such as __________,___________

A

aniline, phenol, and resorcinol
tribromoaniline, tribromophenol

107
Q
  • aka Koppeschaar’s Solution
  • No primary standard used
A

0.1 N Bromine VS

107
Q

Secondary standard of 0.1 N Bromine VS

A

0.1N Na2S2O3 VS

108
Q

Residual Iodometry

A

Assay of Phenol

108
Q

spec of Assay of Phenol

A

99-100.5 %

109
Q

Each mL of 0.1 N bromine

A

1.569 mg of phenol

110
Q

may be used as the oxidizing agent in the assay of a number of substances,
such as iodides, arsenite, and other reducing
agents.

A

Potassium iodate

110
Q

end point of 0.1 M Sodium Nitrite VS

A

determined by the liberation of iodine from iodide

111
Q

The assay of the sulfa drugs and other
compounds containing an aryl amino group
by diazotization with sodium nitrite are not
strictly iodometric methods.

A

Diazotization Assay with Nitrite

112
Q

primary standard of 0.1 M Sodium Nitrite VS

A

Sulfanilamide RS

113
Q

unstable if not kept cold, it will decompose forming phenol products which are capable of reacting further with HNO3

A

Diazonium salt

114
Q

Dried at 105 for 3 hours, water, HCl, 25 mL,
intermediate blue ring when touched to starch
iodide paper, identical to the assay procedure.

A

0.1 M Sodium Nitrite VS

114
Q
  • 0.1 M NaNO2
  • Starch iodide paper
A

Assay of Sulfathiazole (C9H9N3O2S2)

115
Q

Titer value of Assay of Sulfathiazole (C9H9N3O2S2)

A

25.53 mg