ACID-BASE TITRATION
maidliu 02.08.2012
Types of Acid-Base Titration
Alkalimetry Determination of basic content in a sample by titrating it with a standard acid solution Acidimetry Determination of acid content in a sample by titrating it with a standard base solution
Titration Curve
The course of an acid-base titration is best followed by examining the pH as the titration progresses. A titration curve provides visual picture of how the property of the titration reaction changes as the titrant is added to the analyte.
Importance of Titration Curve
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Helps choose the proper titrants and indicators to be used for the analysis Permits to study the effects of many parameters Determine the conditions for an acceptable titration
pH calculations is necessary to construct a theoretical titration curve.
Determining the Equivalence Point
Equivalence points in acid-base titrations are determined most often using chemical indicators that change color at or near equivalence point. Acid-base indicators are weak organic acids or bases whose conjugate forms have different colors. It must be weaker than the analyte acid or base so that it reacts last with the titrant.
Equilibrium for Indicator
The behavior of an acid-type indicator: HIn + H2O H3O+ + In (acid color) (base color)
The behavior of an base-type indicator: In + H2O OH + InH+ (base color) (acid color)
Acid-Base Indicator
Human eye is not sensitive to color difference in a solution containing a mixture of HIn and In .
An average observer visualizes color imparted by a typical indicator within concentration ratio: [Hin]/[In] = 10 0.1
This ratio vary considerably from indicator to indicator.
Acid-Base Indicator
Diagram showing the relationship between pH and an indicators color.
Determining the Equivalence point
The inflection point (the point in titration having the greatest slope) very nearly coincides with the equivalence point.
To minimize titration error, an indicators entire transition pH range must fall within the rapid change in pH at the equivalence point.
Reagents for Acid/Base Titrations
Standard Solutions (Titrant) Use of strong acids or strong bases react more completely with an analyte, yielding a sharper endpoint Primary Standards Acid/Base Indicators
Acid Titrants
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Hydrochloric acid , HCl
2. 3.
Widely used for titration of bases It is a strong acid; dilute solutions are stable with little or reducing power; chloride ion does not form precipitates with most cations Concentrated acid is not a primary standard
Perchloric acid, HClO4 Sulfuric acid, H2SO4
HSO4 is a weak acid Forms insoluble sulfates with a number of common cations
Primary Standard Bases
Primary standard bases are used for standardization of acids.
1. -
Sodium carbonate, Na2CO3 Most often used for the standardization of acid solutions High purity solid are commercially available, but it is hygroscopic
Na2CO3 + 2H3O+ H2CO3 + 2Na+ + 2H2O
Primary Standard Bases
Two endpoints are observed in the titration of Na2CO3 Conversion of CO3 2 to HCO , pH 8.3 3 Formation of CO2 - The second endpoint is used for the standardization bec change in pH is greater than the first.
Primary Standard Bases
2. Sodium tetraborate, Na2B4O710H2O Also known as borax; it has high molar mass Cannot be heated to remove water Stored in dessicator over an aqueous solution saturated with NaCl and sucrose (ensures no dehydration to occur)
Na2B4O7 + 2H3O+ + 3H2O 2Na+ + 4H3BO3
Primary Standard Bases
3. Tris(hydroxymethyl)aminomethane, (HOCH2)2CNH2 TRIS or THAM, available in primary-standard purity Substantially greater molar mass per mole of protons consumed
(HOCH2)2CNH2 + H3O+ (HOCH2)2CNH3+ + H2 O
Sample Problem
A 0.4512g of primary standard grade Na2CO3 (105.99 g/mol) required 36.44mL of an HCl solution to reach the endpoint in the reaction. What is the molarity of the HCl?
Answer: 0.2336M HCl
Sample Problem
Titration of a 0.7439-g sample of impure Na2B4O7 required 31.64mL 0.1081M HCl. Express the results in terms of percent: Na2B4O7 B2O3
Answer: 46.25% Na2B4O7, 32.01% B2O3
Sample Problem
A solution of HClO4 was standardized by dissolving 0.4125g of primary standard grade HgO (216.59 g/mol) in a solution of KBr:
HgO(s)+ 4Br + H2O HgBr42 + 2OH The liberated OH consumed 46.51mL of the acid. Calculate the molarity of the HClO4.
Answer: 8.190 x 102 M HClO4
Base Titrant
1.
Sodium hydroxide, NaOH
Used almost exclusively for titrating acids in solutions Primary-standard-grade purity is not available Dilute NaOH solutions are stable can be stored in plastic containers. It slowly reacts with glass to form soluble silicates. Has a cementing property; often glass stoppers are freeze tightly to the mouth of the container. It must be protected from carbon dioxide CO + 2OH CO 2 + H O
Primary Standard Acids
1.
Potassium hydrogen phthalate, KHC8H4O4 Often abbreviated KHP, an excellent primary standard Available in pure state, soluble in water, has high molar mass Not hygroscopic and can be heated to 135oCwithout decomposition KHC8H4O4 +OH K+ + C8H4O4 + H2O
Primary Standard Acids
2. Benzoic acid, C6H5COOH Available in sufficient purity Not very soluble in water; most often mixed with water-alcohol and non-aqueous solvents C6H5COOH + OH C6H5COO + H2O 3. Potassium hydrogen iodate, KH(IO3)2 Strong acid that can be titrated using any indicator with transition range between pH 4-10
Sample Problem
A 300.0-mg sample containing H3PO4 and inert material was diluted with water and titrated with 0.05000M NaOH. The endpoint was reached after 29.00mL of the titrant was added. Calculate the % H3PO4 in the sample. H3PO4 + NaOH Na2HPO4 + 2H2O
Answer: 23.68% H3PO4
Acid-Base Indicators
1. Phthalein indicators
Phenolphthalein is the best known indicator in this group. Indicator transition range: pH 8.0-9.8 Acid form (colorless) Base form (red) Not soluble in water; usually prepared in ethanol
Acid-Base Indicators
2. Azo indicators
Exhibit color change from red to yellow Methyl red , pH 4.2-6.2 Methyl orange, pH 3.1- 4.4
