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# Continued on acid-base titration

## Terms used in titration

- pH - Pka - Equivalent point - Indicator - End point. - Concentration unit.

pH
pH is a measure of hydrogen ion concentration; a measure of the acidity or alkalinity of a solution. Aqueous solutions at 25C with a pH less than seven are acidic, while those with a pH greater than seven are basic or alkaline. A pH level of is 7.0 at 25C is defined as 'neutral' because the concentration of H3O+ equals the concentration of OH in pure water.

pKa and Ka
The Ka value is a value used to describe the tendency of compounds or ions to dissociate. The Ka value is also called the dissociation constant, the ionization constant, and the acid constant. The definition of Ka is: [H+].[B] / [HB], where B is the conjugate base of the acid HB. The pKa value is defined from Ka, and can be calculated from the Ka value from the equation pKa = -Log10(Ka)

## The equivalence point

Or stoichiometric point, of a chemical reaction is the point at which an added titrant is stoichiometrically equal to the number of moles of substance (known as analyte) present in the sample: the smallest amount of titrant that is sufficient to fully neutralize or react with the analyte. In some cases there are multiple equivalence points which are multiples of the first equivalent point, such as in the titration of a diprotic acid.

## The endpoint /pH indicator:

(related to, but not the same as the equivalence point) refers to the point at which the indicator changes color in a colorimetric titration. This is a substance that changes color in response to a chemical change. An acid-base indicator (e.g., phenolphthalein) changes color depending on the pH. Redox indicators are also frequently used. A drop of indicator solution is added to the titration at the start; when the color changes the endpoint has been reached, this is an approximation of the equivalence point.

Normality
Normality is another way of expressing the concentration of a solution. It is based on an alternate chemical unit of mass called the equivalent weight. The normality of a solution is the concentration expressed as the number of equivalent weights (equivalents) of solute per liter of solution. A 1 normal (1 N) solution contains 1 equivalent weight of solute per liter of solution. HCl(aq) + NaOH(aq) 1 mole 1 mole
(36.5 grams) (40.0 grams)

NaCl(aq) + H2O

## Types of Acid-Base titration

A) Strong acid / base against strong base / acid titrations: In this titration, the solution has a low pH and climbs as the strong base is added. As the solution nears the point where all of the H+ are neutralized, the pH rises sharply and then levels out again as the solution becomes more basic as more OH- ions are added. (Note that the strong base-strong acid titration curve is identical to the strong acid-strong base titration, but flipped vertically.) Phenolphthalein / methyl orange and methyl red fall with in the range of the inflection of this group.

Titration curve

The curve shows a strong acid being titrated by a strong base. There is the initial slow rise in pH until the reaction nears the point where just enough base is added to neutralize all the initial acid. This point is called the equivalence point. For a strong acid/base reaction, this occurs at pH = 7. As the solution passes the equivalence point, the pH slows its increase where the solution approaches the pH of the titration solution.

B) Weak acid and strong base titration: In this titration, a weak acid only partially dissociates from its salt. The pH will rise normally at first, but as it reaches a zone where the solution seems to be buffered, the slope levels out. After this zone, the pH rises sharply through its equivalence point and levels out again like the strong acid/strong base reaction. phenolphthalein is a suitable indicator as its pH range is 8-9.8. However, methyl orange is not suitable as its pH range is 3.1 to 4.5.

There are two main points to notice about this curve: The first is the half-equivalence point. This point occurs halfway through a buffered region where the pH barely changes for a lot of base added. The halfequivalence point is when just enough base is added for half of the acid to be converted to the conjugate base. When this happens, the concentration of H+ ions equals the Ka value of the acid. The second point is the higher equivalence point. Once the acid has been neutralized, notice the point is above pH=7. When a weak acid is neutralized, the solution that remains is basic because of the acid's conjugate base remains in solution.

C) Weak base and strong acid titration: As in the weak acid-strong base titration, there are three major differences between this curve (in blue) and a strong base-strong acid one (in black): 1. The weak-acid solution has a lower initial pH. 2. The pH drops more rapidly at the start, but less rapidly near the equivalence point. 3. The pH at the equivalence point does not equal 7.00. methyl orange is a suitable indicator while phenolphthalein is not suitable.

D) Polyprotic acid and strong acid titration: In this titration, acids have more than one H+ ion to give up. These acids are called polyprotic acids. For example, sulfuric acid (H2SO4)is a diprotic acid. It has two H+ ions it can give up. The first ion will break off in water by the dissociation H2SO4 H+ + HSO4 The second H+ comes from the dissociation of HSO4- by HSO4- H+ + SO42-

The curve shows the same trend as a weak acid titration where the pH does not change for a while, spikes up and levels off again. The difference occurs when the second acid reaction is taking place. The same curve happens again where a slow change in pH is followed by a spike and leveling off. Each 'hump' has it's own half-equivalence point. The first hump's point occurs when just enough base is added to the solution to convert half the H+ ions from the first dissociation to its conjugate base, or it's Ka value. The second hump's half-equivalence point occurs at the point where half the secondary acid is converted to the secondary conjugate base or that acid's Ka value.

Indicators table

Procedure
Reagents: 1- 0.1 N Hydrochloric Acid (Reagent Grade). 2- Phenolphthalein Indicator (0.5 g in 50 ml ETOH +50 ml H2O). 3- Standard NaOH Solution (0.1 N).

- Titration with Standard Base: 1- Rinse a buret 2 times with 5 ml portions of a standard 0.1 N NaOH solution then fill (from part A) and cover with a test tube. 2- Introduce (to the nearest 0.03 ml) approximately 25 ml of the HCL solution into each of the 250 ml Erlenmeyer flasks, touch the buret tip to the inside of the flask each time and rinse down with a few ml of water.

(Note: the number of meq of an acid will remain the same upon small additions of water). 3- Add two drops of phenolphthalein indicator to each sample just prior to titrating with standard base. 4- Titrate with the standard NaOH solution until the faintest pink tinge persists for at least 30 seconds. 5- Calculate the normality of the HCL solution.

Calculation
HCl(aq) + NaOH(aq) NaCl(aq) + H2O 1 mole 1 mole (36.5 grams) (40.0 grams)

## Meq HCL = Meq NaOH

V (ml) HCL * N HCL = V (ml) NaOH * N NaOH N HCL = V (ml) NaOH * N NaOH /V (ml) HCL