Acetic acid titration with strong base

Titrating a Weak Acid with a Strong Base For this example let s consider the titration of 50.0 mL of 0.100 M acetic acid, CH3COOH, with 0.100 M NaOH. Again, we start by calculating the volume of NaOH needed to reach the equivalence point thus... 

A weak acid-strong base titration. The curve represents the titration of 50.00 mL of 1.000 M acetic acid, HC2H3O2. with 1.000 /W NaOH. The solution at the equivalence point is basic (pH = 9.22). Phenolphthalein is a suitable indicator. Methyl red would change color much too early, when only about 33 mL of NaOH had been added. Bromthymol blue would change color slightly too quickly. 

FIGURE 5.1 Acid-base titration curves (a) 0.10 M HCI (strong acid) titrated with 0.10 M NaOH (strong base), (b) 0.010 M HCI titrated with 0.010 M NaOH, and (c) 0.10 M acetic acid (weak acid) titrated with 0.10 M NaOH. 

It is interesting to compare the case of a strong acid titrated with a strong base (in the last section) with the titration of a weak acid, such as acetic acid, with a strong base, such as NaOH. The difference between the weak acid-strong base case and the strong acid-strong base case just discussed is that for the same... 

Figure 3-13. Potentiometric pH titration of acetic acid with strong base.

In the titration of a weak acid with a strong base, we must consider the acid dissociation equilibrium of a weak acid (Kg) to calculate [H30 ], after the addition of a strong base. Let us consider the titration of 100 mL of a 0.1 M solution of acetic acid (CH3COOH) with 0.1 M NaOH solution. 

Reacting, or "titrating" acetic acid CH3COOH with a strong base (e.g., NaOH) causes small pH changes, until close to the end point the titration reaction is... 

It is thus possible to calculate the whole of the pH-neutralization curve of a weak acid by a strong base equations (45) and (47) are used for the beginning and end, respectively, and equation (43), without the activity corrections, for the intermediate points. The pH values obtained in this manner for the titration of 100 cc. of 0.1 n acetic acid, for which ka is taken on 1.75 X 10 with 0.1 n sodium hydroxide are quoted in Table LXXI. 

The calculation of the titration curve differs from the strong acid-strong base case in that now equilibrium (reflected in the of the weak acid) enters the picture. As an example, consider the titration of 100.0 mL of a 0.1000 M solution of acetic acid (CH3COOH) with 0.1000 M NaOH. For this titration,... 

For the titration of single weak acid with strong base, such as that of acetic acid with NaOff, we have instead of (4.3-1)... 

Another method of analyzing a mixture of bases is to utilize the difference in the basicity of its components. As an example, let us take a mixture of aromatic and aliphatic amines. Since aliphatic amines are more strongly basic, one would expect to get a titration curve with two breaks, one for the aliphatic amine and one for the aromatic amine. However, you must not use glacial acetic acid for this titration because you will get a curve similar to curve B in Fig. 1. In other words, you get one potentiometric end point for the sum of the two. The reason is that glacial acetic acid reacts with aliphatic amines to form the acetate ion, which has about the same basic strength as the aromatic amine. Glacial acetic acid levels these two amines to the same strength. What you have to do is employ a nonaqueous solvent like acetonitrile and titrate with perchloric acid dissolved in dioxane. If you do this. 

A typical weak acid-strong base titration is that of acetic acid with sodium hydroxide. The net ionic equation for the reaction is... 

It may be noted that very weak acids, such as boric acid and phenol, which cannot be titrated potentiometrically in aqueous solution, can be titrated conductimetrically with relative ease. Mixtures of certain acids can be titrated more accurately by conductimetric than by potentiometric (pH) methods. Thus mixtures of hydrochloric acid (or any other strong acid) and acetic (ethanoic) acid (or any other weak acid of comparable strength) can be titrated with a weak base (e.g. aqueous ammonia) or with a strong base (e.g. sodium hydroxide) reasonably satisfactory end points are obtained. 

Weak acid with a strong base. In the titration of a weak acid with a strong base, the shape of the curve will depend upon the concentration and the dissociation constant Ka of the acid. Thus in the neutralisation of acetic acid (Ka— 1.8 x 10-5) with sodium hydroxide solution, the salt (sodium acetate) which is formed during the first part of the titration tends to repress the ionisation of the acetic acid still present so that its conductance decreases. The rising salt concentration will, however, tend to produce an increase in conductance. In consequence of these opposing influences the titration curves may have minima, the position of which will depend upon the concentration and upon the strength of the weak acid. As the titration proceeds, a somewhat indefinite break will occur at the end point, and the graph will become linear after all the acid has been neutralised. Some curves for acetic acid-sodium hydroxide titrations are shown in Fig. 13.2(h) clearly it is not possible to fix an accurate end point. 

Weak acids with weak bases. The titration of a weak acid and a weak base can be readily carried out, and frequently it is preferable to employ this procedure rather than use a strong base. Curve (c) in Fig. 13.2 is the titration curve of 0.003 M acetic acid with 0.0973 M aqueous ammonia solution. The neutralisation curve up to the equivalence point is similar to that obtained with sodium hydroxide solution, since both sodium and ammonium acetates are strong electrolytes after the equivalence point an excess of aqueous ammonia solution has little effect upon the conductance, as its dissociation is depressed by the ammonium salt present in the solution. The advantages over the use of strong alkali are that the end point is easier to detect, and in dilute solution the influence of carbon dioxide may be neglected. 

Mixture of a strong add and a weak add with a strong base. Upon adding a strong base to a mixture of a strong acid and a weak acid (e.g. hydrochloric and acetic acids), the conductance falls until the strong acid is neutralised, then rises as the weak acid is converted into its salt, and finally rises more steeply as excess alkali is introduced. Such a titration curve is shown as S in Fig. 13.2(d). 

In a few instances where precipitation prevents conductometry at electrodes in direct contact with the analyte solution, use has been made of high-frequency titration, e.g., with the metal plates outside a measuring capacity cell (see pp. 19 21 and 25) examples are the titration of organic bases with perchloric acid in glacial acetic acid105 and of strong or weak acids with sodium methoxide in DMF106. 

To select an indicator for an acid-base titration it is necessary to know the pH of the end point before using equation (5.5) or standard indicator tables. The end point pH may be calculated using equations (3.27), (3.29) or (3.30). Alternatively, an experimentally determined titration curve may be used (see next section). As an example, consider the titration of acetic acid (0.1 mol dm 3), a weak acid, with sodium hydroxide (0.1 mol dm-3), a strong base. At the end point, a solution of sodium acetate (0.05 mol dm 3) is obtained. Equation (3.28) then yields... 

FIGURE 5.2 A family of acid-base titration curves for a 0.10 M strong acid (HC1) and three weak acids, as indicated (0.10 M each), titrated with 0.10 M NaOH (strong base). HAc is a representation of acetic acid. 

In these equations, HA symbolizes a weak acid and A symbolizes the anion of the weak acid. The calculations are beyond our scope. However, we can correlate the value of the equilibrium constant for a weak acid ionization, Ka, with the position of the titration curve. The weaker the acid, the smaller the IQ and the higher the level of the initial steady increase. Figure 5.2 shows a family of curves representing several acids at a concentration of 0.10 M titrated with a strong base. The curves for HC1 and acetic acid (represented as HAc) are shown, as well as two curves for two acids even weaker than acetic acid. (The IQ s are indicated.)... 

The function Data EqAH2, m simulates the pH-titration of a weak diprotic acid, AH2, in acid excess, with a strong base. The computation of the equilibria is similar to the examples Eql. m and Eq2. m given in the Chapters Example General 3-Component Titration (p.56) and Example pH Titration of Acetic Acid (p.58). From the present point of view, the important aspect is that all variables are collected in one structure s. The model is now stored in s.Model, the logP values in s. log beta, etc. Importantly, all the information contained in s is returned to the invoking programs. 

Errors may occur in the Gran titration procedure if weakly acidic species with dissociation constants (expressed as pKd) in the range of the extract pH are present. In particular, curvature or reduction (or both) of the slope of the Gran exponential plot results (24), because weak acid dissociation and titration of released free acidity take place during the portion of the titration used for end-point determination. Fortuitously, some of the common, weak carboxylic acids (e.g., formic and acetic) are not stable toward microbial decomposition when collected in aerosol samples from the atmosphere, so much of the historical data base on strong acid content of aerosols does not suffer from this positive error source, unless of course the microbial processes produce additional strong acids. 

Commercial vinegar contains 5-6% acetic acid. Acetic acid, CH3COOH, is a monoprotic acid. Therefore, its concentration expressed in molarity or normality is the same. It is a weak acid and when titrated with a strong base such as NaOH, upon completion of the titration, there is a sudden change in the pH in the range from 6.0 to 9.0. The best way to monitor such a change is to use the indicator phenolphthalein, which changes from colorless to a pink hue at pH 8.0-9.0. 

PROBLEM 6.16.3. Sketch curves for the progress of a titration of 50 mL of 2 x 10 4 M acetic acid, a weak acid (Ka 1.75 x 10 4mol/L), with a strong base, 4 x 10-4 M NaOH. The equivalence point of the titration will be reached when 25 mL of NaOH will have been added. The following regions require different equations to be solved ... 

---