Chapter 15: Complex acid/base system

15 A- Mixtures of strong and weak acid or strong and weak

base.
15 B- Polyfunctionals acids and bases
15 C- Buffer solutions involvin polyprotic acids
15 D- Calculations of the pH of solution NaHA
15 E- Titrations curve for polyfunctional Acids
15 F- Titration curve for polyfunctional Bases
15 G- Titration curves for amphiprotic species
Mixture of Strong and weak acid or
strong and weak base
• Each of the components in a mixture containing a strong acid and a weak
acid (or a strong base and a weak base) can be determined provided that
the concentrations of the two are of the same order of magnitude and that
the dissociation constant for the weak acid or base is somewhat less than
about 10-4
15B- Polyfunctional acids and bases

• There are several species of interest in analytical chemistry that have two
or more ccidic or basic functional groups. These species are said to exhibit
polyfunctional acidic or basic behavior.
 A buffer solution is one resist changes in pH when the small quantities of
an acid or an alkaline are added to it. An acidic buffer solution is simply one
which has a pH less than 7. Acidic buffer solutions are commonly made from
a weak acid and one of its salts often a sodium salt.

 Polyprotic Acid is an acid that can donate more than one proton or
hydrogen atom per molecule to an aqueous solution. Example: (H2SO4) is a
ployprotic acid because it can donate two hydrogen atoms to an aqueous
solution.
Buffer Solutions Involving Polyprotic Acids

Two buffer systems can be prepared from a weak basic acid and its salts. The first consists
of free acid H2A and its conjugate base NaHA, and the second makes use of the acid NaHA
and its conjugate base Na2A. The pH of the NaHA/Na2A system is higher than that of the
H2A/NaHA system because the acid dissociation constant for HA2 is always less than that
for H2A.We can write enough independent equations to permit a rigorous calculation of the
hydronium ion concentration for either of these systems. Ordinarily, however, it is
permissible to introduce the simplifying assumption that only one of the equilibria is
important in determining the hydronium ion concentration of the solution. Thus, for a buffer
prepared from H2A and NaHA, the dissociation of HA2 to yield A22 can usually be neglected
so that the calculation is based only on the first dissociation. With this simplification, the
hydronium ion concentration is calculated by the method described in Section 9C-1 for a
simple buffer solution. As shown in Example 15-4, the validity of the assumption can be
checked by calculating an approximate concentration of A22 and comparing this value with
the concentrations of H2A and HA2.
We can write enough independent equations to permit a rigorous calculation
of the hydronium ion concentration for either of these systems. Ordinarily, however,
it is permissible to introduce the simplifying assumption that only one of the
equilibria is important in determining the hydronium ion concentration of the
solution. Thus, for a buffer prepared from H2A and NaHA, the dissociation of
HA2 to yield A22 can usually be neglected so that the calculation is based only on
the first dissociation. With this simplification, the hydronium ion concentration is
calculated by the method described in Section 9C-1 for a simple buffer solution.
As shown in Example 15-4, the validity of the assumption can be checked by
calculating an approximate concentration of A22 and comparing this value with the
concentraion of H2A and HA-
Calculation of the pH of Solutions of NaHA

We have not yet considered how to calculate the pH of solutions of salts that have
both acidic and basic properties, that is, salts that are amphiprotic. Such salts are
formed during neutralization titrations of polyfunctional acids and bases. For
example, when 1 mol of NaOH is added to a solution containing 1 mol of the acid
H2A, 1 mol of NaHA is formed. The pH of this solution is determined by two
equilibria established between HA- and water.
Titration Curves for Polyfunctional Acids

-Compounds with two or more acidic functional groups yield multiple end points in
a titration if the groups differ sufficiently in strength as acids.

Titration Curves for Polyfunctional Bases

-The construction of a titration curve for a polyfunctional base is pretty much the
same issue as polyfunctional acid titration curve.

-Alpha values are useful in visualizing the changes in the concentration of various
species that occur in a titration of a monoprotic weak acid. These curves give a
comprehensive picture of all concentration changes that occur during the titration.
Titration curves are graphs that display the information gathered by a titration. The i
nformation is displayed on a two-dimensional axis, typically with chemical volume o
n the horizontal axis and solution pH on the vertical axis. The curve of the graph sho
ws the change in solution pH as the volume of the chemical changes due to the add
ition of the titrant. Chemical volume is an independent variable on the graph, while p
H (which changes as the volume of the measured chemical increases) is a depende
nt variable.

Titrations are a form of chemical analysis, useful in determining the concentration of

a specific chemical component within a solution. A titration is used when the chemic
al being measured is known, but its volume within the solution is not known. In a titr
ation, a measured amount of a solution with a known concentration (known as the tit
rant) is added to the solution with an unknown concentration (known as the analyte)
. After any chemical reaction between the two solutions is complete, measurements
are taken to determine the volume of the chemical being measured that's present in
the final solution. Because the makeup of the titrant is known, and all chemicals in t
he solutions have been identified, this information is used to determine how much of
the chemical is in the analyte.
Chapter 16: Applications of Neutralization
Titration
A neutralization reaction is when an acid and a base react to form water and a salt and
involves the combination of H+ ions and OH- ions to generate water. The neutralization of
a strong acid and strong base has a pH equal to 7.

*A neutralization reaction is a reaction between an acid and base to produce a salt and water

HCl + NaOH → NaCl + H2O

Most common strong acids and bases

Strong Acids Strong Bases
HCl LiOH
HBr NaOH
HI KOH
HClO4 RbOH
HNO3 CsOH
Ca(OH)2
Sr(OH)2
Ba(OH)2
 A titration is a technique where a solution of known concentration is used to determine
the concentration of an unknown solution. Typically, the titrant (the know solution) is
added from a burette to a known quantity of the analyte (the unknown solution) until the
reaction is complete.

Basic setup for titration

The equivalence point is the point in a titration where the amount of titrant added is enough to completely
neutralize the analyte solution. The moles of titrant (standard solution) equal the moles of the solution with
unknown concentration.
An acid-base indicator (e.g., phenolphthalein) changes color depending on the pH. 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.

Titrations: Equivalence point is always pH 7

Titration Calculations
Macid x Vacid = Mbase x Vbase
MAx VA x nA = MB x VB x nB for modified version of equation
M= molarity, V= volume, nA= # of Hydrogen ion, nB= # of hydroxide ion
Titration Formula Questions:
Titration Calculations
Macid x Vacid = Mbase x Vbase
MAx VA x nA = MB x VB x nB for modified version of equation
M= molarity, V= volume, nA= # of Hydrogen ion, nB= # of hydroxide ion
Titration Formula Questions:

1.Calculate the concentration of a 25 mL NaOH solution if 35 mL of 1.25 M HCl is needed to titrate to the
equivalence point.
NaOH + HCl → NaCl + H2O

Answer:
In this equation the mole ratio of NaOH (base) and HCl (acid) is 1:1 as determined by the balanced
chemical equation. The equivalence point is where the moles of titrant and analyte in the reaction are equal.
Macid x Vacid = Mbase x Vbase
1.25x 35 = Mbase x 25
43.75 = Mbase x 25
1.75 = Mbase

2. If 42.5mL of 1.3 M KOH are used to neutralize 50.0 mL of H2SO4. Find the molarity of H2SO4.

KOH + H2SO4 → K2SO4 + H2O

H+ (Acid) OH- (Base) MAx VA x nA = MB x VB x nB

H2SO4 KOH
VA= 50.0 mL VB= 42.5 mL MA = MB x VB x nB
MA= ? MB= 1.3 M VA x nA
nA= 2 nB= 1 MA= 1.3 M x 42. 5mL x 1
50.0 mL x 2
MA= 0.55 M