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Holler, Crouch, Skoog and Wests Fundamentals of Analytical Chemistry, 9th Ed., Brook/Cole, 2014.
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Among the strong electrolytes listed are acids, bases, and salts.
A salt is produced in the reaction of an acid with a base.
Ex., NaCl, Na2SO4, and NaOOCCH3 (sodium acetate).
Acids and bases
According to the Brnsted-Lowry theory, an acid is a proton donor, and a
base is a proton acceptor. For a molecule to behave as an acid, it must
encounter a proton acceptor (or base) and vice versa.
Conjugate Acids and Bases
A conjugate base is formed when an acid loses a proton.
For example, acetate ion is the conjugate base of acetic acid.
A conjugate acid is formed when a base accepts a proton.
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Acid1 and base1 act as a conjugate acid/base pair, or just a conjugate pair.
Similarly, every base accepts a proton to produce a conjugate acid. When
these two processes are combined, the result is an acid/base, or
neutralization reaction.
This reaction proceeds to an extent that depends on the relative
tendencies of the two bases to accept a proton (or the two acids to
donate a proton).
Ammonia (base1) reacts with water (acid2) to give the conjugate acid
ammonium ion (acid1) and hydroxide ion (base2) of the acid water.
Chemical equilibrium
Many reactions never result in complete conversion of reactants to
products. They proceed to a state of chemical equilibrium in which
the ratio of concentrations of reactants and products is constant.
Equilibrium-constant expressions are algebraic equations that
describe the concentration relationships among reactants and
products at equilibrium.
The Equilibrium State
The final position of a chemical equilibrium is independent of the
route to the equilibrium state.
This relationship can be altered by applying stressors such as
changes in temperature, in pressure, or in total concentration of a
reactant or a product.
These effects can be predicted qualitatively by the Le Chteliers
principle.
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Buffer solutions
A buffer solution resists changes in pH when it is diluted or when
acids or bases are added to it.
Bsolutions are prepared from a conjugate acid/base pair.
Buffers are used in chemical applications whenever it is important
to maintain the pH of a solution at a constant and predetermined
level.
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Reducing Agents
Chelates
Chelates are cyclical metal-organic compounds in which the metal is a
part of one or more five- or six-membered rings.
Heme is a part of homoglobin, the oxygen-carrying molecule in human
blood. The four six-membered rings ate formed with Fe2+.
Heme
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Dimethylglyoxine
Sodium Tetraphenylborate
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Standard Solutions
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Acid/Base Indicators
The equilibrium-constant expression for the dissociation of an acidtype indicator takes the form
Ka = [H3O+][In-]
[HIN]
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Figure 14- 4 Titration curves for NaOH with HCl. Curve A: 50.00 mL of 0.0500M NaOH
with 0.1000M HCl. Curve B: 50.00 mL of 0.00500M NaOH with 0.01000M HCl.
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1.
At the beginning, the solution contains only a weak acid or a weak base,
and the pH is calculated from the concentration of that solute and its
dissociation constant.
2. After various increments of titrant have been added (up to, but not
including, the equivalence point), the solution consists of a series of buffers.
The pH of each buffer can be calculated from the analytical concentrations
of the conjugate base or acid and the concentrations of the weak acid or
base that remains.
3. At the equivalence point, the solution contains only the conjugate of the
weak acid or base being titrated (that is, a salt), and the pH is calculated
from the concentration of this product.
4. Beyond the equivalence point, the excess of strong acid or base titrant
suppresses the acidic or basic character of the reaction product to such an
extent that the pH is governed largely by the concentration of the excess
titrant.
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The hydronium ions produced from the first reaction suppress the dissociation of
water to such an extent that the contribution of hydronium ions from the second
equilibrium is negligible.
The sum of the molar concentrations of the weak acid and its conjugate base must
equal the analytical concentration of the acid cHA
Thus, we get the mass-balance equation
Substituting [H3O+] for [A-] yields
which rearranges to
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Which rearranges to
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The initial pH values are higher and the equivalence-point pH is lower for
the more dilute solution (Curve B).
At intermediate titrant volumes, however, the pH values differ only slightly
because of the buffering action of the acetic acid/sodium acetate system
that is present in this region.
Choosing an Indicator
The choice of indicator is more
limited in the cases of Figures 14-5
and 14-6.
Figure 14-6 The effect of acid strength (dissociation constant) on titration curves. Each curve
represents the titration of 50.00 mL of 0.1000M weak acid with 0.1000M strong base.
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Figure 14-8 Plots of relative amounts of acetic acid and acetate ion during a titration.
The straight lines show the change in relative amounts of HOAc (0) and OAc- (1)
during the titration of 50.00 mL of 0.1000 M acetic acid. The curved line is the
titration curve for the system.
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Alpha values are unitless ratios whose sum must equal unity. These values depend
only on [H3O+] and Ka.
[HOAc]/cT = 0 Thus,
Similarly,
Figure 14F-4 (a) the titration curve of 50.00 mL of 0.1000 M weak acid with 0.1000 M NaOH
is shown as collected by a pH meter. (b) The second derivative is shown on expanded scale.
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