A solution containing appreciable amounts of a weak conjugate acid-base pair is called a buffer solution. The solution has the ability to resist changes in $\ce{pH}$ upon the addition of small amounts of either acid or base. Usually, a buffer solution can be prepared by using a weak acid or a weak base, and it's salt.
Why a buffer solution can resist changes in $\ce{pH}$?
Because both acid and base coexist in a buffer solution under equilibrium. The acid can react with any added $\ce{OH-}$ and the base can react with any added $\ce{H+}$.
An example is a solution with comparable amounts of $\ce{CH3COOH}$ and $\ce{CH3COONa}$. $\ce{CH3COONa}$ ionize completely in water to give:
$$\ce{CH3COONa ->[\ce{H2O}] CH3COO- (aq) + Na+ (aq)}$$
If an acid is added, $\ce{H+}$ will be consumed by $\ce{CH3COO-}$
$$\ce{CH3COO- (aq) + H+ (aq) -> CH3COOH (aq)}$$
If a base is added, $\ce{OH-}$ will be consumed by $\ce{CH3COOH}$
$$\ce{CH3COOH(aq) + OH- (aq) -> CH3COO- (aq) + H2O (l)}$$
This buffer system can be written as either $\ce{CH3COONa/CH3COOH}$ or $\ce{CH3COO- /CH3COOH}$.
Calculate the $\ce{pH}$ of a Buffer System
$\ce{CH3COOH}$ | $\ce{H+}$ | $\ce{CH3COO-}$ | |
---|---|---|---|
Initial (M): | $1.0$ | $0$ | $1.0$ |
Change (M): | $-x$ | $+x$ | $+x$ |
Equilibrium (M): | $(1.0-x)$ | $x$ | $(1.0+x)$ |
from sympy import *
x= symbols('x')
solve(x*(1.0+x)/(1.0-x)-1.8e-5)
# Ignore the nagtive value.
[-1.00003599935203, 1.79993520349897e-5]
$\ce{CH3COOH}$ | $\ce{H+}$ | $\ce{CH3COO-}$ | |
---|---|---|---|
Initial (M): | $1.1$ | $0$ | $0.9$ |
Change (M): | $-x$ | $+x$ | $+x$ |
Equilibrium (M): | $(1.1-x)$ | $x$ | $(0.9+x)$ |
solve(x*(0.9+x)/(1.1-x)-1.8e-5)
# Ignore the nagtive value.
[-0.900039999022290, 2.19990222895745e-5]
Preparing a Buffer Solution with a Specific $\ce{pH}$
$$\ce{p}K_a=- \log K_a$$
Because for an acid
$$\ce{acid <=> {conjugate\ base} + H+}$$
the $K_a$ value equals
$$K_a=\frac{[\text{conjugate base}][\ce{H+}]}{[\text{acid}]}$$
We have
$$[\ce{H+}]=K_a\times\frac{[\text{acid}]}{[\text{conjugate base}]}$$
Thus
$$\ce{pH}=\ce{p}K_a - \log\frac{[\text{acid}]}{[\text{conjugate base}]}$$
or
$$\ce{pH}=\ce{p}K_a + \log\frac{[\text{conjugate base}]}{[\text{acid}]}\quad\text{(1)}$$
Use this equation to calculate the ratio between an acid and its conjugate base in order to prepare a buffer solution with a specific $\ce{pH}$.
To prepare a buffer solution, we choose a weak acid whose $\ce{p}K_a$ is close to the desired $\ce{pH}$. Thus the acid and its conjugate base would have comparable concentration in the buffer solution.
Requirements
- Understand what is a buffer solution and why a buffer solution can resist the change of $\ce{pH}$.
- Know how to calculate the $\ce{pH}$ of a buffer solution and the $\ce{pH}$ change after adding a little amount of acid or base.
- Know how to prepare a buffer solution with a specific $\ce{pH}$.
Strong Acid-Strong Base Titrations
The $\ce{pH}$ value changes sharply around the equivalence point.
At the equivalence point, $\ce{pH}=7$.
Weak Acid-Strong Base Titrations
At the equivalence point, $\ce{pH}>7$.
Strong Acid-Weak Base Titrations
At the equivalence point, $\ce{pH}<7$.
Calculate the $\ce{pH}$ during a titration process
$\ce{CH3COO-}$ | $\ce{CH3COOH}$ | $\ce{OH-}$ | |
---|---|---|---|
Initial (M): | $0.050$ | $0$ | $0$ |
Change (M): | $-x$ | $+x$ | $+x$ |
Equilibrium (M): | $(0.050-x)$ | $x$ | $x$ |
Acid Base Indicators
Indicators are substances that have distinctly different colors in acidic and basic media.
A given indicator changes from the acid color to the base color in a certain $\ce{pH}$ range.
The titration curve usually has a steep part around the equivalence point. Only when the indicator would change its color within this steep portion of the curve, the indicator can be used in such titration experiment.
An indicator is typically a weak acid or weak base. The color change happens when $\ce{pH}$ is close to its $\ce{p}K_a$. The color change interval (or $\ce{pH}$ interval) for an acid-base indicator is defined as the range of pH values over which a change in color is observed, and for most indicators this range is approximately $\ce{p}K_a \pm 1$.
Requirements
- Calculate the $\ce{pH}$ in a titration process.
- Tell which indicator or indicators could be used in given acid-base titration curves.
Solubility Product,$K_{sp}$ , is the product of the molar concentrations of the constituent ions, each raised to the power of its stoichiometric coefficient in the equilibrium equation.
Values of $K_{sp}$ of some slightly soluble ionic compounds are summerized in Table 17.2.
In the reaction
$$\ce{AgCl(s) <=> Ag+ (aq) + Cl- (aq)}$$
$$K_{sp}=[\ce{Ag+}][\ce{Cl-}]$$
Knowing the concentrations of $\ce{Ag+}$ and $\ce{Cl-}$, the ion product, $Q$, can be calculated as
$$Q=[\ce{Ag+}][\ce{Cl-}]$$
Compare $Q$ with $K_{sp}$.
Molar solubility: the number of moles of solute in 1 L of a saturated solution;
Solubility: the number of grams of solute in 1 L of a saturated solution.
Compared with pure water, the solubility of an ionic compound is less in aqueous solutions containing a common ion (one also produced by dissolution of the ionic compound). This is an example of a phenomenon known as the common ion effect, which is a consequence of the law of mass action that may be explained using Le ChÂtelier’s principle.
The common ion effect and solubility. One example is to calculate the molar solubility of $\ce{AgCl}$ in a $\ce{AgNO3}$ solution.
Knowing the solubility, calculate the value of $K_{sp}$.
Knowing the value of $K_{sp}$, calculate the solubility.
Predict precipitation reactions. Calculate the value of $Q$ and compare to $K_{sp}$ to determine whether precipitation would happen.
Calculate the concentration concerning common ion effect.
Requirements
- Understand the concepts: solubility product, molar solubility, solubility.
- Predict whether precipitation would happen by comparing $Q$ with $K_{sp}$.
- Knowing the solubility, calculate the value of $K_{sp}$; or knowing the value of $K_{sp}$, calculate the solubility.
- Calculate the concentration concerning common ion effect.
Complex ions are formed when metal cations (Lewis acids which are electron-pair acceptors) combine with Lewis bases (electron-pair donors). An example is:
$$\ce{Ag+ (aq) + 2NH3 (aq) <=> Ag(NH3)2^+ (aq)}\qquad K_f=\frac{[\ce{Ag(NH3)2^+}]}{[\ce{Ag+}][\ce{NH3}]^2}$$
Formation constant, $K_f$, is the equilibrium constant for complex ion formation. The larger $K_f$ is, the more stable the complex ion is.
Calculate the concentration of naked metal ions in an complex equilibrium.
Phenomenon of $\ce{Al(OH)3}$ reacts with acids and bases.
$$\ce{Al(OH)3 (s) + 3H+ (aq) -> Al^3+ (aq) + 3H2O(l)}$$
$$\ce{Al(OH)3 (s) + OH- (aq) <=> Al(OH)4^- (aq)}$$
Requirements
- Understant what are complex ions and what is the formation constant.
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return HTML(styles)
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