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AP Chemistry The Chemistry of Acids and Bases: Acid-Base Theories
AP Chemistry The Chemistry of Acids and Bases: Acid-Base Theories
Acids and bases are extremely important in many everyday applications: our own bloodstream, our
environment, cleaning materials, and industry. (Sulfuric acid is an economic indicator!)
ACID-BASE THEORIES
ARRHENIUS DEFINITION
acid--donates a hydrogen ion (H+) in water
base--donates a hydroxide ion in water (OH−)
This theory was limited to substances with those "parts"; ammonia is a MAJOR exception!
BRONSTED-LOWRY DEFINITION
acid--donates a proton in water
base--accepts a proton in water
This theory is better; it explains ammonia as a base! This is the main theory that we will use for our
acid/base discussion.
LEWIS DEFINITION
acid--accepts an electron pair
base--donates an electron pair
This theory explains all traditional acids and bases plus a host of coordination compounds and is used
widely in organic chemistry. Uses coordinate covalent bonds.
*AP is a registered trademark of the College Board, which was not involved in the production of, and does not endorse, this product.
© 2008 by René McCormick. All rights reserved.
In each of the acid examples---notice the formation of H3O+ -- this species is named the hydronium ion.
It lets you know that the solution is acidic!
( hydronium, H3O+--H+ riding piggy-back on a water molecule; water is polar and the
+ charge of the “naked” proton is greatly attracted to Mickey's chin!)
Notice the formation of OH− in each of the alkaline examples. This species is named the hydroxide ion.
It lets you know that the resulting solution is basic!
You try!!
Exercise 1
a) In the following reaction, identify the acid on the left and its CB on the right. Similarly identify the
base on the left and its CA on the right.
polyprotic bases--accept more than one H+; anions with −2 and −3 charges (ex. PO43− ; HPO42−)
Write the simple dissociation (ionization) reaction (omitting water) for each of the following acids.
Strong
Weak
STRONG BASES
Hydroxides OR oxides of IA and IIA metals (except Mg and Be)
o Solubility plays a role (those that are very soluble are strong!)
THE STRONGER THE ACID THE WEAKER ITS CB, the converse is also true.
The vast majority of acid/bases are weak. Remember, this means they do not ionize much.
That means a equilibrium is established and it lies far to the left (reactant favored).
The equilibrium expression for acids is known as the Ka (the acid dissociation constant). It is set
up the same way as any other equilibrium expression. Many common weak acids are oxyacids, like
phosphoric acid and nitrous acid. Other common weak acids are organic acids—
those that contain a carboxyl group, the COOH group, like acetic acid and
benzoic acid.
Ka = [H3O+][A−] <<1
[HA]
Write the Ka expression for acetic acid. (Note: Water is a pure liquid and is thus, left out of the
equilibrium expression.)
Weak bases (bases without OH−) react with water to produce a hydroxide ion. Common examples
of weak bases are ammonia (NH3), methylamine (CH3NH2), and ethylamine (C2H5NH2). The lone
pair on N forms a bond with a H+. Most weak bases involve N.
Kb = [HB+][OH−] << 1
[B]
♦ Notice that Ka and Kb expressions look very similar. The difference is that a base
produces the hydroxide ion in solution, while the acid produces the hydronium ion in
solution.
♦ Another note on this point: H+ and H3O+ are both equivalent terms here.
Often water is left completely out of the equation since it does not appear in the
equilibrium. This has become an accepted practice. (* However, water is very
important in causing the acid to dissociate.)
Using table 14.2, arrange the following species according to their strength as bases:
Fredrich Kohlrausch, around 1900, found that no matter how pure water is, it still conducts a
minute amount of electric current. This proves that water self-ionizes.
• Since the water molecule is amphoteric, it may dissociate with itself to a slight extent.
• Only about 2 in a billion water molecules are ionized at any instant!
• The equilibrium expression used here is referred to as the autoionization constant for
water, Kw
• In pure water or dilute aqueous solutions, the concentration of water can be considered to be
a constant (55.6 M), so we include that with the equilibrium constant and write the
expression as:
♦ Knowing this value allows us to calculate the OH− and H+ concentration for various
situations.
♦ [OH−] = [H+] solution is neutral (in pure water, each of these is 1.0 × 10−7)
♦ [OH−] > [H+] solution is basic
♦ [OH−] < [H+] solution is acidic
a. Using Le Chatelier’s principle, predict whether the reaction below is exothermic or endothermic.
A: endothermic
−
B: [H ] = [OH ] = 3 × 10-7 M
+
Example: The problem states a 1.15 M solution blah, blah, blah. That is your
cue to report a pH with 3 decimal places. If the problem had stated a 1.2 M
solution blah, blah, blah, then you would report your calculated pH to 2
decimal places. How did this ever get started? If you care…read the next bullet…otherwise go
directly to Exercise 6!
In the old days, before calculators (Can you imagine?), students used log tables to work problems
involving logarithms. If the logarithm was 7.45, then the “7” was the characteristic and the “.45” part
was the mantissa. In fact, it is the mantissa that communicates the accuracy of the measurement.
The characteristic is simply a place holder.
Calculate either the [H+] or [OH−] from the information given for each of the following solutions at 25°C,
and state whether the solution is neutral, acidic, or basic.
c. 10.0 M H+
b. 1.0 M H+
A: pH = 11.00
pOH = 3.00
B: pH = 0.00
pOH = 14.00
Exercise 8 Calculating pH
The pH of a sample of human blood was measured to be 7.41 at 25°C. Calculate pOH, [H+], and [OH−] for
the sample.
pOH = 6.59
[H+] = 3.9 × 10-8 M
−
[OH ] = 2.6 × 10-7 M
A: pH = 1.00
B: pH = 10.00
pH = 12.70
Example
Calculate the pH of a 1.00 × 10−4 M solution of acetic acid. The Ka of acetic acid is 1.8 × 10−5.
⎡⎣ H + ⎤⎦ ⎡⎣ C2 H 3O 2 − ⎤⎦ −5 x2
Ka = = 1.8 ×10 =
HC2 H 3O 2 1×10−4 − x
See that –x term in the denominator? That is your invitation to cross multiply and distribute the Ka value
across the term so that you get x2 = 1.8 × 10−9 – 1.8 × 10−5x ; collect like terms and use either the solver on
your graphing calculator or a quadratic formula solving program you’ve loaded on your calculator (all of
this to avoid arithmetic mistakes!) to solve for x. You should determine that x = [H+] = 3.44 × 10−4 and
that the pH = − log (3.44 × 10−4) = 3.46 (2 SF).
Often, the –x term in a Ka expression can be neglected. That simplifies the math tremendously since you
are now spared the tedium of having to use the quadratic formula.
How do you know when to neglect x? Easy. Look at the original concentration and compare it to 100 Ka
(or 100 Kb). IF the initial concentration is large by comparison, you can neglect subtracting the x term.
We could not neglect x in the example we just worked since 100 Ka for acetic acid would equal 1.8 × 10−3
or 0.0018 which is too close to our initial acid concentration of 0.0001.
Suppose our initial concentration had been 0.10 M for the acetic acid in the example problem we just
worked. For acetic acid, 100Ka = 1.8 × 10−3 or 0.0018. That’s essentially subtracting zero from 0.10 M.
Aside from that if you did subtract it, you’d still follow the “least decimal place” subtraction sig. fig. rule
and report 0.10 M as your answer to the subtraction.
OK, I’ll humor you and apply the quadratic formula to the example we just worked changing the initial
concentration to 0.10 M. First I’ll do the quadratic formula and then I’ll work it by “neglecting x”.
Example
Calculate the pH of a 10.10 M solution of acetic acid. The Ka of acetic acid is 1.8 × 10−5.
⎡⎣ H + ⎤⎦ ⎡⎣ C2 H 3O 2 − ⎤⎦ x2
Ka = = 1.8 ×10−5 =
HC2 H 3O 2 0.10 − x
By cross multiplying and NOT neglecting x, you get x2 = 1.8 × 10−6 – 1.8 × 10−5x ; collect like terms and
use either the solver on your graphing calculator or a quadratic formula solving program you’ve loaded on
your calculator (all of this to avoid arithmetic mistakes!) to solve for x. You should determine that
x = [H+] = 0.0013327 (way too many sig. figs, I know!)
x2 = 1.8 × 10−6
So, take the square root of each side to get
x = 0.00134 = ⎡⎣ H + ⎤⎦
pH = − log (.001341) = 2.87 (2 SF) which is mighty, mighty close, so it is a really good approximation.
So, what’s the good news? The AP exam does not have equilibrium problems that require the quadratic
formula. Feel better? No promises about your homework, though! ☺
The hypochlorite ion (OCl−) is a strong oxidizing agent often found in household bleaches and
disinfectants. It is also the active ingredient that forms when swimming pool water is treated with chlorine.
In addition to its oxidizing abilities, the hypochlorite ion has a relatively high affinity for protons (it is a
much stronger base than Cl-, for example) and forms the weakly acidic hypochlorous acid
(HOCl, Ka = 3.5 × 10-8). Calculate the pH of a 0.100 M aqueous solution of hypochlorous acid.
pH = 4.23
Determination of the pH of a Mixture of Weak Acids
Calculate the pH of a solution that contains 1.00 M HCN (Ka = 6.2 × 10−10) and 5.00 M HNO2
(Ka = 4.0 × 10−4). Also calculate the concentration of cyanide ion (CN−) in this solution at equilibrium.
pH = 1.35
[CN−] = 1.4 × 10−8 M
Calculate the percent dissociation of acetic acid (Ka = 1.8 × 10−5) in each of the following solutions.
a. 1.00 M HC2H3O2
b. 0.100 M HC2H3O2
A: = 0.42 %
B: = 1.3 %
Lactic acid (HC3H5O3) is a waste product that accumulates in muscle tissue during exertion, leading to pain
and a feeling of fatigue. In a 0.100 M aqueous solution, lactic acid is 3.7% dissociated. Calculate the
value of Ka for this acid.
Determination of the pH of a weak base is very similar to the determination of the pH of a weak acid.
Follow the same steps. Remember, however, that x is the [OH−] and taking the negative log of x will
give you the pOH and not the pH!
pH = 12.20
pH = 12.32
Acids with more than one ionizable hydrogen will ionize in steps. Each dissociation has its own
Ka value.
The first dissociation will be the greatest and subsequent dissociations will have much smaller
equilibrium constants. As each H+ is removed, the remaining acid gets weaker and therefore has a
smaller Ka. As the negative charge on the acid increases it becomes more difficult to remove the
positively charged proton.
Looking at the Ka values, it is obvious that only the first dissociation will be
important in determining the pH of the solution.
Calculate the pH of a 5.0 M H3PO4 solution and the equilibrium concentrations of the species H3PO4,
H2PO4-, HPO42-, and PO43-.
pH = 0.72
[H3PO4] = 4.8 M
[H2PO4-] = 0.19 M
[HPO42-] = 6.2 × 10−8 M
[PO43-] = 1.6 × 10−19 M
pH = 0.00
pH = 1.84
Neutral Salts--Salts that are formed from the cation of a strong base reacting with the anion of a
strong acid are neutral. Beware of solubility issues! One salt such is NaNO3. Think about which
acid reacted with which base to form the salt…if both the acid and base are strong, then the salt is
neutral.
Basic Salts--Salts that are formed from the cation of a strong base reacting with the anion of a weak
acid are basic. Again, beware of solubility issues! The anion hydrolyzes the water molecule to
produce hydroxide ions and thus a basic solution. K2C2H3O2 should be basic since C2H3O2− is the
CB of the weak acid HC2H3O2, while K+ does not hydrolyze appreciably.
C2H3O2− + H2O R OH− + HC2H3O2
strong base weak acid
Acidic Salts- Salts that are formed from the cation of a weak base reacting with the anion of a
strong acid are acidic. The cation hydrolyzes the water molecule to produce hydronium ions and
thus an acidic solution. NH4Cl should be weakly acidic, since NH4+ hydrolyzes to give an acidic
solution, while Cl− does not hydrolyze.
NH4+ + H2O R H3O+ + NH3
strong acid weak base
1. Look at the salt and ask yourself which acid and which base reacted to form it?
3. Embrace the fact that “strong wins” and predict whether the salt is acidic or basic based
on that victory.
⎯⎯
a. If you predict basic, write ←⎯→ OH−
⎯
⎯⎯
→ H+
b. If you predict acidic, write ←⎯
⎯
4. Relish in the fact that “strong is a spectator”. Which means the remaining ion of the salt
is the reactant along with water.
5. Write water as HOH to make it easier to see how the hydroxide or hydrogen ion was
formed.
Example:
Question: What is the qualitative pH of Fe(NO3)3?
Predict whether an aqueous solution of each of the following salts will be acidic, basic, or neutral. Prove
with appropriate equations.
a. NaC2H3O2
b. NH4NO3
c. Al2(SO4)3
Calculate the pH of a 0.30 M NaF solution. The Ka value for HF is 7.2 × 10−4.
pH = 8.31
Calculate the pH of a 0.10 M NH4Cl solution. The Kb value for NH3 is 1.8 × 10−5.
pH = 5.13
Calculate the pH of a 0.010 M AlCl3 solution. The Ka value for Al(H2O)63+ is 1.4 × 10−5.
pH = 3.43
Yes, this is the dot guy and the structures guy--he was extremely busy making your life difficult!
Exercise 24
Tell whether each of the following is a Lewis acid or base: Draw structures as proof.
a) PH3
b) BCl3
c) H2S
d) SF4