Chem 4

AP*Chemistry
The Chemistry of Acids and Bases

"ACID"--Latin word acidus, meaning sour. (lemon)
"ALKALI"--Arabic word for the ashes that come from burning certain plants;
water solutions feel slippery and taste bitter. (soap)
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.
THE BRONSTED-LOWRY CONCEPT OF ACIDS AND BASES
Using this theory, you should be able to write weak acid/base dissociation equations and identify acid,
base, conjugate acid and conjugate base.
conjugate acid-base pair--A pair of compounds that differ by the presence of one H+ unit. This
idea is critical when it comes to understanding buffer systems. Pay close attention now and it
will pay off later!
HNO3 + H2 H3O+ + NO3
acid
base CA
CB
neutral compound as an acid
NH4+ + H2O R H3O+ + NH3

acid
base CA CB
cation as an acid
H2PO4 + H2O R H3O+ + HPO42

acid
base CA
CB
anion as an acid
*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 Ren 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!)
NH3 + H2O R NH4+ + OH

base acid CA CB
neutral compound
CO32 + H2O R HCO3 + OH

base
acid CA
CB
anion
PO43 + H2O R HPO42 + OH

base acid CA
CB
anion
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.
HBr + NH3 NH4+ + Br
b) What is the conjugate base of H2S?
c) What is the conjugate acid of NO3-?
ACIDS DONATE ONLY ONE PROTON AT A TIME!!!

monoprotic--acids donating one H+ (ex. HC2H3O2)
diprotic--acids donating two H+'s (ex. H2C2O4)
polyprotic--acids donating many H+'s (ex. H3PO4)
polyprotic bases--accept more than one H+; anions with 2 and 3 charges (ex. PO43 ; HPO42)
The Chemistry of Acids & Bases
Amphiprotic or amphoteric --molecules or ions that can behave as EITHER acids or bases;
water, anions of weak acids (look at the examples abovesometimes water was an acid,
sometimes it acted as a base)
Exercise 2
Acid Dissociation (Ionization) Reactions
Write the simple dissociation (ionization) reaction (omitting water) for each of the following acids.
a. Hydrochloric acid (HCl)
b. Acetic acid (HC2H3O2)
c. The ammonium ion (NH4+)
d. The anilinium ion (C6H5NH3+)
e. The hydrated aluminum(III) ion [Al(H2O)6]3+
A: HCl(aq)
B: HC2H3O2(aq)
R H+(aq) + C2H3O2-(aq)
C: NH4+(aq)
D: C6H5NH3+(aq)
E: Al(H2O)63+(aq)
R H+(aq) + Cl-(aq)
R H+(aq) + NH3(aq)
R H+(aq) + C6H5NH2(aq)
R H+(aq) + [Al(H2O)5OH]2+(aq)
RELATIVE STRENGTHS OF ACIDS AND BASES

Strength is determined by the position of the "dissociation" equilibrium.
Strong acids/strong bases
1. dissociates completely in water
2.
have very large dissociation or K values
Strong
1.
2.
Weak
Weak acids/weak bases

dissociate only to a slight extent in water
dissociation constant is very small
Do Not confuse concentration with strength!

STRONG ACIDS: Memorize these SIX
Hydrohalic acids: HCl, HBr, HInote HF is missing!
Nitric: HNO3
Sulfuric: H2SO4
Perchloric: HClO4
The more oxygen present in the polyatomic ion of an oxyacid, the stronger its acid WITHIN that group.
Thats a trend, but not an explanation. So, why? First, notice that the H of the acid is bound to an oxygen
and NOT any other nonmetal present. Oxygen is very electronegative and attracts the electrons of the OH
bonds toward itself. If you add more oxygens, then this effect is magnified and there is increasing electron
density in the region of the molecule that is opposite the H. The added electron density weakens the bond,
thus less energy is required to break the bond and the acid dissociates more readily which we describe as
strong.
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.
WEAK ACIDS AND BASES:

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.
For weak acid reactions:
HA + H2O R H3O+ + A
Ka = [H3O+][A]
[HA]
<<1
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.
The equilibrium expression for bases is known as the Kb.

for weak base reactions:
B + H2O R HB+ + OH
Kb = [HB+][OH]
[B]
<< 1
Write the Kb expression for ammonia.
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.)
Exercise 3
Relative Base Strength
Using table 14.2, arrange the following species according to their strength as bases:
H2O, F, Cl, NO2, and CN.
Cl- < H2O < F- < NO2- < CN-
WATER, THE HYDRONIUM ION, AUTO-IONIZATION, AND THE pH SCALE

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!
H2O(l)
H2O(l)
H3O+(aq)
OH(aq)
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:
Kw = [H3O+][OH] = 1.008 1014 @ 25C = Ka Kb
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 1.0 107)
[OH] > [H+] solution is basic
[OH] < [H+] solution is acidic
Exercise 5
Autoionization of Water
At 60C, the value of Kw is 1 1013.

a. Using Le Chateliers principle, predict whether the reaction below is exothermic or endothermic.
2H2O(l) R H3O+(aq) + OH(aq)
b. Calculate [H+] and [OH] in a neutral solution at 60C.

A: endothermic
B: [H ] = [OH ] = 3 10-7 M
+
The pH Scale
Used to designate the [H+] in most aqueous solutions where [H+] is small.
pH = log [H+]
pOH = log [OH]
pH + pOH = 14
If pH is between zero and 6.999, the solution is acidic, if pH is 7.000, the
solution is neutral and if the pH is above 7.000, the solution is basic.
Reporting the correct number of sig. figs on a pH is problematic since it is a
logarithmic scale. The rule is to report as many decimal places on a pH as
there are in the least accurate measurement you are given.
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 careread the next bulletotherwise 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.
Exercise 6
Calculating [H+] and [OH]
Calculate either the [H+] or [OH] from the information given for each of the following solutions at 25C,
and state whether the solution is neutral, acidic, or basic.
a. 1.0 105 M OH
b. 1.0 107 M OH
c. 10.0 M H+
A: [H+] = 1.0 10-9 M, basic

B: [H+] = 1.0 10-7 M, neutral
C: [OH] = 1.0 10-15 M, acidic
Exercise 7
Calculating pH and pOH
Calculate pH and pOH for each of the following solutions at 25C.

a. 1.0 103 M OH
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 25C. Calculate pOH, [H+], and [OH] for
the sample.
pOH = 6.59
[H+] = 3.9 10-8 M
[OH ] = 2.6 10-7 M
Exercise 9
pH of Strong Acids
a. Calculate the pH of 0.10 M HNO3.

b. Calculate the pH of 1.0 1010 M HCl.
A: pH = 1.00
B: pH = 10.00
10
Exercise 10
The pH of Strong Bases
Calculate the pH of a 5.0 102 M NaOH solution.
pH = 12.70
Calculating pH of Weak Acid Solutions

Calculating pH of weak acids involves setting up an equilibrium. Always start by writing the balanced
equation, setting up the acid equilibrium expression (Ka), defining initial concentrations, changes, and
final concentrations in terms of x, substituting values and variables into the Ka expression and solving
for x. Use the RICE TABLE method you learned in general equilibrium!
Example
Calculate the pH of a 1.00 104 M solution of acetic acid. The Ka of acetic acid is 1.8 105.
Reaction
Initial
Change
Equilibrium
HC2H3O2
R
4
1.00 10
x
(1.00 104 ) x
H+
0
+x
x
+ C2H3O2
0
+x
x
H + C2 H 3O 2
x2
5
Ka =
= 1.8 10 =
HC2 H 3O 2
1104 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 = 1.8 109 1.8 105x ; collect like terms and use either the solver on
your graphing calculator or a quadratic formula solving program youve loaded on your calculator (all of
this to avoid arithmetic mistakes!) to solve for x. You should determine that x = [H+] = 3.44 104 and
that the pH = log (3.44 104) = 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 1.8 103
or 0.0018 which is too close to our initial acid concentration of 0.0001.
11
Need proof?
Suppose our initial concentration had been 0.10 M for the acetic acid in the example problem we just
worked. For acetic acid, 100Ka = 1.8 103 or 0.0018. Thats essentially subtracting zero from 0.10 M.
Aside from that if you did subtract it, youd still follow the least decimal place subtraction sig. fig. rule
and report 0.10 M as your answer to the subtraction.
OK, Ill humor you and apply the quadratic formula to the example we just worked changing the initial
concentration to 0.10 M. First Ill do the quadratic formula and then Ill work it by neglecting x.
Example
Calculate the pH of a 10.10 M solution of acetic acid. The Ka of acetic acid is 1.8 105.
Reaction
Initial
Change
Equilibrium
HC2H3O2
0.10
x
0.10 x
H+
0
+x
x
+ C2H3O2
0
+x
x
H + C2 H 3O 2
x2
Ka =
= 1.8 105 =
HC2 H 3O 2
0.10 x
By cross multiplying and NOT neglecting x, you get x2 = 1.8 106 1.8 105x ; collect like terms and
use either the solver on your graphing calculator or a quadratic formula solving program youve 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!)
and that the pH = log (0.0013327) = 2.88 (2 SF)
Had we neglected x, the math simplifies to
H + C2 H 3O 2
x2
Ka =
= 1.8 105 =
and x2 = 1.8 106
HC2 H 3O 2
0.10 x
So, take the square root of each side to get
x2 =
1.8 106
x = 0.00134 = H +
pH = log (.001341) = 2.87 (2 SF) which is mighty, mighty close, so it is a really good approximation.
So, whats the good news? The AP exam does not have equilibrium problems that require the quadratic
formula. Feel better? No promises about your homework, though!
12
Exercise 11
The pH of Weak Acids
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

13
Only the acid with the largest Ka value will contribute an appreciable [H+]. Determine the pH based
on this acid and ignore any others.
Exercise 12
The pH of Weak Acid Mixtures
Calculate the pH of a solution that contains 1.00 M HCN (Ka = 6.2 1010) and 5.00 M HNO2
(Ka = 4.0 104). Also calculate the concentration of cyanide ion (CN) in this solution at equilibrium.
pH = 1.35
[CN] = 1.4 108 M
Exercise 13
Calculating Percent Dissociation
Calculate the percent dissociation of acetic acid (Ka = 1.8 105) in each of the following solutions.
a. 1.00 M HC2H3O2
b. 0.100 M HC2H3O2
A: = 0.42 %
B: = 1.3 %
14
Exercise 14
Calculating Ka from Percent Dissociation
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.
Ka= 1.4 104
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!
Exercise 15
The pH of Weak Bases I
Calculate the pH for a 15.0 M solution of NH3 (Kb = 1.8 105).
pH = 12.20
Exercise 16
The pH of Weak Bases II
15
Calculate the pH of a 1.0 M solution of methylamine (Kb = 4.38 104).
pH = 12.32
Calculating pH of polyprotic acids

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.
Example:
Consider the dissociation of phosphoric acid.

H3PO4(aq) + H2O(l) R H3O+(aq) + H2PO4 (aq) Ka1 = 7.5 10-3
H2PO4-(aq) + H2O(l)R H3O+(aq) + HPO42(aq)
Ka2 = 6.2 10-8
HPO42-(aq) + H2O(l) R H3O+(aq) + PO43(aq)
Ka3 = 4.8 10-13
Looking at the Ka values, it is obvious that only the first dissociation will be
important in determining the pH of the solution.
16
Except for H2SO4, polyprotic acids have Ka2 and Ka3 values so much weaker than their Ka1 value
that the 2nd and 3rd (if applicable) dissociation can be ignored. The [H+] obtained from this 2nd
and 3rd dissociation is negligible compared to the [H+] from the 1st dissociation. Because H2SO4
is a strong acid in its first dissociation and a weak acid in its second, we need to consider both if the
concentration is more dilute than 1.0 M. The quadratic equation is needed to work this type of
problem.
Exercise 17
The pH of a Polyprotic Acid
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-] = 6.2 108 M
[PO43-] = 1.6 1019 M
Exercise 18
The pH of a Sulfuric Acid
Calculate the pH of a 1.0 M H2SO4 solution.
pH = 0.00
17
Exercise 19
The pH of a Sulfuric Acid
Calculate the pH of a 1.0 102 M H2SO4 solution.
pH = 1.84
ACID-BASE PROPERTIES OF SALTS: HYDROLYSIS (Splitting of water)

Salts are produced when an acid and base react. Salts are not always neutral. Some hydrolyze with water
to produce aqueous solutions with pHs other than 7.00.
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 saltif 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.
H2O R
H3O+ + NH3
NH4+ +
strong acid weak base
If both the cation and the anion contribute to the pH
situation, compare Ka to Kb.
If Kb is larger, basic! The converse is also true.
18
Heres how to think this through:

1. Look at the salt and ask yourself which acid and which base reacted to form it?
2. Ask yourself strong or weak? for each.
3. Embrace the fact that strong wins and predict whether the salt is acidic or basic based
on that victory.
OH
a. If you predict basic, write
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?
1.
2.
3.
4.
Which acid reacted? Nitric

Strong or weak? Strong
Which base reacted? Iron(III) hydroxide
Strong or weak? Weak
Strong wins! acidic so we write:
H+ to get started
+ HOH
Strong is also a spectator so, cross out the spectator and the remaining ion is the other
reactant; Fe(NO3)3
3 H+ + Fe(OH)3
Complete hydrolysis reaction: Fe3+ + 3 HOH
Exercise 20
The Acid-Base Properties of Salts
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
19
Exercise 21
Salts as Weak Bases
Calculate the pH of a 0.30 M NaF solution. The Ka value for HF is 7.2 104.
pH = 8.31
Exercise 22
Salts as Weak Acids I
Calculate the pH of a 0.10 M NH4Cl solution. The Kb value for NH3 is 1.8 105.
pH = 5.13
Exercise 23
Salts as Weak Acids II
Calculate the pH of a 0.010 M AlCl3 solution. The Ka value for Al(H2O)63+ is 1.4 105.
pH = 3.43
20
THE LEWIS CONCEPT OF ACIDS AND BASES

acid--can accept a pair of electrons to form a coordinate covalent bond
base--can donate a pair of electrons to form a coordinate covalent bond
Yes, this is the dot guy and the structures guy--he was extremely busy making your life difficult!
BF3--most famous of all!!
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
21
Exercise 25
Lewis Acids and Basis
For each reaction, identify the Lewis acid and base.

a. Ni2+(aq) + 6NH3(aq) Ni(NH3)62+(aq)
b. H+(aq) + H2O(aq) R H3O+(aq)
A: Lewis acid = nickel(II) ion

Lewis base = ammonia
B: Lewis acid = proton
Lewis base = water molecule
22
AP* Chemistry
Buffers Made Easy
(At least as easy as they are going to get!)
There are many ways to solve buffer problems. Some folks prefer using simply the equilibrium
expression, some prefer Henderson-Hasselbalch and some Ive converted to my way, which is probably
closer to the latter than the former. Some of the methods are more time intensive than others. Never
lose sight of the fact that your students need a method that works for THEM. This method should be
reliable and quick since they will always be under a time crunch! After moderate success with every
method I could find, this handout presents the approach Ive found the most student-friendly. Is it the
method WE learned? NO! If youve had trouble teaching buffers, or your students have had trouble
working buffer problems, give this a try.
First, we need to know what a buffer is, what it does, and how it does it. A buffer is just a case of the
common ion effect.
IS:
A buffer is a solution of a weak acid or base and its salt [which is its conjugate].
DOES:
A buffer resists a change in pH.
HOW IT WORKS:
Since a buffer consists of both an acid or base and its conjugate which
is its complement, an acid and a base are present in all buffer solutions. If a small amount of strong acid
is added to the buffer, there is a base component ready and waiting to neutralize the invader.
There are a few background concepts/skills at which students need to be proficient before any method of
solving buffer problems becomes effective:
Students must know the conjugate A/B concept to be successful at buffer problems. This means
they understand that HA has A- as its conjugate and that NaA is not only the salt, but that any
soluble salt releases the conjugate
pH = log [H+]
Ka Kb = Kw
Realize that any titration involving a weak A/B is a buffer problem. If I titrate HA with NaOH,
then as soon as the first drop splashes into the container, Ive made NaA which promptly
dissociates into A
I use one and only one formula to solve buffer problems, this lessens student [and in my case, teacher]
confusion! Here it is:
Acid
=
K
a
Base
If acid is added to the buffer, simply add acid to the numerator AND subtract the same quantity from the
base since it was self-sacrificing and neutralized the acid. If base is added, simply add the base to the
denominator and subtract from the numerator. Add or subtract in moles NOT molarity! Moles = M V
When equal concentrations (or moles) of Acid and Base are present [which occurs at the equivalence
point of a titration] the ratio of acid to base equals ONE and therefore, the pH = pKa. IF you are asked
to construct a buffer of a specific pH and given a table of Kas, choose a Ka with an exponent close to
the desired pH and use equal concentrations of the acid and base.
Lets try it! Heres a common calculate the pH of a buffer before and after an invader is added.
Convert to moles when doing the adding and subtracting! The Ka of formic acid is 1.8 104
Exercise 1
Calculate the pH of 0.500 L of a buffer solution composed of 0.50 M formic acid and 0.70 M sodium
formate before and after adding 10.0 mL of 1.00 M HCl.
PREPARING BUFFER SOLUTIONS:

Use 0.10 M to 1.0 M solutions of reagents & choose an acid whose Ka is near the [H3O+] concentration
we want. The pKa should be as close to the pH desired as possible. Adjust the ratio of weak A/B and its
salt to fine tune the pH.
Exercise 2
Using an acetic acid\sodium acetate buffer solution, what ratio of acid to conjugate base will you need to
maintain the pH at 5.00? Explain how you would make up such a solution.
It is the relative # of moles of acid/CB or base/CA that is important since they are in the same solution
and share the same solution volume.
2
Buffers Made Easy
This allows companies to make concentrated versions of buffer and let the customer dilute--this will not
affect the # of moles present--just the dilution of those moles.
What if youre given a Kb?
Exercise 3
A buffered solution contains 0.25 M NH3 ( Kb = 1.8 105) and 0.40 M NH4Cl.
a) Calculate the pH of this solution.
b) Calculate the pH when 0.10 mol of gaseous HCl is added to 1.0 L of the buffered solution.
Exercise 4
A chemist needs a solution buffered at pH 4.30 and can choose from the following list of acids and their
soluble salt:
a. chloroacetic acid Ka = 1.35 103
b. propanoic acid
Ka = 1.3 105
c. benzoic acid
Ka = 6.4 105
d. hypochlorus acid Ka = 3.5 108
Calculate the ratio of A/B required for each system to yield a pH of 4.30. Which system works best?
3
Buffers Made Easy
ACID-BASE TITRATION CURVES

Only when the acid AND base are both strong is the pH at the equivalence point 7. Any other
conditions and you get to do a nasty equilibrium problem. Its really a stoichiometry problem with a
limiting reactant. The excess is responsible for the pH
Weak acid + strong base ) eq. pt. > pH 7
Strong acid + weak base ) eq. pt. < pH 7
There is a distinction between the equivalence point and the end point. The end point is when the
indicator changes color. If youve made a careful choice, the equivalence point, when the number of
moles of acid = number of moles of base, will be achieved at the same time.
Exercise 5
For the titration of 50.0 mL of 0.200 M HNO3 with 0.100 M NaOH calculate the pH of the solution at
the following selected points of the titration:
a) NO NaOH has been added:
b) 10.0 mL of NaOH has been added:
c) 20.0 mL (total as opposed to additional) of NaOH has been added:
d) 50.0 mL (total) of NaOH has been added:
e) 100.0 mL (total) of NaOH has been added:
f) 200.0 mL (total) of NaOH has been added:
4
Buffers Made Easy
FIVE POINTS OF INTEREST ALONG A TITRATION CURVE for weak acids/bases:

1. The pH before the titration begins. Treat as usual, the acid or base in the flask determines the
pH. If weak, a RICE table is in order.
2. The pH on the way to the equivalence point. You are in the land of buffer as soon as the
first drop from the buret makes a splash and reacts to form the salt. Whatever is in the
Acid
to solve for the hydrogen ion
Base
burette is the added part. Use H + = Ka
concentration and subsequently the pH. Either the acid or the base [whichever is in the
burette] starts at ZERO.
Acid
on the
3. The pH at the midpoint of the titration ( equivalence point): H + = Ka
Base
+
way to the equivalence point as explained above; once the midpoint is reached, [H ] = Ka
since of the acid or base has been neutralized, AND the resulting solution in the beaker is
composed of the half that remains AND the salt. That means the A/B term is a big tall ONE
so, it follows that pH = pKa.
4. The pH at the equivalence point.you are simply calculating the pH of the salt, all the acid
or base is now neutralized [to salt + water!]. Write the hydrolysis reaction as the R of your
RICE table. [Examples follow the fifth point of interest]
5. The pH beyond the equivalence pointits stoichiometry again with a limiting reactant.
Calculate the molarity of the EXCESS and solve for either pH directly (excess H+) or pOH
(excess OH) and subtract it from 14 to arrive at pH. Be sure to track the total volume when
calculating the molarity!
LEARNING TO WRITE SALT HYDROLYSIS REACTIONS
Recall that when quantities of acid and base react, a neutralization reaction takes place and the
products of such a reaction are salt and water. The trouble is that not all salts are neutral.
However, reasoning through the pH of a salt is easy as is writing the subsequent hydrolysis
reaction. Ponder the following points:
Hydrolysis translates into water splitting but the salt is also split. The rest of this will
be much easier if you think of H2O as HOH and as a reactant. Essentially, a hydrolysis
reaction is the reverse of a neutralization reaction and is written in net ionic form for all
soluble salts.
IF a strong base is reacted with a weak acid, Strong wins! and the salt is basic, thus
OH forms as a product.
IF a strong acid is reacted with a weak base, Strong wins! and the salt is acidic, thus
H+ forms as a product.
The Strong portion of the acid or base is source of the Spectator ion.
The remaining ion (or neutral molecule) is the reactant that reacts with the water.
5
Buffers Made Easy
Example 1 Write the hydrolysis reaction for the salt, NaCN.

Explanation: First, recognize NaCN as a salt if that information is not giventhe polyatomic ion
is a dead give away! Next, ask yourself which acid reacted with which base to generate the salt
in the first place?
Which base? NaOH. Which acid? HCN.
Now, ask yourself: Is the base strong or weak? NaOH, strong. Is the acid strong or weak? HCN,
weak. Strong wins!, so it is a basic salt, AND Strong is also the Spectator. So, sodium ion
is not in the net ionic hydrolysis equation, leaving CN as the reacting species. Ah, you are
ready to write the hydrolysis reaction.
Start the same way every time you try to write a hydrolysis reactiondraw the arrow in the
center of your answer space!
Its a hydrolysis reaction, water is a reactant and splits into H+ and OH, so write it as HOH until
you get the hang of this process. Your reaction looks like this so far:
+
HOH
Recap what you now know: NaCN is a basic salt. Since it is basic, OH is a product. Your
reaction improves
+
HOH
OH
More knowledge: Na+ is a spectator (since Strong, Spectatorits an alliteration, get it?
Strong and Spectator both start with an S.) leaving CN as the other reactant. Your reaction
improves yet again
CN
HOH
OH
Now, thinkthinkthink. IF HOH released OH as a product, then H+ is left to react with the
negative cyanide ion. Your final improvement to the reaction finishes it off
CN
HOH
OH + HCN
Why is this such a big deal? A hydrolysis reaction is what you must plop into your RICE table
to solve for the pH (or pOH) of an acid-base titration where either participant is weak.
BECAUSE, at the equivalence point moles acid = moles base = moles salt formed. Just be sure
and calculate the molarity of the salt by tracking the total volume before putting its concentration
into the rice table.
6
Buffers Made Easy
Example 2 Write the hydrolysis reactions for the following salts:

a)
b)
c)
d)
KNO2
NH4NO3
CH3NH3Cl
NaClO2
a) Basic salt
NO2
HOH
OH + HNO2
b) Acidic salt
NH4+
HOH
H+
c) Acidic salt
e) Basic salt
CH3NH3+ +
ClO2
HOH H+
HOH
+ NH4OH
+ CH3NH3OH
OH + HClO2
Exercise 6
Hydrogen cyanide gas (HCN), a powerful respiratory inhibitor, is highly toxic. It is a very weak
acid (Ka = 6.2 1010) when dissolved in water. If a 50.0 mL sample of 0.100 M HCN is titrated
with 0.100 M NaOH, calculate the pH of the solution
a) after 8.00 mL of 0.100 M NaOH has been added.
b) at the halfway point of the titration.
c) at the equivalence point of the titration.
7
Buffers Made Easy
CHOOSING INDICATORS FOR TITRATIONS

Choose and indicator with a Ka near that of the acid youre titrating AND whose color changes strongly at
the equivalence point. Those blasted e words! moles acid equal moles base at the equivalence pointthe
color changes at the end point. Choose your indicator wisely, and the two coincide!
Exercise 7
Use table 15.8 to decide which indicator would be best to use in the titration of ammonia with hydrochloric
acid.
Exercise 8
Bromthymol blue has a Ka value of 1.0 107, is yellow in its HIn form and blue in its In- form. Suppose
we put a few drops of this indicator in a strongly acidic solution. If the solution is then titrated with NaOH,
at what pH will the indicator color change first be visible?
Shall we try this with some retired AP questions?

[Go to the AP Buffers Free Response Questions handout.]
AP* Buffer Equilibrium Free Response Questions
page 1
Essay Questions
1972
Given a solution of ammonium chloride, what additional reagent or reagents are needed to prepare a buffer
from the ammonium chloride solution?
Explain how this buffer solution resists a change in pH when:
(a) Moderate amounts of strong acid are added.
(b) Moderate amounts of strong base are added.
(c) A portion of the buffer solution is diluted with an equal volume of water.
1983
(a) Specify the properties of a buffer solution. Describe the components and the composition of effective
buffer solutions.
(b) An employer is interviewing four applicants for a job as a laboratory technician and asks each how to
prepare a buffer solution with a pH close to 9.
Archie A.
Beula B.
Carla C.
Dexter D.
says he would mix acetic acid and sodium acetate solutions.

says she would mix NH4Cl and HCl solutions.
says she would mix NH4Cl and NH3 solutions.
says he would mix NH3 and NaOH solutions.
Which of these applicants has given an appropriate procedure? Explain your answer, referring to your
discussion in part (a). Explain what is wrong with the erroneous procedures.
(No calculations are necessary, but the following acidity constants may be helpful: acetic acid,
Ka = 1.8 105 NH4+, Ka = 5.6 1010)
(1) AP is a registered trademark of the College Board. The College Board was not involved in the production of and does not endorse this product. (2) Test Questions
are Copyright 1984-2008 by College Entrance Examination Board, Princeton, NJ. All rights reserved. For face-to-face teaching purposes, classroom teachers are
permitted to reproduce the questions. Web or Mass distribution prohibited.
1988
A 30.00 milliliter sample of a weak monoprotic acid was titrated with a standardized solution of NaOH.
A pH meter was used to measure the pH after each increment of NaOH was added, and the curve above was
constructed.
(a) Explain how this curve could be used to determine the molarity of the acid.
(b) Explain how this curve could be used to determine the dissociation constant Ka of the weak monoprotic
acid.
(c) If you were to repeat the titration using a indicator in the acid to signal the endpoint, which of the following
indicators should you select? Give the reason for your choice.
Methyl red
Cresol red
Alizarin yellow
Ka = 1 105
Ka = 1 108
Ka = 1 1011
(d) Sketch the titration curve that would result if the weak monoprotic acid were replaced by a strong
monoprotic acid, such as HCl of the same molarity. Identify differences between this titration curve and the
curve shown above.
page 3
1992
The equations and constants for the dissociation of three different acids are given below.
Ka = 4.2 107
HCO3 p H+ + CO32
H2PO4 p H+ + HPO42
Ka = 6.2 108
HSO4 p H+ + SO42
Ka = 1.3 102
(a) From the systems above, identify the conjugate pair that is best for preparing a buffer with a
pH of 7.2. Explain your choice.
(b) Explain briefly how you would prepare the buffer solution described in (a) with the conjugate pair you
have chosen.
(c) If the concentrations of both the acid and the conjugate base you have chosen were doubled, how would
the pH be affected? Explain how the capacity of the buffer is affected by this change in concentrations of
acid and base.
(d) Explain briefly how you could prepare the buffer solution in (a) if you had available the solid salt of the
only one member of the conjugate pair and solution of a strong acid and a strong base.
1998
An approximately 0.1-molar solution of NaOH is to be standardized by titration. Assume that the
following materials are available.
Clean, dry 50 mL buret
250 mL Erlenmeyer flask
Wash bottle filled with distilled
water
Analytical balance
Phenolphthalein indicator solution
Potassium hydrogen phthalate, KHP, a pure solid
monoprotic acid (to be used as the primary standard)
(a) Briefly describe the steps you would take, using materials listed above, to standardize the NaOH
solution.
(b) Describe (i.e., set up) the calculations necessary to determine the concentration of the NaOH
solution.
page 4
(c) After the NaOH solution has been standardized, it is

used to titrate a weak monoprotic acid, HX. The
equivalence point is reached when 25.0 mL of NaOH
solution has been added. In the space provided at the
right, sketch the titration curve, showing the pH
changes that occur as the volume of NaOH solution
added increases from 0 to 35.0 mL. Clearly label the
equivalence point on the curve.
(d) Describe how the value of the acid-dissociation constant, Ka, for the weak acid HX could be
determined from the titration curve in part (c).
(e) The graph below shows the results obtained by titrating a different weak acid, H2Y, with the
standardized NaOH solution. Identify the negative ion that is present in the highest concentration
at the point in the titration represented by the letter A on the curve.
page 5
2000
A volume of 30.0 mL of 0.10 M NH3(aq) is titrated with 0.20 M HCl(aq). The value of the base-dissociation
constant, Kb, for NH3 in water is 1.8 105 at 25C.
(a) Write the net-ionic equation for the reaction of NH3(aq) with HCl(aq).
(b) Using the axes provided below, sketch the titration curve that results when a total of
40.0 mL of 0.20 M HCl(aq) is added dropwise to the 30.0 mL volume of 0.10 M NH3(aq).
(c) From the table below, select the most appropriate indicator for the titration. Justify your choice.
(d) If equal volumes of 0.10 M NH3(aq)and 0.10 M NH4Cl(aq) are mixed, is the resulting solution
acidic, neutral, or basic? Explain.
page 6
Problems
1970
(a) What is the pH of a 2.0 molar solution of acetic acid. Ka acetic acid = 1.8 105?
(b) A buffer solution is prepared by adding 0.10 liter of 2.0 molar acetic acid solution to 0.1 liter of a
1.0 molar sodium hydroxide solution. Compute the hydrogen ion concentration of the buffer
solution.
(c) Suppose that 0.10 liter of 0.50 molar hydrochloric acid is added to 0.040 liter of the buffer prepared
in (b). Compute the hydrogen ion concentration of the resulting solution.
1977
The value of the ionization constant, Ka, for hypochlorous acid, HOCl, is 3.1 108.
(a) Calculate the hydronium ion concentration of a 0.050 molar solution of HOCl.
(b) Calculate the concentration of hydronium ion in a solution prepared by mixing equal volumes of
0.050 molar HOCl and 0.020 molar sodium hypochlorite, NaOCl.
(c) A solution is prepared by the disproportionation reaction below. Cl2 + H2O p HCl + HOCl
Calculate the pH of the solution if enough chlorine is added to water to make the concentration of HOCl
equal to 0.0040 molar.
1982
A buffer solution contains 0.40 mole of formic acid, HCOOH, and 0.60 mole of sodium formate,
HCOONa, in 1.00 liter of solution. The ionization constant, Ka, of formic acid is 1.8 104.
(a) Calculate the pH of this solution.
(b) If 100. milliliters of this buffer solution is diluted to a volume of 1.00 liter with pure water, the pH
does not change. Discuss why the pH remains constant on dilution.
(c) A 5.00 milliliter sample of 1.00 molar HCl is added to 100. milliliters of the original buffer solution.
Calculate the [H3O+] of the resulting solution.
(d) A 800. milliliter sample of 2.00 molar formic acid is mixed with 200. milliliters of 4.80 molar NaOH.
Calculate the [H3O+] of the resulting solution.
1984
Sodium benzoate, C6H5COONa, is the salt of the weak acid, benzoic acid, C6H5COOH. A 0.10 molar solution
of sodium benzoate has a pH of 8.60 at room temperature.
(a) Calculate the [OH] in the sodium benzoate solution described above.
(b) Calculate the value for the equilibrium constant for the reaction:
C6H5COO + H2O p C6H5COOH + OH
(c) Calculate the value of Ka, the acid dissociation constant for benzoic acid.
(d) A saturated solution of benzoic acid is prepared by adding excess solid benzoic acid to pure water at
room temperature. Since this saturated solution has a pH of 2.88, calculate the molar solubility of
benzoic acid at room temperature.
page 7
1991
The acid ionization constant, Ka, for propanoic acid, C2H5COOH, is 1.3 105.
(a) Calculate the hydrogen ion concentration, [H+], in a 0.20 molar solution of propanoic acid.
(b) Calculate the percentage of propanoic acid molecules that are ionized in the solution in (a).
(c) What is the ratio of the concentration of propanoate ion, C2H5COO, to that of propanoic acid in
a buffer solution with a pH of 5.20?
(d) In a 100. milliliter sample of a different buffer solution, the propanoic acid concentration is 0.35 molar
and the sodium propanoate concentration is 0.50 molar. To this buffer solution, 0.0040 mole of solid
NaOH is added. Calculate the pH of the resulting solution.
1993
CH3NH2 + H2O p CH3NH3+ + OH
Methylamine, CH3NH2, is a weak base that reacts according to the equation above. The value of the ionization
constant, Kb, is 5.25 104. Methylamine forms salts such as methylamonium nitrate, (CH3NH3+)(NO3).
(a) Calculate the hydroxide ion concentration, [OH], of a 0.225 molar aqueous solution of methylamine.
(b) Calculate the pH of a solution made by adding 0.0100 mole of solid methylamonium nitrate to
120.0 milliliters of a 0.225 molar solution of methylamine. Assume no volume change occurs.
(c) How many moles of either NaOH or HCl (state clearly which you choose) should be added to the solution
in (b) to produce a solution that has a pH of 11.00? Assume that no volume change occurs.
(d) A volume of 100. milliliters of distilled water is added to the solution in (c). How is the pH of the solution
affected? Explain.
1996
HOCl p OCl + H+
Hypochlorous acid, HOCl, is a weak acid commonly used as a bleaching agent. The acid-dissociation
constant, Ka, for the reaction represented above is 3.2 108.
(a) Calculate the [H+] of a 0.14-molar solution of HOCl.
(b) Write the correctly balanced net ionic equation for the reaction that occurs NaOCl is dissolved in
water and calculate the numerical value of the equilibrium constant for the reaction.
(c) Calculate the pH of a solution made by combining 40.0 milliliters of 0.14-molar HOCl and
10.0 milliliters of 0.56-molar NaOH.
(d) How many millimoles of solid NaOH must be added to 50.0 milliliters of 0.20-molar HOCl to obtain
a buffer solution that has a pH of 7.49? Assume that the addition of the solid NaOH results in a
negligible change in volume.
(e) Household bleach is made by dissolving chlorine gas in water, as represented below.
Cl2(g) + H2O p H+ + Cl + HOCl(aq)
Calculate the pH of such a solution if the concentration of HOCl in the solution is 0.065 molar.
page 8
2001
Answer the following questions about acetylsalicylic acid, the active ingredient in aspirin.
(a) The amount of acetylsalicylic acid in a single aspirin tablet is 325 mg, yet the tablet has a mass
of 2.00 g. Calculate the mass percent of acetylsalicylic acid in the tablet.
(b) The elements contained in acetylsalicylic acid are hydrogen, carbon, and oxygen. The combustion
of 3.000 g of the pure compound yields 1.200 g of water and 3.72 L of dry carbon dioxide,
measured at 750. mm Hg and 25C. Calculate the mass, in g, of each element in the 3.000 g
sample.
(c) A student dissolved 1.625 g of pure acetylsalicylic acid in distilled water and titrated the resulting
solution to the equivalence point using 88.43 mL of 0.102 M NaOH(aq). Assuming that
acetylsalicylic acid has only one ionizable hydrogen, calculate the molar mass of the acid.
(d) A 2.00 103 mole sample of pure acetylsalicylic acid was dissolved in 15.00 mL of water and
then titrated with 0.100 M NaOH(aq). The equivalence point was reached after 20.00 mL of the
NaOH solution had been added. Using the data from the titration, shown in the table below,
determine
(i)
(ii)
the value of the acid dissociation constant, Ka , for acetylsalicylic acid and
the pH of the solution after a total volume of 25.00 mL of the NaOH solution had been
added (assume that volumes are additive).
page 9
2002B
HC3H5O3(aq) p H+(aq) + C3H5O3(aq)
Lactic acid, HC3H5O3, is a monoprotic acid that dissociates in aqueous solution, as represented by the
equation above. Lactic acid is 1.66 percent dissociated in 0.50 M HC3H5O3 (aq) at 298 K. For parts (a)
through (d) below, assume the temperature remains at 298 K.
(a) Write the expression for the acid-dissociation constant, Ka , for lactic acid and calculate its value.
(b) Calculate the pH of 0.50 M HC3H5O3.
(c) Calculate the pH of a solution formed by dissolving 0.045 mole of solid sodium lactate, NaC3H5O3,
in 250. mL of 0.50 M HC3H5O3. Assume that volume change is negligible.
(d) A 100. mL sample of 0.10 M HCl is added to 100. mL of 0.50 M HC3H5O3. Calculate the molar
concentration of lactate ion, C3H5O3, in the resulting solution.
2003
C6H5NH2(aq) + H2O(l) p C6H5NH3+(aq) + OH(aq)
Aniline, a weak base, reacts with water according to the reaction represented above.
(a) Write the equilibrium constant expression, Kb , for the reaction represented above.
(b) A sample of aniline is dissolved in water to produce 25.0 mL of a 0.10 M solution.
The pH of the solution is 8.82. Calculate the equilibrium constant, Kb , for this reaction.
(c) The solution prepared in part (b) is titrated with 0.10 M HCl. Calculate the pH of the solution
when 5.0 mL of the acid has been added.
(d) Calculate the pH at the equivalence point of the titration in part (c).
(e) The pKa values for several indicators are given below. Which of the indicators listed is most suitable
for this titration? Justify your answer.
Indicator
pKa
Erythrosine
Litmus
3
7
Thymolphthalein
10
page 10
2005
HC3H5O2(aq) p C3H5O2(aq) + H+(aq)
Ka = 1.34 105
Propanoic acid, HC3H5O2 , ionizes in water according to the equation above.

(a) Write the equilibrium-constant expression for the reaction.
(b) Calculate the pH of a 0.265 M solution of propanoic acid.
(c) A 0.496 g sample of sodium propanoate, NaC3H5O2 , is added to a 50.0 mL sample of
a 0.265 M solution of propanoic acid. Assuming that no change in the volume of the solution
occurs, calculate each of the following.
(i) The concentration of the propanoate ion, C3H5O2 (aq), in the solution
+
(ii) The concentration of the H (aq) ion in the solution
The methanoate ion, HCO2(aq), reacts with water to form methanoic acid and hydroxide ion, as shown in
the following equation.
HCO2(aq) + H2O(l) p HCO2H(aq) + OH(aq)
(d) Given that [OH ] is 4.18 10
M in a 0.309 M solution of sodium methanoate, calculate each of
the following.
(i) The value of Kb for the methanoate ion, HCO2(aq)
(ii) The value of Ka for methanoic acid, HCO2H
(e) Which acid is stronger, propanoic acid or methanoic acid? Justify your answer.
2006B
C6H5COOH(s) p C6H5COO (aq) + H+(aq)
Ka = 6.46 105
Benzoic acid, C6H5COOH, dissociates in water as shown in the equation above. A 25.0 mL sample of an
aqueous solution of pure benzoic acid is titrated using standardized 0.150 M NaOH.
(a) After addition of 15.0 mL of the 0.150 M NaOH, the pH of the resulting solution is 4.37. Calculate
each of the following.
(i) [H+] in the solution
(ii) [OH] in the solution
(iii) The number of moles of NaOH added
(iv) The number of moles of C6H5COO (aq) in the solution
(v) The number of moles of C6H5COOH in the solution
page 11
(b) State whether the solution at the equivalence point of the titration is acidic, basic, or neutral.
Explain your reasoning.
In a different titration, a 0.7529 g sample of a mixture of solid C6H5COOH and solid NaCl is dissolved in
water and titrated with 0.150 M NaOH. The equivalence point is reached when 24.78 mL of the base
solution is added.
(c) Calculate each of the following.
(i) The mass, in grams, of benzoic acid in the solid sample
(ii) The mass percentage of benzoic acid in the solid sample
AP* Chemistry
Demystifying Titration Curves
This handout is meant to accompany the instructional video found at either http://www.vimeo.com/19007364 or
http://www.edutube.org/en/video/ap-chemistry-interpreting-titration-curves. This wont make a lick of sense
unless you watch the video containing the explanations!
AP* Acid-Base Equilibrium Free Response Questions
page 1
Essay Questions
1986
H2SO3
HSO3
HClO4
HClO3
H3BO3
Oxyacids, such as those above, contain an atom bonded to one or more oxygen atoms; one or more of
these oxygen atoms may also be bonded to hydrogen.
(a) Discuss the factors that are often used to predict correctly the strengths of the oxyacids listed above.
(b) Arrange the examples above in the order of increasing acid strength.
1990
Give a brief explanation for each of the following.
(a) For the diprotic acid H2S, the first dissociation constant is larger than the second dissociation constant
by about 105 (K1 = 105 K2).
(b) In water, NaOH is a base but HOCl is an acid.
(c) HCl and HI are equally strong acids in water but, in pure acetic acid, HI is a stronger acid than HCl.
(d) When each is dissolved in water, HCl is a much stronger acid than HF.
1994
A chemical reaction occurs when 100. milliliters of 0.200-molar HCl is added dropwise to 100. milliliters
of 0.100-molar Na3PO4 solution.
(a) Write the two net ionic equations for the formation of the major products.
(b) Identify the species that acts as both a Brnsted acid and as a Brnsted base in the equation in (a),
Draw the Lewis electron-dot diagram for this species.
(c) Sketch a graph using the axes provided, showing the shape of the titration curve that results when
100. milliliters of the HCl solution is added slowly from a buret to the Na3PO4 solution. Account for the
shape of the curve.
(d) Write the equation for the reaction that occurs if a few additional milliliters of the HCl solution are added
to the solution resulting from the titration in (c).
(1) AP is a registered trademarK of the College Board. The College Board was not involved in the production of and does not endorse this product. (2) Test
Questions are Copyright 1984-2008 by College Entrance Examination Board, Princeton, NJ. All rights reserved. For face-to-face teaching purposes,
classroom teachers are permitted to reproduce the questions. Web or Mass distribution prohibited.
page 2
2000
A volume of 30.0 mL of 0.10 M NH3(aq) is titrated with 0.20 M HCl(aq). The value of the basedissociation constant, Kb , for NH3 in water is 1.8 105 at 25C.
(a) Write the net-ionic equation for the reaction of NH3(aq) with HCl(aq).
(b) Using the axes provided below, sketch the titration curve that results when a total of 40.0 mL
of 0.20 M HCl(aq) is added dropwise to the 30.0 mL volume of 0.10 M NH3(aq) .
(c) From the table below, select the most appropriate indicator for the titration. Justify your choice.
(d) If equal volumes of 0.10 M NH3(aq) and 0.10 M NH4Cl(aq) are mixed, is the resulting solution
acidic, neutral, or basic? Explain.
2010B
5. A solution of 0.100 M HCl and a solution of 0.100 M NaOH are prepared. A 40.0 mL sample of one of the
solutions is added to a beaker and then titrated with the other solution. A pH electrode is used to obtain the data
that are plotted in the titration curve shown above.
(a) Identify the solution that was initially added to the beaker. Explain your reasoning.
(b) On the titration curve above, circle the point that corresponds to the equivalence point.
(c) At the equivalence point, how many moles of titrant have been added?
(d) The same titration is to be performed again, this time using an indicator. Use the information in the table
below to select the best indicator for the titration. Explain your choice.
Indicator
pH Range of
Color Change
Methyl violet
0 1.6
Methyl red
46
Alizarin yellow
10 12
(e) What is the difference between the equivalence point of a titration and the end point of a titration?
(f) On the grid provided below, sketch the titration curve that would result if the solutions in the
beaker and buret were reversed (i.e., if 40.0 mL of the solution used in the buret in the previous titration
were titrated with the solution that was in the beaker).
of a titration?
page 4
Problems
1987
The percentage by weight of nitric acid, HNO3, in a sample of concentrated nitric acid is to be determined.
(a) Initially a NaOH solution was standardized by titration with a sample of potassium hydrogen
phthalate, KHC8H4O4, a monoprotic acid often used as a primary standard. A sample of pure
KHC8H4O4 weighing 1.518 grams was dissolved in water and titrated with the NaOH solution. To
reach the equivalence point, 26.90 milliliters of base was required. Calculate the molarity of the
NaOH solution. (Molecular weight: KHC8H4O4 = 204.2)
(b) A 10.00 milliliter sample of the concentrated nitric acid was diluted with water to a total volume of
500.00 milliliters. Then 25.00 milliliters of the diluted acid solution was titrated with the standardized
NaOH solution prepared in part (a). The equivalence point was reached after 28.35 milliliters of the
base had been added. Calculate the molarity of the concentrated nitric acid.
(c) The density of the concentrated nitric acid used in this experiment was determined to be 1.42 grams
per milliliter. Determine the percentage by weight of HNO3 in the original sample of concentrated
nitric acid.
1996
Concentrated sulfuric acid (18.4-molar H2SO4) has a density of 1.84 grams per milliliter. After dilution with
water to 5.20-molar, the solution has a density of 1.38 grams per milliliter and can be used as an electrolyte in
lead storage batteries for automobiles.
(a) Calculate the volume of concentrated acid required to prepare 1.00 liter of 5.20-molar H2SO4.
(b) Determine the mass percent of H2SO4 in the original concentrated solution.
(c) Calculate the volume of 5.20-molar H2SO4 that can be completely neutralized with 10.5 grams of sodium
bicarbonate NaHCO3.
(d) What is the molality of the 5.20-molar H2SO4?
AP* Thermodynamics Free Response Questions
page 1
Essay Questions
1991
BCl3(g) + NH3(g) p Cl3BNH3(s)
The reaction represented above is a reversible reaction.
(a) Predict the sign of the entropy change, S, as the reaction proceeds to the right. Explain your prediction.
(b) If the reaction spontaneously proceeds to the right, predict the sign of the enthalpy change, H. Explain your
prediction.
(c) The direction in which the reaction spontaneously proceeds changes as the temperature is increased above a
specific temperature. Explain.
(d) What is the value of the equilibrium constant at the temperature referred to in (c); that is, the specific
temperature at which the direction of the spontaneous reaction changes? Explain.
1993
2 C4H10(g) + 13 O2(g) 8 CO2(g) + 10 H2O(l)
The reaction represented above is spontaneous at 25C. Assume that all reactants and products are in their standard
state.
(a) Predict the sign of S for the reaction and justify your prediction.
(b) What is the sign of G for the reaction? How would the sign and magnitude of G be affected by an increase
in temperature to 50C? Explain your answer.
(c) What must be the sign of H for the reaction at 25C? How does the total bond energy of the reactants
compare to that of the products?
(d) When the reactants are place together in a container, no change is observed even though the reaction is known
to be spontaneous. Explain this observation.
1994
2 H2S(g) + SO2(g) 3 S(s) + 2 H2O(g)
At 298 K, the standard enthalpy change, H for the reaction represented above is -145 kilojoules.
(a) Predict the sign of the standard entropy change, S, for the reaction. Explain the basis for your prediction.
(b) At 298 K, the forward reaction (i.e., toward the right) is spontaneous. What change, if any, would occur in the
value of G for this reaction as the temperature is increased? Explain your reasoning using thermodynamic
principles.
(c) What change, if any, would occur in the value of the equilibrium constant, Keq, for the situation described in
(b)? Explain your reasoning.
(d) The absolute temperature at which the forward reaction becomes nonspontaneous can be predicted. Write the
equation that is used to make the prediction. Why does this equation predict only an approximate value for the
temperature?
page 2
1997
For the gaseous equilibrium represented below, it is observed that greater amounts of PCl3 and Cl2 are produced
as the temperature is increased.
PCl5(g) p PCl3(g) + Cl2(g)
(a) What is the sign of S for the reaction? Explain.
(b) What change, if any, will occur in G for the reaction as the temperature is increased. Explain your
reasoning in terms of thermodynamic principles.
(c) If He gas is added to the original reaction mixture at constant volume and temperature, what will happen to
the partial pressure of Cl2? Explain.
(d) If the volume of the original reaction is decreased at constant temperature to half the original volume, what
will happen to the number of moles of Cl2 in the reaction vessel? Explain.
1999
Answer the following questions in terms of thermodynamic principles and concepts of kinetic molecular
theory.
(a) Consider the reaction represented below, which is spontaneous at 298 K.
CO2(g) + 2 NH3(g) CO(NH2)2(s) + H2O(l); H298 = 134 kJ
(i)
For the reaction, indicate whether the standard entropy change, S298, is positive, or
negative, or zero. Justify your answer.
(ii)
Which factor, the change in enthalpy, H298, or the change in entropy, S298, provides
the principal driving force for the reaction at 298 K? Explain.
(iii) For the reaction, how is the value of the standard free energy change, G, affected by an
increase in temperature? Explain.
(b) Some reactions that are predicted by their sign of G to be spontaneous at room temperature do
not proceed at a measurable rate at room temperature.
(i) Account for this apparent contradiction.
(ii) A suitable catalyst increases the rate of such a reaction. What effect does the catalyst have
on G for the reaction? Explain.

2000
page 3
O3(g) + NO(g) O2(g) + NO2(g)
Consider the reaction represented above.

(a) Referring to the data in the table below, calculate the standard enthalpy change, H, for the reaction at
25C. Be sure to show your work.
(b) Make a qualitative prediction about the magnitude of the standard entropy change, S, for the reaction
at25C. Justify your answer.
(c) On the basis of your answers to parts (a) and (b), predict the sign of the standard free-energy change,
G, for the reaction at 25C. Explain your reasoning.
(d) Use the information in the table below to write the rate-law expression for the reaction, and explain how
you obtained your answer.
(e) The following three-step mechanism is proposed for the reaction. Identify the step that must be the
slowest in order for this mechanism to be consistent with the rate-law expression derived in part (d).
Explain.
Step I:
Step II:
Step III:
O3 + NO O + NO3
O + O3 2 O2
NO3 + NO 2 NO2
page 4
2003
Answer the following questions that relate to the chemistry of nitrogen.
(a) Two nitrogen atoms combine to form a nitrogen molecule, as represented by the following equation.
2 N(g) N2(g)
Using the table of average bond energies below, determine the enthalpy change, H, for the reaction.
Bond
Average Bond Energy (kJ mol1)
NN
N=N
160
420
NN
950
(b) The reaction between nitrogen and hydrogen to form ammonia is represented below.
N2(g) + 3 H2(g)
2 NH3(g)
H = 92.2 kJ
Predict the sign of the standard entropy change, S, for the reaction. Justify your answer.
(c) The value of G for the reaction represented in part (b) is negative at low temperatures but positive at high
temperatures. Explain.
(d) When N2(g) and H2(g) are placed in a sealed container at a low temperature, no measurable amount of
NH3(g) is produced. Explain.
2004B
N2(g) + 2 H2(g) p N2H4(g)
H 298 = +95.4 kJ mol1; S 298 = 176 J K1 mol1
Answer the following questions about the reaction represented above using principles of thermodynamics.
(a)
(b)
(c)
(d)
(e)
On the basis of the thermodynamic data given above, compare the sum of the bond strengths of the
reactants to the sum of the bond strengths of the product. Justify your answer.
Does the entropy change of the reaction favor the reactants or the product? Justify your answer.
For the reaction under the conditions specified, which is favored, the reactants or the product? Justify
your answer.
Explain how to determine the value of the equilibrium constant, Keq, for the reaction. (Do not do any
calculations.)
Predict whether the value of Keq for the reaction is greater than 1,equal to 1, or less than 1. Justify your
prediction.
page 5
Problems
1990
Standard Free Energies of Formation at 298 K
Substance
C2H4Cl2(g)
C2H5Cl(g)
HCl(g)
Cl2(g)
Gf 298 K, kJ mol1
80.3
60.5
95.3
0
Average Bond Dissociation Energies at 298 K

Bond
CH
CC
CCl
ClCl
HCl
Energy, kJ mol1
414
347
377
243
431
The tables above contain information for determining thermodynamic properties of the reaction below.
C2H5Cl(g) + Cl2(g) C2H4Cl2(g) + HCl(g)
(a)
(b)
(c)
(d)
Calculate the H for the reaction above, using the table of average bond dissociation energies.
Calculate the S for the reaction at 298 K, using data from either table as needed.
Calculate the value of Keq for the reaction at 298 K.
What is the effect of an increase in temperature on the value of the equilibrium constant? Explain
your answer.
1992
Cl2(g) + 3 F2(g) 2 ClF3(g)
ClF3 can be prepared by the reaction represented by the equation above. For ClF3 the standard enthalpy of
formation, Hf,is 163.2 kilojoules/mole and the standard free energy of formation, Gf, is 123.0
kilojoules/mole.
(a) Calculate the value of the equilibrium constant for the reaction at 298K.
(b) Calculate the standard entropy change, S, for the reaction at 298K.
(c) If ClF3 were produced as a liquid rather than as a gas, how would the sign and the magnitude of S
for the reaction be affected? Explain.
(d) At 298K the absolute entropies of Cl2(g) and ClF3(g) are 222.96 joules per mole Kelvin and 281.50
joules per mole Kelvin, respectively.
(i) Account for the larger entropy of ClF3(g) relative to that of Cl2(g).
(ii) Calculate the value of the absolute entropy of F2(g) at 298K.
page 6
1995
Propane, C3H8, is a hydrocarbon that is commonly used as fuel for cooking.
(a) Write a balanced equation for the complete combustion of propane gas, which yields CO2(g) and H2O(l) .
(b) Calculate the volume of air at 30C and 1.00 atmosphere that is needed to burn completely 10.0 grams of
propane. Assume that air is 21.0 percent O2 by volume.
(c) The heat of combustion of propane is -2,220.1 kJ/mol. Calculate the heat of formation, Hf of propane
given that Hf of H2O(l) = 285.3 kJ/mol and Hf of CO2(g) = 393.5 kJ/mol.
(d) Assuming that all of the heat evolved in burning 30.0 grams of propane is transferred to 8.00 kilograms of
water (specific heat = 4.18 J/g.K), calculate the increase in temperature of water.
1998
C6H5OH(s) + 7 O2(g) 6 CO2(g) + 3 H2O(l)
When a 2.000-gram sample of pure phenol, C6H5OH(s), is completely burned according to the equation
above, 64.98 kilojoules of heat is released. Use the information in the table below to answer the questions
that follow.
Substance
Standard Heat of
Formation, Hf,
at 25C (kJ/mol)
Absolute Entropy, S,
at 25C (J/mol-K)
C(graphite)
0.00
5.69
CO2(g)
393.5
213.6
H2(g)
0.00
130.6
H2O(l)
285.85
69.91
O2(g)
0.00
205.0
144.0
C6H5OH(s)
(a) Calculate the molar heat of combustion of phenol in kilojoules per mole at 25C.
(b) Calculate the standard heat of formation, Hf, of phenol in kilojoules per mole at 25C.
(c) Calculate the value of the standard free-energy change, G for the combustion of phenol at 25C.
(d) If the volume of the combustion container is 10.0 liters, calculate the final pressure in the container
when the temperature is changed to 110C. (Assume no oxygen remains unreacted and that all
products are gaseous.)
page 7
2003B
In an experiment, a sample of an unknown, pure gaseous hydrocarbon was analyzed. Results showed that
the sample contained 6.000 g of carbon and 1.344 g of hydrogen.
(a) Determine the empirical formula of the hydrocarbon.
(b) The density of the hydrocarbon at 25C and 1.09 atm is 1.96 g L1.
(i) Calculate the molar mass of the hydrocarbon.
(ii) Determine the molecular formula of the hydrocarbon.
In another experiment, liquid heptane, C7H16 (l), is completely combusted to produce CO2(g) and H2O(l),
as represented by the following equation.
C7H16(l) + 11 O2(g) 7 CO2(g) + 8 H2O(l)
The heat of combustion, Hcomb, for one mole of C7H16(l) is 4.85 103 kJ.
(c)
Using the information in the table below, calculate the value of Hf for C7H16 (l) in kJ mol1.
A 0.0108 mol sample of C7H16 (l) is combusted in a bomb calorimeter.
(d)
(i) Calculate the amount of heat released to the calorimeter.

(ii) Given that the total heat capacity of the calorimeter is 9.273 kJ C
, calculate the temperature
change of the calorimeter.

2004
2 Fe(s) +
O2(g) Fe2O3(s)
Hf = 824 kJ mol1
Iron reacts with oxygen to produce iron(III) oxide, as represented by the equation above. A 75.0 g sample
of Fe(s) is mixed with 11.5 L of O2(g) at 2.66 atm and 298 K.
(a) Calculate the number of moles of each of the following before the reaction begins.
(i) Fe(s)
(ii) O2(g)
(b) Identify the limiting reactant when the mixture is heated to produce Fe2O3(s). Support your answer
with calculations.
page 8
(c) Calculate the number of moles of Fe2O3(s) produced when the reaction proceeds to completion.
(d) The standard free energy of formation, Gf , of Fe2O3(s) is 740. kJ mol at 298 K.
(i) Calculate the standard entropy of formation, Sf , of Fe2O3(s) at 298 K. Include units with
your answer.
(ii) Which is more responsible for the spontaneity of the formation reaction at 298 K, the standard
enthalpy of formation, Hf , or the standard entropy of formation, Sf ? Justify your answer.
The reaction represented below also produces iron(III) oxide. The value of H for the reaction
is 280. kJ per mole of Fe2O3(s) formed.
2 FeO(s) +
O2(g) Fe2O3(s)
Calculate the standard enthalpy of formation, , Hf, of FeO(s).

2006B
Answer the following questions about the thermodynamics of the reactions represented below.
Reaction X:
I2(s) +
Cl2(g) p ICl(g)
Hf = 18 kJ mol1, S298 = 78 J K1 mol1
Reaction Y:
I2(s) +
Br2(l) p IBr(g)
Hf = 41 kJ mol1,
S298 = 124 J K1 mol1
(a) Is reaction X, represented above, spontaneous under standard conditions? Justify your answer with a
calculation.
(b) Calculate the value of the equilibrium constant, Keq, for reaction X at 25C.
(c) What effect will an increase in temperature have on the equilibrium constant for reaction X ?
Explain your answer.
(d) Explain why the standard entropy change is greater for reaction Y than for reaction X.
(e) Above what temperature will the value of the equilibrium constant for reaction Y be greater than 1.0 ?
Justify your answer with calculations.
(f) For the vaporization of solid iodine, I2(s) I2(g), the value of H298 is 62 kJ mol1. Using this
information, calculate the value of H298 for the reaction represented below.
I2(g) + Cl2(g) p 2 ICl(g)
AP* Chemistry
Entropy and Free Energy
WHAT DRIVES A REACTION TO BE THERMODYNAMICALLY FAVORABLE?
ENTHALPY (H) heat exchange (exothermic reactions are generally favored)
ENTROPY (S) dispersal (disorder) of the matter and energy of a system (more
dispersal/disorder is favored) Nature tends toward chaos! Think about your room at the
end of the week. Your mom knows this concept all too well.
Thermodynamically favored processes or reactions are those that involve both a
decrease in the internal energy of the components (H < 0) and an increase in entropy
of the components (S > 0). These processes are necessarily thermodynamically
favored (G < 0) or negative. If you are using an older textbook, you may see these
reactions referred to as spontaneous. Avoid that language as you answer free-response questions!
Thermodynamically favored processes occur without outside intervention once the energy of activation has
been reached. Thermodynamics does not predict nor take into account the rate of the reaction. That is the
realm of kinetics. Some reactions are very fast (like combustion of hydrogen) other reactions are very slow
(like graphite turning to diamond) but both are thermodynamically favored.
The first law of thermodynamics: Energy can never be created nor destroyed. Therefore, the energy of the
universe is constant. This is simply a statement of the law of conservation of energy youve know about for
quite some time.
The second law of thermodynamics: the universe is constantly increasing the dispersal of matter and energy.
Rudolph Clausius discovered it and gave it its symbol.
The third law of thermodynamics: the entropy of a perfect crystal at 0 K is zero.
[Not a lot of perfect crystals out there so, entropy values are RARELY ever zeroeven elements]
So what? This means the absolute entropy of a substance can then be determined at any temp. higher than
zero K. (Handy to know if you ever need to defend why G & H for elements = 0. . . . BUT S does not!)
Domain of thermodynamics
(the final and initial states)
*AP is a registered trademark of the College Board, which was not involved in the production of this product. Special thanks to the contributions
of Lisa McGaw and David Wentz. 2013 by Ren McCormick. All rights reserved.
What is entropy? Its difficult to narrow this concept down to a single definition, but lets try anyway!
Entropy is a thermodynamic function that describes the number of arrangements (positions and/or energy
levels) that are available to a system existing in a given state. Entropy is closely related to probability. The
key concept is that the more ways a particular state can be achieved; the greater is the likelihood (probability)
of finding that state. In Englishnature spontaneously proceeds toward the states that have the highest
probabilities of existing.
Lets use a simple example, an ideal gas expanding into an evacuated
bulb. WHY is this process thermodynamically favorable? Simple, the
driving force is probability. Because there are more ways of having
the gas evenly spread throughout the container than there are ways for
it to be in any other possible state, the gas disperses attaining a
uniform distribution. The consequences are dramatic for large
numbers of molecules, as you can see at right.
Lets simplify! How many possible microstates exist for a sample of
four ideal gas molecules in two bulbs of equal volume?
(Why ideal gas molecules? There are no pesky attractive forces to
influence their motion.)
Predicting the entropy of a system is based on physical evidence:
The greater the dispersal of matter and/or energy in a system, the larger the entropy.
The entropy of a substance always increases as it changes from solid to liquid to gas.
When a pure solid or liquid dissolves in a solvent, the entropy of the substance increases (Carbonates are an
exception! Carbonates interact with water and actually bring MORE order to the system.)
When a gas molecule escapes from a solvent, the entropy increases
Entropy generally increases with increasing molecular complexity (crystal structure: KCl vs. CaCl2) since there are
more MOVING electrons!
Reactions increasing the number of moles of particles often increase entropy.
In general, the greater the number of arrangements, the higher the entropy of the system!
2
Entropy & Free Energy
Exercise 1
Predicting Entropy Changes
Predict the sign of the entropy change for each of the following processes. Justify your answers.
a) Solid sugar is added to water to form a solution.
b) Iodine vapor condenses on a cold surface to form crystals.
a) positive
b) negative
Calculating Entropy from tables of standard values:
(You already know how to solve problems like this, just pay close attention to the UNITS!)
BIG MAMMA, verse 2:
Srxn = S (products) - S (reactants)
S is + when dispersal/disorder increases (favored)

S is when dispersal/disorder decreases
NOTE: Units are usually J/(molrxn K) (not kJ!)
Exercise 2
Calculate the entropy change at 25C, in J/(molrxn K) for:
2 SO2(g) + O2(g) 2 SO3(g)
Given the following data:
SO2(g)
248.1 J/(mol K)
205.3 J/(mol K)
O2(g)
SO3(g)
256.6 J/(mol K)
188.3 J/(molrxn K)
3
ENTROPY CHANGES AS THEY RELATE TO REVERSIBLE PHASE CHANGES

Phase changes occur at constant temperature and represent a system which is also in equilibrium G = 0.
o
S surroundings
H
q
heat transferred
J
=
=
expressed in
T
temperature at which change occurs T
molrxn K
**Where the heat supplied (endothermic) (q > 0) or evolved (exothermic) (q < 0) is divided by the
temperature in Kelvins
** It is important here to note if the reaction is endothermic or exothermic. The actual significance of this is
really dependent on the temperature at which the process occurs. (i.e., If you gave a millionaire $100 it would
not make much difference in his happiness; if you gave a poor college student $100 it would create a totally
different expression of happiness!)
EX:
water ( @ 100 C) water (g @ 100C)
The entropy will increase for the forward reaction (vaporizing) since the reaction produces water in a less
condensed state, thus the molecules are more dispersed.
Exercise 3
Determining Ssurr
In the metallurgy of antimony, the pure metal is recovered via different reactions, depending on the
composition of the ore. For example, iron is used to reduce antimony in sulfide ores:
Sb2S3(s) + 3 Fe(s) 2 Sb(s) + 3 FeS(s)
H = 125 kJ/molrxn
Carbon is used as the reducing agent for oxide ores:

Sb4O6(s) + 6 C(s) 4 Sb(s) + 6 CO(g)
H = 778 kJ/molrxn
Calculate Ssurr for each of these reactions at 25C and 1 atm.
419 J/K molrxn & 2.61 103 J/Kmolrxn

4
ENTROPY SUMMARY:
S = + MORE DISPERSAL (FAVORED CONDITION)
S = LESS DISPSERSAL
Whether a reaction will occur spontaneously may be determined by looking at the S of the universe.
S system + S surroundings = S universe
IF S universe is +, then reaction is thermodynamically favorable
IF S universe is , then reaction is NOT thermodynamically favorable
Consider
2 H2 (g) + O2 (g) H2O (g) ignite & rxn is fast!
Ssystem = 88.9 J/( molrxn K)
Therefore, the entropy declines mainly due to 3 moles of gas 2 moles of gas which is a more condensed or
less dispersed state!
To confirm we need to know entropy of surroundings!
Ssurroundings = q surroundings
T
Hsystem = 483.6 kJ/mol
The First Law of Thermodynamics demands that this energy is transferred from the system to the
surroundings so...
Note that the change (increase or decrease) in the entropy of the surroundings is the result of energy flow
into or from the surroundings as a function of temperature, such that,
H surrounings H system
S surroundings=
=
;
T
T
Hsystem = Hsurroundings
OR
(483.6 kJ) = +483.6 kJ
Now, Ssurroundings = Hsurroundings = + 483.6 kJ/molrxn = 1,620 J/( molrxn K)

T
298 K
Now we can find Suniverse
Ssystem + Ssurroundings = Suniverse
J
J
J
88.9
+ 1620
=
1530
(molrxn K)
(molrxn K)
(molrxn K)
Even though the entropy of the system declines, the entropy change for the surroundings is SO VERY large
that the overall change for the universe is positive.
Bottom line: A process is thermodynamically favorable in spite of a negative entropy change as long as it is
EXTREMELY exothermic. In other words, sufficient exothermicity offsets system ordering.
5
What is FREE ENERGY?

The calculation of Gibbs free energy, G is what ultimately decides whether a reaction is thermodynamically
favored or not. A NEGATIVE sign on G indicates the reaction is thermodynamically favored.
G can be calculated several ways and links thermochemistry, entropy, equilibrium and electrochem together!
1. Big Mamma Equation, verse 3: Grxn = G (products) G (reactants)
You already know how to calculate enthalpy and entropy, just substitute free energy values using
tables of standard values! So, calculating the standard molar free energy of formation is simply the
same song, 3rd verse. BOTH Hf and Gf = 0 for elements in their standard state and both bear
units of kJ/molrxn. You have no idea how handy this is going to be with regard to solving homework
problems and acing quizzes & exams! The Big Mamma equations are simply different versions of
Hesss Law.
But, aw shucks! Youve got to stop and look up S values rather them being zero as well. (Note the
lack of a delta. Thats not a typo! ) Only a perfect diamond at absolute zero has a S value = 0.
2. Granddaddy Equation for calculating Gibbs Free Energy for a system at constant
temperature : G = H - TS
By far, one of the most beneficial equations to learn for the AP exam! Case in point, taking favored
equilibrium conditions where G = 0, into consideration, the equation rearranges rather quickly to
allow you to determine the absolute temperature at which a process becomes thermodynamically
favorable. Shall we? (At least indulge me!)
G = H T S
0 = H T S at equilibrium
H = T S (negative signs cancel)
T S = H
H
T =
S
3. Hesss Law of Summation for a new reaction when given a series of chemical reactions and the
G for each reaction. Hesss Law of Summation works exactly the same as in the enthalpy
calculations; arrange a series of chemical equations for which you know the Grxn to obtain the
goal equation. If you need to reverse an equation, then you change the sign of Grxn and cross off
common moles of substances as you sum the equations to deliver the goal equation. If you double an
equation to obtain the goal, double the value of Grxn, if you halve a reaction halve the value of
Grxn for that reaction, etc.
4. Rat Link equation for calculating G at standard conditions using the given temperature and
equilibrium constant, K: G = RTlnK
Be sure to use the energy R 8.3145 J/molK
(I predict youll use this one the most!) In this case, the system is at equilibrium, so G = 0 and K
represents the equilibrium constant under standard conditions.
6
Kp =
Preactants
still raised to power of coefficients
Pproducts
Knowing that K P = K c ( RT ) , where n is equal to the change in the number of moles of gas for the
reaction.
n
5. Solving for G using the minus nunfe equation given the standard cell potential, Faradays
constant and the number of moles of electrons involved. Sounds far scarier than it is!
G = nFE where n = number of moles of electrons transferred in a balanced redox reaction, F is
Faradays constant 96,485 Coulombs/mole e and E is the standard cell potential for the
electrochemical process. Its also handy to know that 1 volt = 1 joule/coulomb so youre units work
out as they should.
Exercise 4
2 H2O() + O2(g) 2 H2O2()
Calculate the free energy of formation for the oxidation of water to produce hydrogen peroxide given the
following information Gof values:
H2O()
56.7 kcal/molrxn
O2(g)
0 kcal/molrxn
H2O2()
27.2 kcal/molrxn
59.0 kcal/molrxn
Exercise 5
2 SO2(g) + O2(g) 2 SO3(g)
The reaction above was carried out at 25C and 1 atm. Calculate H, S, and G using the following data:
H = 198 kJ/molrxn; S = 187 J/Kmolrxn; G = 142 kJ/molrxn
7
Exercise 6
Cdiamond(s) + O2(g) CO2(g) G= 397 kJ

Cgraphite(s) + O2(g) CO2(g) G= 394 kJ
Calculate G for the reaction

Cdiamond(s)Cgraphite(s)
+3 kJ/molrxn
Exercise 7
The overall reaction for the corrosion (rusting) of iron by oxygen is
4 Fe(s) + 3 O2(g) 2 Fe2O3(s)
Using the following data, calculate the equilibrium constant for this reaction at 25C.
K = 10261
The Gibbs equation can also be used to calculate the phase change temperature of a substance. During the
phase change, the system is in equilibrium, thus the value of G is zero.
8
Exercise 8
Calculate the thermodynamic boiling point of H2O() H2O(g) given the following information:
Hvap = +44 kJ/molrxn
Svap = 118.8 J/(Kmolrxn)
370 K
Exercise 9
For the reaction 2 CO(g) + O2(g) 2 CO2(g), the G for the reaction is 257.2 kJ/molrxn. Calculate the
equilibrium constant at 25C.
1.27 1045
SUMMARY:
If G is NEGATIVE, the reaction is thermodynamically favorable and Ecell would be POSITIVE
If G is ZERO, the reaction is at equilibrium and Ecell would also be ZERO
If G is POSITIVE, the reaction is NOT thermodynamically favorable and Ecell would be NEGATIVE
9
Conditions of G:
H
negative
positive
negative
positive
S
positive
positive
negative
negative
Result
thermodynamically favorable at all temperatures
thermodynamically favorable at high temperatures
thermodynamically favorable at low temperatures
NOT thermodynamically favorable, EVER
Relationship of G to K and E:
G
0
negative
positive
K
at equilibrium; K = 1
>1, products favored
<1, reactants favored
E
0
positive
negative
COMMON MISCONCEPTIONS ABOUT THERMODYNAMIC FAVORIBILITY

IF G > 0 (positive thus NOT thermodynamically), the process cannot occur Not true! External sources of
energy can be used to drive change in these cases.
Consider the following:
1. Electric current is applied to charge a battery. You probably describe the equilibrium condition for a
battery as dead. Its not dead, it just reached equilibrium (and you can recharge it, but never to full
capacity again).
2. Light and photon absorption in the photosystems of a chloroplast causing photoionization during
photosynthesis.
3. Coupling a thermodynamically unfavorable reaction with one that is favorable as in the conversion of
ATP to ADP in biological systems.
IF G is large and negative, the process must proceed at a measurable rate. Not true!
Consider the following:
There are kinetic controls related to high activation energies such as
1. reactant molecules being held together by strong covalent bonds or strong IMFs
2. a required collision orientation
3. a required energy associated with collisions correctly oriented
10
AP* Chemistry
ELECTROCHEMISTRY
Terms to Know:
Electrochemistry the study of the interchange of chemical and electrical energy
Voltaic or Galvanic Cell IS a battery but not a dry cell; generates useful electrical energy
Electrolytic Cell requires useful electrical energy to drive a thermodynamically unfavorable reaction
OIL RIG oxidation is loss, reduction is gain (of electrons)
Oxidation the loss of electrons, increase in charge
Reduction the gain of electrons, reduction of charge
Oxidation number the assigned charge on an atom
Electrochemistry Involves TWO MAIN TYPES Of Electrochemical Cells:

1. Galvanic (voltaic) cells which are thermodynamically favorable chemical reactions (battery)
2. Electrolytic cells which are thermodynamically unfavorable and require external e source
(a direct current or DC power source)
BOTH of these fit into the category entitled Electrochemical cells
*AP is a registered trademark of the College Board, which was not involved in the production of this product. 2013 by Ren McCormick.
All rights reserved.
GALVANIC or VOLTAIC CELL ANATOMY
Anode the electrode where oxidation occurs. After a period of time, the anode may appear to become
smaller as it falls into solution. (Zn in our illustration below)
Cathode the electrode where reduction occurs. After a period of time it may appear larger, due to ions
from solution plating onto it. (Cu in our illustration below)
Inert electrodes used when a gas is involved OR ion to ion involved such as Fe3+ being reduced to Fe2+
rather than Fe0; made of Pt (expensive) or graphite (cheap)
Salt bridge used to maintain electrical neutrality in a galvanic cell; may be filled with agar which contains
a neutral salt
Electron flow ALWAYS through the wire from anode to cathode (alphabetical order)
Voltmeter measures the cell potential (emf) in volts.
Examine the diagram above. Take note of the following mnemonic devices (easy ways to remember stuff):
All of the following refer to the construction of a thermodynamically favorable cell one that can act as a
battery:
AN OX oxidation occurs at the anode (may show mass decrease)
RED CAT reduction occurs at the cathode (may show mass increase)
FAT CAT The electrons in a voltaic or galvanic cell ALWAYS flow
From the Anode To the CAThode

Ca+hode the cathode is + in galvanic (voltaic) cells, so it stands to reason the anode is negative
Salt Bridge bridge between cells whose purpose is to provide ions to balance the charge.
Usually made of a salt filled agar (KNO3) or a porous disk may be present instead.
EPA in an electrolytic cell, there is a positive anode.
.
Electrochemistry
Galvanic cells involve oxidation-reduction or redox reactions. Balance this redox reaction:
MnO4 + Fe2+ Mn2+ + Fe3+
[acidic]
RED:
OX:
Overall rxn:
If we place MnO4 and Fe2+ in the same container, the electrons are transferred directly when the reactants
collide. No useful work is obtained from the chemical energy involved which is instead, released as heat!
We can harness this energy if we separate the oxidizing agent from the reducing agent, thus requiring the e
transfer to occur through a wire! We can harness the energy that way to run a motor, light a bulb, etc.
Sustained electron flow cannot occur in the picture above.
Why not? As soon as electrons flow, a separation of charge occurs which in turn stops the flow of electrons.
How do we fix it? Add a salt bridge or allow flow through a porous disk.
Salt Bridge its job is to balance the

charge using an electrolyte [usually in a Ushaped tube filled with agar that has the salt
dissolved into it before it gels]. It connects
the two compartments, ions flow from it,
AND it keeps each cell neutral.
Use KNO3 as the salt when constructing
your own diagram so that no precipitation
occurs!
porous disk or cup also allows both cells

to remain neutral by allowing ions to flow
cell potential Ecell, Emf, or cellit is a measure of the electromotive force or the pull of the electrons as
they travel from the anode to the cathode [more on that later!]
volt (V) the unit of electrical potential; equal to 1 joule of work per coulomb of charge transferred
voltmeter measures electrical potential; some energy is lost as heat [resistance] which keeps the
voltmeter reading a tad lower than the actual or calculated voltage. Digital voltmeters have less
resistance. If you want to get picky and eliminate the error introduced by resistance, you attach a
variable-external power source called a potentiometer. Adjust it so that zero current flowsthe
accurate voltage is then equal in magnitude but opposite in sign to the reading on the potentiometer.
Heres a nice animation from YouTube: http://www.youtube.com/watch?v=raOj8QGDkPA
.
Electrochemistry
ORIGIN OF STANDARD REDUCTION POTENTIALS
Each half-reaction has a cell potential

Each potential is measured against a standard, which is the
standard hydrogen electrode [consists of a piece of inert
Platinum that is bathed by hydrogen gas at
1 atm].
The hydrogen electrode is assigned a value of 0.00 V
much like the isotope C-12 is assigned an atomic mass of
exactly 12.000 amu and all other atomic masses are measured relative to it.
standard conditions 1 atm for gases, 1.0M for solutions and 25C for all (298 K)
naught, we use the naught to indicate standard conditions [Experiencing a thermo flashback?]
That means Ecell, Emf, or cell become Ecello , Emfo , or cello when
measurements are taken at standard conditions. Youll soon learn
how these change when the conditions are non-standard!
The diagram to the right illustrates what really happens when a

Galvanic cell is constructed from zinc sulfate and copper(II)
sulfate using the respective metals as electrodes.
Notice that 1.0 M solutions of each salt are used

Notice an overall voltage of 1.10 V for the process
So, how do we construct a fully functional Galvanic or Voltaic cell?

First, we must make wise choices depending on materials available and cost. Knowing how to choose wisely is
our next lesson! We need to interpret the data given on the table of standard reduction potentials as we engineer
our Galvanic or Voltaic cell.
Interpreting a Table of Standard Electrode Potentials

Elements that have the most positive reduction potentials are easily reduced (in general, non-metals)
Elements that have the least positive reduction potentials are easily oxidized (in general, metals)
The reduction potential table can also be used as an activity series. Metals having less positive reduction
potentials are more active and will replace metals with more positive potentials.
.
Electrochemistry
Let the engineering begin! The MORE POSITIVE reduction potential gets to indeed be reduced IF
you are trying to set up a cell that can act as a galvanic or voltaic cell (a battery in other words).
There once was a table of reduction potentials in the reference tables of the AP Chemistry exam.
Currently, we expect the data will be given in either a small table or simply embedded within the text
of the question. For your homework, youll need to consult a table similar to this one.
Calculating Standard Cell Potential Symbolized by Ecell OR Emf OR cell [Ill mix and match!]
1. Decide which element is oxidized or reduced using the table of reduction potentials. Once again,
THE Metal with the MORE POSITIVE REDUCTION POTENITAL gets to be REDUCED.
So, it stands to reason that the other metal is oxidized!
2. Write both equations AS IS from the chart with their associated voltages.
3. Reverse the equation that will be oxidized and change the sign of its voltage [this is now Eoxidation]
4. Balance the two half reactions **do not multiply voltage values** Why not?
J
A volt is equivalent to a J/coulomb or which is a ratio.
c
5. Add the two half reactions and the voltages together.
6. Ecell = Eoxidation + Ereduction
.
Electrochemistry
means standard conditions: 1atm, 1M, 25C

5
ANIONS from the salt move

to the anode while
CATIONS from the salt
move to the cathode!
Exercise 1
a. Consider a galvanic cell based on the reaction
Al3+(aq) + Mg(s) Al(s) + Mg2+(aq)
Give the balanced cell reaction and calculate E for the cell.
b. A galvanic cell is based on the reaction [youll need a more complete table of reduction potentials!]
MnO4(aq) + H+(aq) + ClO3(aq) ClO4(aq) + Mn2+(aq) + H2O(l)
Give the balanced cell reaction and calculate E for the cell.
A: 0.71 V
B: 0.32 V
.
Electrochemistry
Exercise 2
Calculate the cell voltage for the galvanic cell that would utilize silver metal and involve iron(II) ion and
iron(III) ion. Draw a diagram of the galvanic cell for the reaction and label completely.
Ecell= 0.03 V
CELL POTENTIAL, ELECTRICAL WORK & FREE ENERGY
It is time to combine the thermodynamics and the electrochemistry, not to mention a wee bit of physics.
The work that can be accomplished when electrons are transferred through a wire depends on the push or
emf which is defined in terms of a potential difference [in volts] between two points in the circuit.
emf (V ) = =
work (J)
charge(C)
Thus one joule of work is produced [or required] when one coulomb of charge is transferred between two
points in the circuit that differ by a potential of one volt
IF work flows OUT of the system, it is assigned a MINUS sign (makes sense since Joules were LOST)
When a cell produces a current, the cell potential is positive and the current can be used to do work
THEREFORE and work have opposite signs!
work (J)
w
=
w = q
charge(C)
q
faraday(F)the charge on one MOLE of electrons = 96,485 coulombs (Think 96,500 when
answering multiple choice questions )
q = # moles of electrons F
For a process carried out at constant temperature and pressure, wmax [neglecting the very small amount
of energy that is lost as friction or heat] is equal to G, therefore.
Go = nFEo
.
Electrochemistry
G = Gibbs free energy

n = number of moles of electrons
F = Faraday constant 96,485
J
V mol
So, it follows that:
Eo implies thermodynamically unfavorable.

+Eo implies thermodynamically favorable (would be a good battery!)
Exercise 3
Using the table of standard reduction potentials, calculate G for the reaction
Cu2+(aq) + Fe(s) Cu(s) + Fe2+(aq)
Explain whether or not this reaction is thermodynamically favorable.
Exercise 4
Using the table of standard reduction potentials, predict whether 1 M HNO3 will dissolve gold metal to form a
1 M Au3+ solution.
= no
.
Electrochemistry
DEPENDENCE OF CELL POTENTIAL ON CONCENTRATION

Voltaic cells at NONstandard conditions: LeChatliers principle can be applied. An increase in the
concentration of a reactant will favor the forward reaction and the cell potential will increase.
The converse is also true!
Exercise 5
For the cell reaction
2Al(s) + 3Mn2+(aq) 2Al3+(aq) + 3Mn(s)
Ecell =
predict whether Ecell is larger or smaller than Ecell for the following cases and justify your answer.
a. [Al3+ ] = 2.0 M, [Mn2+ ] = 1.0 M
b. [Al3+ ] = 1.0 M, [Mn2+] = 3.0 M
a. smaller
b. larger
NMSI Disclaimer: The curriculum framework for the course excludes the quantitative treatment of the Nernst Equation, but we feel it is in the
best interest of the student to learn this concept for two reasons:
1)
It makes students more college ready, especially the students that will earn a qualifying score and obtain full credit for the university
course.
2)
At least half of the students in any given AP Chemistry course are mathematically inclined and may actually understand a concept better
through the application of the mathematics of Q and how it relates back to LeChteliers Principle.
For a more quantitative approach at nonstandard conditions use the Nernst Equation:
E = E
RT
ln Q
nF
R = Gas constant 8.315 J/K mol

F = Faraday constant
coefficient
Q = reaction quotient =
[ products]
coefficient
[ reactants ]
E = Energy produced by reaction

T = Temperature in Kelvins
n = # of electrons exchanged in BALANCED redox equation
Rearranged, another useful form
NERNST EQUATION:
.
Electrochemistry
E = E
0.0592
log Q @ 25C (298K)
n
As E declines with reactants being converted into products, E eventually reaches zero.
Zero potential means reaction is at equilibrium [dead battery]. Also note, Q = K AND G = 0 as well.
CONCENTRATION CELLS
We can construct a cell where both compartments contain the same components
BUT at different concentrations
Notice the difference in the concentrations pictured at left. Because the right
compartment contains 1.0 M Ag+ and the left compartment contains 0.10 M Ag+,
there will be a driving force to transfer electrons from left to right. Silver will be
deposited on the right electrode, thus lowering the concentration of Ag+ in the
right compartment. In the left compartment the silver electrode dissolves
[producing Ag+ ions] to raise the concentration of Ag+ in solution.
Exercise 6
Determine the direction of electron flow and designate the anode and cathode for the cell represented here.
left
right
Exercise 7
Determine Eocell and Ecell based on the following half-reactions:
VO2+ + 2H+ + e VO2+ + H2O
Zn2+ + 2e Zn
E= 1.00 V
E = 0.76V
Where,
T = 25C
[VO2+] = 2.0 M
[H+] = 0.50 M
[VO2+] = 1.0 102 M
[Zn2+] = 1.0 101 M
Eocell = 1.76 V
Ecell = 1.89 V
.
Electrochemistry
10
AP* Electrochemistry Free Response Questions
page 1
Galvanic (Voltaic) Cells

1988
An electrochemical cell consists of a tin electrode in an acidic solution of 1.00 molar Sn2+ connected by a salt
bridge to a second compartment with a silver electrode in an acidic solution of 1.00 molar Ag+.
(a) Write the equation for the half-cell reaction occurring at each electrode. Indicate which half-reaction
occurs at the anode.
(b) Write the balanced chemical equation for the overall spontaneous cell reaction that occurs when the
circuit is complete. Calculate the standard voltage, E, for this cell reaction.
(c) Calculate the equilibrium constant for this cell reaction at 298 K.
(d) A cell similar to the one described above is constructed with solutions that have initial concentrations of
1.00 molar Sn2+ and 0.0200 molar Ag+. Calculate the initial voltage, E, of this cell.
1993
A galvanic cell is constructed using a chromium electrode in a 1.00-molar solution of Cr(NO3)3 and a copper
electrode in a 1.00-molar solution of Cu(NO3)2. Both solutions are at 25C.
(a) Write a balanced net ionic equation for the spontaneous reaction that occurs as the cell operates. Identify
the oxidizing agent and the reducing agent.
(b) A partial diagram of the cell is shown below.
1. Which metal is the cathode?

2. What additional component is necessary to make the cell operate?
3. What function does the component in (ii) serve?
(c) How does the potential of this cell change if the concentration of Cr(NO3)3 is changed to 3.00-molar
at 25C? Explain.
page 2
1996
Sr(s) + Mg2+ Sr2+ + Mg(s)
Consider the reaction represented above that occurs at 25C. All reactants and products are in their standard
states. The value of the equilibrium constant, Keq, for the reaction is 4.2 1017 at 25C.
(a)
Predict the sign of the standard cell potential, E, for a cell based on the reaction. Explain your prediction.
(b)
(c)
Identify the oxidizing agent for the spontaneous reaction.

If the reaction were carried out at 60C instead of 25C, how would the cell potential change? Justify
your answer.
How would the cell potential change if the reaction were carried out at 25C with a 1.0-molar solution of
Mg(NO3)2 and a 0.10-molar solution of Sr(NO3)2? Explain.
When the cell reaction in (d) reaches equilibrium, what is the cell potential?
(d)
(e)
1998
Answer the following questions regarding the electrochemical cell shown above.
(a) Write the balanced net-ionic equation for the spontaneous reaction that occurs as the cell operates,
and determine the cell voltage.
(b) In which direction do anions flow in the salt bridge as the cell operates? Justify your answer.
(c) If 10.0 mL of 3.0-molar AgNO3 solution is added to the half-cell on the right, what will happen to
the cell voltage? Explain.
(d) If 1.0 grams of solid NaCl is added to each half-cell, what will happen to the cell voltage? Explain.
(e) If 20.0 mL of distilled water is added to both half-cells, the cell voltage decreases. Explain.
page 3
2001
Answer the following questions that refer to the galvanic cell shown in the diagram above.
(a) Identify the anode of the cell and write the half-reaction that occurs there.
(b) Write the net ionic equation for the overall reaction that occurs as the cell operates and calculate the
value of the standard cell potential, Ecell.
(c) Indicate how the value of Ecell would be affected if the concentration of Ni(NO3)2(aq) was changed
from 1.0 M to 0.10 M and the concentration of Zn(NO3)2(aq) remained at 1.0 M. Justify your
answer.
(d) Specify whether the value of Keq for the cell reaction is less than 1, greater than 1, or equal to 1.
Justify your answer.
page 4
2002B
The diagram below shows the experimental setup for a typical electrochemical cell that contains two
standard half-cells. The cell operates according to the reaction represented by the following equation.
Zn(s) + Ni2+(aq) Ni(s) + Zn2+(aq)
(a) Identify M and M2+ in the diagram and specify the initial concentration for M2+ in solution.
(b) Indicate which of the metal electrodes is the cathode. Write the balanced equation for the reaction
that occurs in the half-cell containing the cathode.
(c) What would be the effect on the cell voltage if the concentration of Zn2+ was reduced to 0.100 M
in the half-cell containing the Zn electrode?
(d) Describe what would happen to the cell voltage if the salt bridge was removed. Explain.
page 5
2003B
Answer the following questions about electrochemistry.
(a) Several different electrochemical cells can be constructed using the materials shown below. Write
the balanced net-ionic equation for the reaction that occurs in the cell that would have the greatest
positive value of Ecell.
(b) Calculate the standard cell potential, Ecell, for the reaction written in part (a).
(c) A cell is constructed based on the reaction in part (a) above. Label the metal used for the anode on
the cell shown in the figure below.
page 6
2004B
The following questions refer to the electrochemical cell shown in the diagram above.
(a) Write a balanced net ionic equation for the spontaneous reaction that takes place in the cell.
(b) Calculate the standard cell potential, E, for the reaction in part (a).
(c) In the diagram above,
(i) label the anode and the cathode on the dotted lines provided, and
(ii) indicate, in the boxes below the half-cells, the concentration of AgNO3 and the concentration of
Zn(NO3)2 that are needed to generate E.
(d) How will the cell potential be affected if KI is added to the silver half-cell? Justify your answer.
page 7
2005
AgNO3(s) Ag+(aq) + NO3(aq)
The dissolving of AgNO3(s) in pure water is represented by the equation above.
(a) Is G for the dissolving of AgNO3(s) positive, negative, or zero? Justify your answer.
(b) Is S for the dissolving of AgNO3(s) positive, negative, or zero? Justify your answer.
(c) The solubility of AgNO3(s) increases with increasing temperature.
(i) What is the sign of H for the dissolving process? Justify your answer.
(ii) Is the answer you gave in part (a) consistent with your answers to parts (b) and (c) (i) ? Explain.
The compound NaI dissolves in pure water according to the equation NaI(s) Na+(aq) + I(aq) . Some of the
information in the table of standard reduction potentials given below may be useful in answering the questions that follow.
(d) An electric current is applied to a 1.0 M NaI solution.

(i)
Write the balanced oxidation half-reaction for the reaction that takes place.
(ii)
Write the balanced reduction half-reaction for the reaction that takes place.
(iii)
Which reaction takes place at the anode, the oxidation reaction or the reduction reaction?
(iv)
All electrolysis reactions have the same sign for G. Is the sign positive or negative? Justify your
answer.
page 8
Electrolytic Cells
1991
Explain each of the following.
(a) When an aqueous solution of NaCl is electrolyzed, Cl2(g) is produced at the anode, but no Na(s) is
produced at the cathode.
(b) The mass of Fe(s) produced when 1 faraday is used to reduce a solution of FeSO4 is 1.5 times the mass
of Fe(s) produced when 1 faraday is used to reduce a solution of FeCl3.
Zn + Pb2+ (1.0 M) Zn2+ (1.0 M) + Pb
(c) The cell that utilized the reaction above has a higher potential when [Zn2+] is decreased and [Pb2+] held
constant, but a lower potential when [Pb2+] is decreased and [Zn2+] is held constant.
(d) The cell that utilizes the reaction given in (c) has the same cell potential as another cell in which [Zn2+]
and [Pb2+] are each 0.10 M.
1992
An unknown metal M forms a soluble compound, M(NO3)2.
(a) A solution of M(NO3)2 is electrolyzed. When a constant current of 2.50 amperes is applied for
35.0 minutes, 3.06 grams of the metal M is deposited. Calculate the molar mass of M and identify the
metal.
(b) The metal identified in (a) is used with zinc to construct a galvanic cell, as shown below. Write the net
ionic equation for the cell reaction and calculate the cell potential, E.
(c) Calculate the value of the standard free energy change, G, at 25C for the reaction in (b).
(d) Calculate the potential, E, for the cell shown in (b) if the initial concentration of ZnSO4 is 0.10-molar,
but the concentration of the M(NO3)2 solution remains unchanged.
page 9
1997
In an electrolytic cell, a current of 0.250 ampere is passed through a solution of a chloride of iron, producing
Fe(s) and Cl2(g).
(a) Write the equation for the reaction that occurs at the anode.
(b) When the cell operates for 2.00 hours, 0.521 gram of iron is deposited at one electrode.
Determine the formula of the chloride of iron in the original solution.
(c) Write the balanced equation for the overall reaction that occurs in the cell.
(d) How many liters of Cl2(g), measured at 25 C and 750 mmHg, are produced when the cell
operates as described in part (b)?
(e) Calculate the current that would produce chlorine gas at a rate of 3.00 grams per hour.
2000
Answer the following questions that relate to electrochemical reactions.
(a) Under standard conditions at 25C, Zn(s) reacts with Co2+(aq) to produce Co(s).
(i) Write the balanced equation for the oxidation half reaction.
(ii) Write the balanced net-ionic equation for the overall reaction.
(iii)Calculate the standard potential, E, for the overall reaction at 25C.
(b) At 25C, H2O2 decomposes according to the following equation.
2 H2O2(aq) 2 H2O(l) + O2(g)
E = 0.55 V
(i) Determine the value of the standard free energy change, G, for the reaction at 25C.
(ii) Determine the value of the equilibrium constant, Keq , for the reaction at 25C.
(iii) The standard reduction potential, E, for the half reaction O2 (g) + 4 H+(aq) + 4 e 2 H2O (l) has a
value of 1.23 V. Using this information in addition to the information given above, determine the value
of the standard reduction potential, E, for the half reaction below.
O2 (g) + 2 H+(aq) + 2 e H2O2(aq)
(c) In an electrolytic cell, Cu(s) is produced by the electrolysis of CuSO4(aq). Calculate the maximum mass
of Cu(s) that can be deposited by a direct current of 100. amperes passed through 5.00 L of
2.00 M CuSO4(aq) for a period of 1.00 hour.
page 10
2007B
2 H2(g) + O2(g) 2 H2O(l)
In a hydrogen-oxygen fuel cell, energy is produced by the overall reaction represented above.
(a) When the fuel cell operates at 25C and 1.00 atm for 78.0 minutes, 0.0746 mol of O2(g) is consumed.
Calculate the volume of H2(g) consumed during the same time period. Express your answer in liters measured
at 25C and 1.00 atm.
(b) Given that the fuel cell reaction takes place in an acidic medium,
(i) write the two half reactions that occur as the cell operates,
(ii) identify the half reaction that takes place at the cathode, and
(iii) determine the value of the standard potential, E, of the cell.
(c) Calculate the charge, in coulombs, that passes through the cell during the 78.0 minutes of operation as
described in part (a).
STANDARD REDUCTION POTENTIALS IN AQUEOUS SOLUTION AT 25C

Half-reaction
-
E (V)
2F
Co
2+
Au(s)
2 Cl -
2 H2 O(l )
2 Br -
2 Hg2+ + 2e -
Hg2 2+
Hg2+ + 2 e -
Hg(l )
Ag(s)
2 Hg(l )
Fe 2+
I 2 (s ) + 2 e -
2 I-
Cu+ + e -
Cu(s)
Cu(s)
Cu+
Sn 4+ + 2e -
Sn 2+
S(s) + 2 H+ + 2 e -
F2 ( g ) + 2 e
Co
3+
Au
+e
3+
+ 3e
Cl2 (g) + 2 e
O2 (g) + 4H+ + 4 e Br2 (l ) + 2 e
Ag + e
Hg2
Fe
2+
3+
+ 2e
+e
Cu
2+
Cu
2+
+ 2e
+e
H 2S(g)
H2 (g)
Pb
2+
+ 2e
Pb(s)
Sn
2+
+ 2e
Sn(s)
Ni(s)
+ 2e
Co(s)
+ 2e
Cd(s)
Cr 2+
Fe 2+ + 2 e -
Fe(s)
Cr(s)
Zn(s)
H 2 ( g ) + 2 OH -
Mn(s)
Al(s)
Be(s)
Mg(s)
2 H + 2e
Ni
2+
+ 2e
Co
2+
Cd
2+
Cr
Cr
3+
+e
3+
Zn
+ 3e
2+
+ 2e
2 H2 O(l ) + 2 e
Mn2+ + 2e Al
3+
Be
+ 3e
2+
Mg
+ 2e
2+
+ 2e
Na(s)
2+
+ 2e
Ca(s)
2+
Sr(s)
Ba(s)
Rb(s)
Na + e
Ca
Sr
Ba
+ 2e
2+
+ 2e
Rb + e
+
K(s)
Cs(s)
Li(s)
K +e
Cs + e
Li + e
2.87
1.82
1.50
1.36
1.23
1.07
0.92
0.85
0.80
0.79
0.77
0.53
0.52
0.34
0.15
0.15
0.14
0.00
0.13
0.14
0.25
0.28
0.40
0.41
0.44
0.74
0.76
0.83
1.18
1.66
1.70
2.37
2.71
2.87
2.89
2.90
2.92
2.92
2.92
3.05
page 1
Galvanic (Voltaic) Cells

1988
An electrochemical cell consists of a tin electrode in an acidic solution of 1.00 molar Sn2+ connected by a salt
bridge to a second compartment with a silver electrode in an acidic solution of 1.00 molar Ag+.
(a) Write the equation for the half-cell reaction occurring at each electrode. Indicate which half-reaction
occurs at the anode.
(b) Write the balanced chemical equation for the overall spontaneous cell reaction that occurs when the
circuit is complete. Calculate the standard voltage, E, for this cell reaction.
(c) Calculate the equilibrium constant for this cell reaction at 298 K.
(d) A cell similar to the one described above is constructed with solutions that have initial concentrations of
1.00 molar Sn2+ and 0.0200 molar Ag+. Calculate the initial voltage, E, of this cell.
1993
A galvanic cell is constructed using a chromium electrode in a 1.00-molar solution of Cr(NO3)3 and a copper
electrode in a 1.00-molar solution of Cu(NO3)2. Both solutions are at 25C.
(a) Write a balanced net ionic equation for the spontaneous reaction that occurs as the cell operates. Identify
the oxidizing agent and the reducing agent.
(b) A partial diagram of the cell is shown below.
1. Which metal is the cathode?

2. What additional component is necessary to make the cell operate?
3. What function does the component in (ii) serve?
(c) How does the potential of this cell change if the concentration of Cr(NO3)3 is changed to 3.00-molar
at 25C? Explain.
page 2
1996
Sr(s) + Mg2+ Sr2+ + Mg(s)
Consider the reaction represented above that occurs at 25C. All reactants and products are in their standard
states. The value of the equilibrium constant, Keq, for the reaction is 4.2 1017 at 25C.
(a)
Predict the sign of the standard cell potential, E, for a cell based on the reaction. Explain your prediction.
(b)
(c)
Identify the oxidizing agent for the spontaneous reaction.

If the reaction were carried out at 60C instead of 25C, how would the cell potential change? Justify
your answer.
How would the cell potential change if the reaction were carried out at 25C with a 1.0-molar solution of
Mg(NO3)2 and a 0.10-molar solution of Sr(NO3)2? Explain.
When the cell reaction in (d) reaches equilibrium, what is the cell potential?
(d)
(e)
1998
Answer the following questions regarding the electrochemical cell shown above.
(a) Write the balanced net-ionic equation for the spontaneous reaction that occurs as the cell operates,
and determine the cell voltage.
(b) In which direction do anions flow in the salt bridge as the cell operates? Justify your answer.
(c) If 10.0 mL of 3.0-molar AgNO3 solution is added to the half-cell on the right, what will happen to
the cell voltage? Explain.
(d) If 1.0 grams of solid NaCl is added to each half-cell, what will happen to the cell voltage? Explain.
(e) If 20.0 mL of distilled water is added to both half-cells, the cell voltage decreases. Explain.
page 3
2001
Answer the following questions that refer to the galvanic cell shown in the diagram above.
(a) Identify the anode of the cell and write the half-reaction that occurs there.
(b) Write the net ionic equation for the overall reaction that occurs as the cell operates and calculate the
value of the standard cell potential, Ecell.
(c) Indicate how the value of Ecell would be affected if the concentration of Ni(NO3)2(aq) was changed
from 1.0 M to 0.10 M and the concentration of Zn(NO3)2(aq) remained at 1.0 M. Justify your
answer.
(d) Specify whether the value of Keq for the cell reaction is less than 1, greater than 1, or equal to 1.
Justify your answer.
page 4
2002B
The diagram below shows the experimental setup for a typical electrochemical cell that contains two
standard half-cells. The cell operates according to the reaction represented by the following equation.
Zn(s) + Ni2+(aq) Ni(s) + Zn2+(aq)
(a) Identify M and M2+ in the diagram and specify the initial concentration for M2+ in solution.
(b) Indicate which of the metal electrodes is the cathode. Write the balanced equation for the reaction
that occurs in the half-cell containing the cathode.
(c) What would be the effect on the cell voltage if the concentration of Zn2+ was reduced to 0.100 M
in the half-cell containing the Zn electrode?
(d) Describe what would happen to the cell voltage if the salt bridge was removed. Explain.
page 5
2003B
Answer the following questions about electrochemistry.
(a) Several different electrochemical cells can be constructed using the materials shown below. Write
the balanced net-ionic equation for the reaction that occurs in the cell that would have the greatest
positive value of Ecell.
(b) Calculate the standard cell potential, Ecell, for the reaction written in part (a).
(c) A cell is constructed based on the reaction in part (a) above. Label the metal used for the anode on
the cell shown in the figure below.
page 6
2004B
The following questions refer to the electrochemical cell shown in the diagram above.
(a) Write a balanced net ionic equation for the spontaneous reaction that takes place in the cell.
(b) Calculate the standard cell potential, E, for the reaction in part (a).
(c) In the diagram above,
(i) label the anode and the cathode on the dotted lines provided, and
(ii) indicate, in the boxes below the half-cells, the concentration of AgNO3 and the concentration of
Zn(NO3)2 that are needed to generate E.
(d) How will the cell potential be affected if KI is added to the silver half-cell? Justify your answer.
page 7
2005
AgNO3(s) Ag+(aq) + NO3(aq)
The dissolving of AgNO3(s) in pure water is represented by the equation above.
(a) Is G for the dissolving of AgNO3(s) positive, negative, or zero? Justify your answer.
(b) Is S for the dissolving of AgNO3(s) positive, negative, or zero? Justify your answer.
(c) The solubility of AgNO3(s) increases with increasing temperature.
(i) What is the sign of H for the dissolving process? Justify your answer.
(ii) Is the answer you gave in part (a) consistent with your answers to parts (b) and (c) (i) ? Explain.
The compound NaI dissolves in pure water according to the equation NaI(s) Na+(aq) + I(aq) . Some of the
information in the table of standard reduction potentials given below may be useful in answering the questions that follow.
(d) An electric current is applied to a 1.0 M NaI solution.

(i)
Write the balanced oxidation half-reaction for the reaction that takes place.
(ii)
Write the balanced reduction half-reaction for the reaction that takes place.
(iii)
Which reaction takes place at the anode, the oxidation reaction or the reduction reaction?
(iv)
All electrolysis reactions have the same sign for G. Is the sign positive or negative? Justify your
answer.
page 8
Electrolytic Cells
1991
Explain each of the following.
(a) When an aqueous solution of NaCl is electrolyzed, Cl2(g) is produced at the anode, but no Na(s) is
produced at the cathode.
(b) The mass of Fe(s) produced when 1 faraday is used to reduce a solution of FeSO4 is 1.5 times the mass
of Fe(s) produced when 1 faraday is used to reduce a solution of FeCl3.
Zn + Pb2+ (1.0 M) Zn2+ (1.0 M) + Pb
(c) The cell that utilized the reaction above has a higher potential when [Zn2+] is decreased and [Pb2+] held
constant, but a lower potential when [Pb2+] is decreased and [Zn2+] is held constant.
(d) The cell that utilizes the reaction given in (c) has the same cell potential as another cell in which [Zn2+]
and [Pb2+] are each 0.10 M.
1992
An unknown metal M forms a soluble compound, M(NO3)2.
(a) A solution of M(NO3)2 is electrolyzed. When a constant current of 2.50 amperes is applied for
35.0 minutes, 3.06 grams of the metal M is deposited. Calculate the molar mass of M and identify the
metal.
(b) The metal identified in (a) is used with zinc to construct a galvanic cell, as shown below. Write the net
ionic equation for the cell reaction and calculate the cell potential, E.
(c) Calculate the value of the standard free energy change, G, at 25C for the reaction in (b).
(d) Calculate the potential, E, for the cell shown in (b) if the initial concentration of ZnSO4 is 0.10-molar,
but the concentration of the M(NO3)2 solution remains unchanged.
page 9
1997
In an electrolytic cell, a current of 0.250 ampere is passed through a solution of a chloride of iron, producing
Fe(s) and Cl2(g).
(a) Write the equation for the reaction that occurs at the anode.
(b) When the cell operates for 2.00 hours, 0.521 gram of iron is deposited at one electrode.
Determine the formula of the chloride of iron in the original solution.
(c) Write the balanced equation for the overall reaction that occurs in the cell.
(d) How many liters of Cl2(g), measured at 25 C and 750 mmHg, are produced when the cell
operates as described in part (b)?
(e) Calculate the current that would produce chlorine gas at a rate of 3.00 grams per hour.
2000
Answer the following questions that relate to electrochemical reactions.
(a) Under standard conditions at 25C, Zn(s) reacts with Co2+(aq) to produce Co(s).
(i) Write the balanced equation for the oxidation half reaction.
(ii) Write the balanced net-ionic equation for the overall reaction.
(iii)Calculate the standard potential, E, for the overall reaction at 25C.
(b) At 25C, H2O2 decomposes according to the following equation.
2 H2O2(aq) 2 H2O(l) + O2(g)
E = 0.55 V
(i) Determine the value of the standard free energy change, G, for the reaction at 25C.
(ii) Determine the value of the equilibrium constant, Keq , for the reaction at 25C.
(iii) The standard reduction potential, E, for the half reaction O2 (g) + 4 H+(aq) + 4 e 2 H2O (l) has a
value of 1.23 V. Using this information in addition to the information given above, determine the value
of the standard reduction potential, E, for the half reaction below.
O2 (g) + 2 H+(aq) + 2 e H2O2(aq)
(c) In an electrolytic cell, Cu(s) is produced by the electrolysis of CuSO4(aq). Calculate the maximum mass
of Cu(s) that can be deposited by a direct current of 100. amperes passed through 5.00 L of
2.00 M CuSO4(aq) for a period of 1.00 hour.
page 10
2007B
2 H2(g) + O2(g) 2 H2O(l)
In a hydrogen-oxygen fuel cell, energy is produced by the overall reaction represented above.
(a) When the fuel cell operates at 25C and 1.00 atm for 78.0 minutes, 0.0746 mol of O2(g) is consumed.
Calculate the volume of H2(g) consumed during the same time period. Express your answer in liters measured
at 25C and 1.00 atm.
(b) Given that the fuel cell reaction takes place in an acidic medium,
(i) write the two half reactions that occur as the cell operates,
(ii) identify the half reaction that takes place at the cathode, and
(iii) determine the value of the standard potential, E, of the cell.
(c) Calculate the charge, in coulombs, that passes through the cell during the 78.0 minutes of operation as
described in part (a).
AP* Stoichiometry Free Response Questions
page 1
1982
Water is added to 4.267 grams of UF6. The only products are 3.730 grams of a solid containing only
uranium, oxygen and fluorine and 0.970 gram of a gas. The gas is 95.0% fluorine, and the remainder is
hydrogen.
(a) From these data, determine the empirical formula of the gas.
(b) What fraction of the fluorine of the original compound is in the solid and what fraction in the gas after
the reaction?
(c) What is the formula of the solid product?
(d) Write a balanced equation for the reaction between UF6 and H2O. Assume that the empirical formula
of the gas is the true formula.
1986
Three volatile compounds X, Y, and Z each contain element Q. The percent by weight of element Q in each
compound was determined. Some of the data obtained are given below.
Compound
Percent by weight
of Element Q
Molecular
Weight
X
Y
Z
64.8%
73.0%
59.3%
?
104.
64.0
(a) The vapor density of compound X at 27C and 750. mm Hg was determined to be 3.53 grams per liter.
Calculate the molecular weight of compound X.
(b) Determine the mass of element Q contained in 1.00 mole of each of the three compounds.
(c) Calculate the most probable value of the atomic weight of element Q.
(d) Compound Z contains carbon, hydrogen, and element Q. When 1.00 gram of compound Z is
oxidized and all of the carbon and hydrogen are converted to oxides, 1.37 grams of CO2 and 0.281
gram of water are produced. Determine the most probable molecular formula of compound Z.
1991
The molecular formula of a hydrocarbon is to be determined by analyzing its combustion products and
investigating its colligative properties.
(a) The hydrocarbon burns completely, producing 7.2 grams of water and 7.2 liters of CO2 at standard
conditions. What is the empirical formula of the hydrocarbon?
(b) Calculate the mass in grams of O2 required for the complete combustion of the sample of the
hydrocarbon described in (a).
(c) The hydrocarbon dissolves readily in CHCl3. The freezing point of a solution prepared by mixing
100. grams of CHCl3 and 0.600 gram of the hydrocarbon is 64.0C. The molal freezing-point
depression constant of CHCl3 is 4.68C/molal and its normal freezing point is 63.5C. Calculate
the molecular weight of the hydrocarbon.
(d) What is the molecular formula of the hydrocarbon?
(1) AP is a registered trademark of the College Board. The College Board was not involved in the production of and does not endorse this product. (2) Test
Questions are Copyright 1984-2008 by College Entrance Examination Board, Princeton, NJ. All rights reserved. For face-to-face teaching purposes,
classroom teachers are permitted to reproduce the questions. Web or Mass distribution prohibited.
page 2
1993
I. 2 Mn2+ + 4 OH + O2(g) 2 MnO2(s) + 2 H2O
II. MnO2(s) + 2 I + 4 H+ Mn2+ + I2(aq) + 2 H2O
III. 2 S2O32 + I2(aq) S4O62 + 2 I
The amount of oxygen, O2, dissolved in water can be determined by titration. First, MnSO4 and NaOH
are added to a sample of water to convert all of the dissolved O2 to MnO2, as shown in equation I
above. Then H2SO4 and KI are added and the reaction represented by equation II proceeds. Finally, the
I2 that is formed is titrated with standard sodium thiosulfate, Na2S2O3, according to equation III.
(a) According to the equation above, how many moles of S2O32 are required for analyzing
1.00 mole of O2 dissolved in water?
(b) A student found that a 50.0-milliliter sample of water required 4.86 milliliters of 0.0112-molar
Na2S2O3 to reach the equivalence point. Calculate the number of moles
of O2 dissolved in this sample.
(c) How would the results in (b) be affected if some I2 were lost before the S2O32 was added? Explain.
(d) What volume of dry O2 measured at 25C and 1.00 atmosphere of pressure would have to be
dissolved in 1.00 liter of pure water in order to prepare a solution of the same concentration as that
obtained in (b)? (cont.)
(e) Name an appropriate indicator for the reaction shown in equation III and describe the change you
would observe at the end point of the titration.
1998
An unknown compound contains only the three elements C,H, and O. A pure sample of the compound
is analyzed and found to be 65.60 percent C and 9.44 percent H by mass.
(a) Determine the empirical formula of the compound.
(b) A solution of 1.570 grams of the compound in 16.08 grams of camphor is observed to freeze
at a temperature 15.2 Celsius degrees below the normal freezing point of pure camphor.
Determine the molar mass and apparent molecular formula of the compound. (The molal
freezing-point depression constant, Kf, for camphor
is 40.0 kgKmol1.)
(c) When 1.570 grams of the compound is vaporized at 300 C and 1.00 atmosphere, the gas
occupies a volume of 577 milliliters. What is the molar mass of the compound based on this
result?
(d) Briefly describe what occurs in solution that accounts for the difference between the results
obtained in parts (b) and (c).
page 3
2000
Answer the following questions about BeC2O4(s) and its hydrate.
(a) Calculate the mass percent of carbon in the hydrated form of the solid that has the formula BeC2O4 3H2O
(b) When heated to 220.C, BeC2O4 3 H2O(s) dehydrates completely as represented below.
BeC2O4 3 H2O(s) BeC2O4(s) + 3 H2O(g)
If 3.21 g of BeC2O4 3 H2O(s) is heated to 220.C, calculate
(i) the mass of BeC2O4(s) formed, and,
(ii) the volume of the H2O(g) released, measured at 220.C and 735 mm Hg.
(c) A 0.345 g sample of anhydrous BeC2O4 , which contains an inert impurity, was dissolved in sufficient
water to produce 100. mL of solution. A 20.0 mL portion of the solution was titrated with KMnO4(aq).
The balanced equation for the reaction that occurred is as follows.
+
2+
16 H (aq) + 2 MnO4 (aq) + 5 C2O4 (aq) 2 Mn (aq) + 10 CO2(g) + 8 H2O(l).

The volume of 0.0150 M KMnO4(aq) required to reach the equivalence point was 17.80 mL.
(i) Identify the reducing agent in the titration reaction.
(ii) For the titration at the equivalence point, calculate the number of moles of each of the
following that reacted.
MnO4 (aq)
2
C2O4 (aq)
(iii) Calculate the total number of moles of C2O42(aq) that were present in the 100. mL of
prepared solution.
(iv) Calculate the mass percent of BeC2O4(s) in the impure 0.345 g sample.
2003B
Answer the following questions that relate to chemical reactions.
(a) Iron(III) oxide can be reduced with carbon monoxide according to the following equation.
Fe2O3(s) + 3 CO(g) 2 Fe(s) + 3 CO2(g)
A 16.2 L sample of CO(g) at 1.50 atm and 200.C is combined with 15.39 g of Fe2O3(s).
(i) How many moles of CO(g) are available for the reaction?
(ii) What is the limiting reactant for the reaction? Justify your answer with calculations.
(iii) How many moles of Fe(s) are formed in the reaction?
page 4
(b) In a reaction vessel, 0.600 mol of Ba(NO3)2(s) and 0.300 mol of H3PO4(aq) are combined with
deionized water to a final volume of 2.00 L. The reaction represented below occurs.
3 Ba(NO3)2(aq) + 2 H3PO4(aq) Ba3(PO4)2(s) + 6 HNO3(aq)
(i) Calculate the mass of Ba3(PO4)2(s) formed.
(ii) Calculate the pH of the resulting solution.
1
(iii) What is the concentration, in mol L , of the nitrate ion, NO3 (aq), after the reaction
reaches completion?

Chem 4

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AP*Chemistry

The Chemistry of Acids and Bases

neutral compound as an acid

NH4+ + H2O R H3O+ + NH3

H2PO4 + H2O R H3O+ + HPO42

NH3 + H2O R NH4+ + OH

CO32 + H2O R HCO3 + OH

PO43 + H2O R HPO42 + OH

ACIDS DONATE ONLY ONE PROTON AT A TIME!!!

The Chemistry of Acids & Bases

Acid Dissociation (Ionization) Reactions

The Chemistry of Acids & Bases

RELATIVE STRENGTHS OF ACIDS AND BASES

Weak acids/weak bases

Do Not confuse concentration with strength!

The Chemistry of Acids & Bases

The Chemistry of Acids & Bases

WEAK ACIDS AND BASES:

The Chemistry of Acids & Bases

The equilibrium expression for bases is known as the Kb.

Write the Kb expression for ammonia.

Relative Base Strength

Cl- < H2O < F- < NO2- < CN-

The Chemistry of Acids & Bases

WATER, THE HYDRONIUM ION, AUTO-IONIZATION, AND THE pH SCALE

At 60C, the value of Kw is 1 1013.

b. Calculate [H+] and [OH] in a neutral solution at 60C.

The Chemistry of Acids & Bases

Calculating [H+] and [OH]

A: [H+] = 1.0 10-9 M, basic

The Chemistry of Acids & Bases

Calculating pH and pOH

Calculate pH and pOH for each of the following solutions at 25C.

[OH ] = 2.6 10-7 M

a. Calculate the pH of 0.10 M HNO3.

The Chemistry of Acids & Bases

The pH of Strong Bases

Calculate the pH of a 5.0 102 M NaOH solution.

Calculating pH of Weak Acid Solutions

The Chemistry of Acids & Bases

The Chemistry of Acids & Bases

The pH of Weak Acids

Determination of the pH of a Mixture of Weak Acids

The pH of Weak Acid Mixtures

Calculating Percent Dissociation

The Chemistry of Acids & Bases

Calculating Ka from Percent Dissociation

Ka= 1.4 104

The pH of Weak Bases I

Calculate the pH for a 15.0 M solution of NH3 (Kb = 1.8 105).

The Chemistry of Acids & Bases

The pH of Weak Bases II

Calculate the pH of a 1.0 M solution of methylamine (Kb = 4.38 104).

Calculating pH of polyprotic acids

Consider the dissociation of phosphoric acid.

Ka2 = 6.2 10-8

HPO42-(aq) + H2O(l) R H3O+(aq) + PO43(aq)

Ka3 = 4.8 10-13

The Chemistry of Acids & Bases

The pH of a Polyprotic Acid

The pH of a Sulfuric Acid

Calculate the pH of a 1.0 M H2SO4 solution.

The Chemistry of Acids & Bases