Chem 162-2012 4/27 Review for Final Exam – Review of 2010 final exam

Dr. Ed Tavss

CHAPTER TITLE REQUESTS

High Priority
16 Acids and Bases 59
17 Acid-Base/Solubility Equilibria 71
19 Electrochemistry 49
14 Chemical Kinetics 29
20 Nuclear Chemistry 41

Low Priority
18 Thermochemistry 18
15 Chemical Equilibrium 25
22 Coordination Chemistry 22
13 Physical Properties of Solutions 13

Chem 162-2012 Final exam review from 2010 final exam 1

 CHAPTERS 16 & 17

pH [H+]
14 Basic 1x10-14

H2O + H2O → +
← H3O + OH Kw = 1x10
- -14
7 Neutral (e.g. H2O) 1x10-7
Kw = [H ][OH ] = 1 x 10-14
+ -

pH + pOH = 14

Kw = Ka x Kcb = Kca x Kb = 1 x 10-14*

*a & b = acid and base; ca & cb = conjugate acid and conjugate base

pKa + pKb = 14 0 Acidic 1x10o

pH units of 1 to 13 is what is commonly used, but pH’s as low as
-1 or as high as 15 are possible. No acids in existence for <-1 or
bases for >+15.

[H+] = 10-pH
pH = -log[H+] pH +
pH = -log[H ]
[H+]
[H+] = 10-pH
Kw = [H+][OH-] = 1 x 10-14
Kw = [H+][OH-] = 1 x 10-14
pH + pOH = 14
pH + pOH = 14

pOH = -log[OH-]
[OH-] = 10-pOH

[OH-] = 10-pOH
pOH pOH = -log[OH ] - [OH-]

Henderson-Hasselbalch equation: pH = pKa + log([B]/[A])

or pOH = pKbase + log([Acid]/[Base])
where acid = acid or conjugate acid, and base = base or conjugate base.
At equal conc. of conj. base and acid, pH = pKa of a buffer
[H+] = Ka = 10-pH

Chem 162-2012 Final exam review from 2010 final exam 2

SEVEN STRONG ACIDS
ET: Discuss strong acids and strong bases and the strengths of their conjugate bases and acids; practice both.

Very weak base

(i.e., not a base;
Ka Acid spectator ion)**
~106 HCl + H2O H 3O + + Cl-
~108 HBr + H2O H 3O + + Br-
~109 HI + H2O H 3O + + I-
H2SO4 + H2O H 3O + + HSO4-***
HNO3 + H2O H 3O + + NO3-
HClO4 + H2O H 3O + + ClO4-
HClO3 + H2O H 3O + + ClO3-)*
*Strong, but not common, acid. Generally not considered as a strong acid.
**These conjugate bases are known as “nominal bases”, i.e., a base by definition, but effectively not a base.
→ +
***Although HSO4- is effectively not a base, it is effective as an acid. HSO4- + H2O ← H3O + SO4
2-

All other acids are weak acids, e.g., HA (acetic acid), H2SO3, RNH3+, BF3

Arrhenius acid: Anything that provides a proton, e.g., HA, H2SO3, RNH3+
BL Acid: Anything tending to give up a proton, e.g., HA, H2SO3, RNH3+
(Lewis Acid: Anything tending to react with an electron pair, e.g., BF3)

STRONG BASES
(Most Group 1A and 2A hydroxides [not HOH])
e.g. Very weak acid
(i.e., not an acid;
Base spectator ion)
-
LiOH OH + Li+
NaOH OH- + Na+
Mg(OH)2 2OH- + Mg2+
Ba(OH)2 2OH- + Ba2+
All other bases are weak bases, e.g., RNH2, CO32-
Arrhenius Base: Anything that provides an OH- group, e.g., NaOH
BL Base: Anything that tends to react with a proton, e.g., NaOH, RNH2, CO32-
Lewis Base: Anything that has available non-bonding electrons, e.g., NaOH, RNH2, CO32-
Chem 162-2012 Final exam review from 2010 final exam 3
Chem 162-2012 Final exam review from 2010 final exam 4
 RELATIONSHIP BETWEEN STRUCTURE
AND STRENGTH OF ACID, H-Z
ET: Impossible to understand this topic based on H&P’s discussion

Let Z = atom which the H is attached to, which is O for oxyacids, or F, Cl,
S, etc. for binary acids.
Strength of acid is determined completely by [homolytic] strength of H-Z
bond. (If the bond is weak, the acid is strong; if the bond is strong, the
acid is weak.*)
*Bond strength correlates inversely with bond polarity. That is, the weaker the bond, the more polar the bond is. Some argue that it is the H-Z bond weakening,
not the increased bond polarity, that results in increased acid strength; others argue that it is the increased bond polarity, not the bond weakening, that results in
increased acid strength.

Two competing factors:

(1) For decreasing H-Z bond strength (i.e., increasing acidity).
• Increasing strength of electron withdrawing effect of Z.
• Increasing bond distance
• Increasing anion size.
(All three factors are effective in dispersing the negative charge of
the bonding electrons, and therefore stabilizing the incipient
conjugate base.)
• Polarity of solvent (e.g. H2O)
(H2O forms an ion-dipole bond with the partially positive H atom.
Therefore, increased polarity of the H helps to weaken the H-Z bond
by pulling off the proton.
(2) For increasing H-Z bond strength (i.e., decreasing acidity).
• Strength of electrostatic interaction of the Hδ+Zδ- bond. This is
governed by decreasing bond distance and small anion size. For
these two reasons the H-F bond is stronger than the H-Cl bond.
For the comparison of strengths of most acids, the electron withdrawing effect of Z is the much more important factor; i.e., the greater the
electronegativity (which directly corresponds to the electron withdrawing effect), the weaker the H-Z bond. The weaker the H-Z bond, the stronger
the acid. (The electrostatic interaction of H-Z bonds for most acids [i.e., oxyacids] is too weak [because of the large distance between the charge
centers] to be a significant factor in acid strength.) Hence, HOF is a stronger acid than HOCl.

For the comparison of vertical group acids, both factors need to be taken into consideration. The more important factor of the two depends on the
H-Z bond distance. The H-Z electrostatic (δ+ δ-) interaction of the two partial charges is the dominant factor when the atoms are close to each other
(according to Coulomb’s law); the closer the two charges (e.g., H-F), the stronger the H-Z bond; the stronger the H-Z bond, the weaker the acid.
Hence, although F has a significant electron-withdrawing effect, the electrostatic interaction is the dominant effect, resulting in H-F being a weak
acid. In descending the vertical group acids in the periodic table (e.g., toward H-I), the electrostatic interaction becomes weaker due to the
increasing distance between the atoms, and the size of the anions [increased size results in greater charge dispersal and therefore more stability]
while the importance of the electrostatic interaction as a factor is diminished. Therefore, the strength of the electron withdrawing effect becomes
more important while descending vertical group acids. Hence, HI is a strong acid due to a significant electron withdrawing effect of the iodine
atom, and an insignificant electrostatic interaction between the distant H and I atoms.
** misleadingly referred to as bond strength in H&P

Chem 162-2012 Final exam review from 2010 final exam 5

 RELATIONSHIPS BETWEEN STRUCTURE AND STRENGTHS
OF ACIDS AND BASES

• Vertical group binary acids: Acid strength increases as period

number (proton-halogen bond distance) increases.
• All other acids: Acid strength increases as electronegativity
increases.

Chem 162-2012 Final exam review from 2010 final exam 6

ET: First discuss equations, then reverse equations invert K, then Ka x Kb = 10-14

Write the equil. equations and identify K’s for the following reactions:

Weak acid + water (e.g., acetic acid + H O): 2 HA + H2O →

← H3O+ + A-
1

Assume Ka = ~1 x 10-5

Conjugate base + water (e.g., sodium acetate + H O): A- + H2O 2

→
← HA + OH-
3

Kcb = Kw/Ka = (1 x 10-14)/(1 x 10-5) = 1 x 10-9

Conjugate base + H3O+ (e.g., sodium acetate + H O ):A- + H3O+ → HA + H2O 3

+
2

K = 1/Ka = 1/(1 x 10-5) = 1 x 105

(or bring to completion; then solve either using HH or
reverse + Ka)

Weak acid + strong base (e.g., acetic acid + sodium hydroxide): HA + OH- → H2O + A-
4

K = 1/(Kw/Ka) = Ka/Kw = (1 x 10-5)/(1 x 10-14) = 1 x 109

(or bring to completion; then solve either using HH or
reverse + Ka)

Weak base + water (e.g., NH + H O): 3 2 RNH2 + H2O ←→ RNH3+ + OH-

Assume Kb = ~1 x 10-5

Conjugate acid + water (e.g., sodium acetate + H O): RNH3+ + H2O ←

→ RNH2 + H3O+
2

Kca = Kw/Kb = (1 x 10-14)/(1 x 10-5) = (1 x 10-9)

Conjugate acid + OH- (e.g., ammonium chloride + OH ): RNH3+ + OH- → RNH2 + H2O -

K = 1/Kb = 1/(1 x 10-5) = 1 x 105

(or bring to completion; then solve either using HH or
reverse + Kb)

Weak base + strong acid (e.g., NH + H O ): RNH2 + H3O+ → RNH3+ + H2O

3 3
+

K = 1/(Kw/Kb) = Kb/Kw = (1 x 10-5)/(1 x 10-14) = 1 x 109

(or bring to completion; then solve either using HH or
reverse + Kb)

Chem 162-2012 Final exam review from 2010 final exam 7

 A titration is a procedure where a base is added to an acid, or an acid is added to a
base until the stoichiometric amount of base or acid is added This is called the
TITATION CURVE OF WEAK ACID
-
WITH
-
STRONG BASE
HA + OH → H2O + A
14 ←
Strong
base
Strong base

12
Weak base
Completion
or
10 Red
End Point
HIn + In- or 9 for SB & WA
Phenolphthalein -
A Equivalence Point 7 for SB & SA
Indicator
or 5 for WB & SA
pH

8
Colorless Stoichiometric Point
or
Neutralization Point
6 1:1
HA:A-

Half-way Point
4 or
Half-equivalency Point
Weak acid HA pH = pKa + log([A-]/[HA])
pH = pKa + log([X]/[X])
2 Weak pH = pKa
5 = pKa
acid Ka = 10-pH = 1 x 10-5
Strong acid

0
0 10 20 30 40
Volume of Titrant (mL)
Henderson-Hasselbalch equation
pH = pKa + log([B]/[A])
At half-way point pH = pKa
[H+162-2012
Chem ] = KFinal
a (=exam
-pH
10review
) from 2010 final exam 8
SIX STRONG ACIDS
ET: Discuss strong acids and strong bases and the strengths of their conjugate bases and acids; practice both.

Very weak base

(i.e., not a base;
Ka Acid spectator ion)**
~106 HCl + H2O H 3O + + Cl-
~108 HBr + H2O H 3O + + Br-
~109 HI + H2O H 3O + + I-
H2SO4 + H2O H 3O + + HSO4-***
HNO3 + H2O H 3O + + NO3-
HClO4 + H2O H 3O + + ClO4-
(HClO3 + H2O H 3O + + ClO3-)*
*Strong, but not common, acid. Generally not considered as a strong acid.
**These conjugate bases are known as “nominal bases”, i.e., a base by definition, but effectively not a base.
→ +
***Although HSO4- is effectively not a base, it is effective as an acid. HSO4- + H2O ← H3O + SO4
2-

All other acids are weak acids, e.g., HA (acetic acid), H2SO3, RNH3+, BF3

Arrhenius acid: Anything that provides a proton, e.g., HA, H2SO3, RNH3+
BL Acid: Anything tending to give up a proton, e.g., HA, H2SO3, RNH3+
(Lewis Acid: Anything tending to react with an electron pair, e.g., BF3)

STRONG BASES
(Most Group 1A and 2A hydroxides [not HOH])
e.g. Very weak acid
(i.e., not an acid;
Base spectator ion)
-
LiOH OH + Li+
NaOH OH- + Na+
Mg(OH)2 2OH- + Mg2+
Ba(OH)2 2OH- + Ba2+
All other bases are weak bases, e.g., RNH2, CO32-
Arrhenius Base: Anything that provides an OH- group, e.g., NaOH
BL Base: Anything that tends to react with a proton, e.g., NaOH, RNH2, CO32-
Lewis Base: Anything that has available non-bonding electrons, e.g., NaOH, RNH2, CO32-
Chem 162-2012 Final exam review from 2010 final exam 9
Chem 162-2010 Final exam
Acids and Bases - Chapters 16 & 17
Acid-base properties of salts concepts
3. Which of the following are BASIC salts?

W. NH4I
X. BaCl2
Y. KNO3
Z. NaF

A. Z only
B. Xand Y
C. Y and Z
D. W only
E. W and X
ET: Get rid of schmutz ions and determine pH of what’s remaining.

NH4I → NH4+ + I-
I- is such a weak base that it doesn’t act basic.
I- + H2O → NR
But NH4+ is a weak acid.
NH4+ + H2O ← → NH3 + H3O+
Therefore, solution is acidic.

BaCl2 → Ba2+ + 2Cl-

Group I and II cations are not acidic.
Ba2+ + H2O → NR
The conjugate bases of strong acids are not basic.
Cl- + H2O → NR
Therefore, this salt is neutral in water.

KNO3 → K+ + NO3-
Group I and II cations are not acidic.
K+ + H2O → NR
The conjugate bases of strong acids are not basic.
NO3- + H2O → NR
Therefore, this salt is neutral in water.

NaF → Na+ + F-
Group I and II cations are not acidic.
Na+ + H2O → NR
F- is a weak conjugate base.
F- + H2O ←→ HF + OH-
Together, NaF provides a basic solution.

Chem 162-2012 Final exam review from 2010 final exam 10

CHEM 162-2000 FINAL EXAM
CHAPTERS 16 & 17 - ACID AND BASE EQUILIBRIA
ACID AND BASE EQUILIBRIA CALCULATIONS

44. Methylamine, CH3NH2 is a weak base with Kb = 3.6x10-4 at 25oC. What is the
equilibrium constant for the following reaction at 25oC?
CH3NH2(aq) + H+(aq) ← → CH3NH3+(aq)

A. 2.8x1011
B. 3.6x1010
C. 1.7x108
D. 3.6x103
E. 2.8x103

→
ET note: This is the same reaction as in the table: CH3NH2(aq) + H3O+(aq) ← CH3NH3 (aq) + H2O.
+
The right side is Kca.

→ CH3NH3+(aq)
CH3NH2(aq) + H+(aq) ←
CH3NH2(aq) + H3O+(aq) ← → CH3NH3+(aq) + H2O

The right side of the equation is Kca.

K = 1/Kca
Kw = Kb x Kca
Kca = Kw/Kb
K = 1/(Kw/Kb) = Kb/Kw = (3.6 x 10-4)/(1 x 10-14) = 3.6 x 1010

Chem 162-2012 Final exam review from 2010 final exam 11

CHEM162-2010 HOURLY EXAM II + ANSWERS
CHAPTERS 16 & 17 - APPLIC OF ACID & BASE EQUILIB. (BUFFERS & TITRATIONS)
BUFFER CALCULATIONS

45. How many moles of solid NH4Cl must be dissolved in 1.00L of a 0.950M
NH3(aq) solution in order to prepare a buffer with a pH of 9.60. Kb(NH3) = 1.8x10-5

A. 2.3 mol
B. 1.6 mol
C. 0.75 mol
D. 0.43 mol
E. 0.34 mol
ET Note: The solution consists of NH3, NH4Cl and H2O. Think HH equation.

pH 9.60
pOH = 4.40
-log[OH-] = 4.40
[OH-] = 4.0 x 10-5
NH3(aq) + → NH4+(aq) + OH-(aq)
H2O ←
Initial 0.950 0 0
Change
Equilibrium 4.0 x 10-5

NH3(aq) + → NH4+(aq) + OH-(aq)

H2O ←
Initial 0.950 Y 0
Change -X +X +X
Equilibrium 0.950-X Y+X 4.0 x 10-5

NH3(aq) + → NH4+(aq) + OH-(aq)

H2O ←
Initial 0.950 Y 0
Change -4.0 x 10-5 +4.0 x 10-5 +4.0 x 10-5
Equilibrium 0.950-(4.0 x 10-5) Y + (4.0 x 10-5) 4.0 x 10-5
Henderson-Hasselbach:
pH = -log Kca + log([A-]/[HA])
pH = -log (Kw/Kb) + log([A-]/[HA])
9.60 = -log((1x10-14)/(1.8 x 10-5)) + log(0.950/Y)
X = 0.4295

Chem 162-2012 Final exam review from 2010 final exam 12

CHEM 162-2010 FINAL EXAM
Chapters 16 & 17a - Acid & Base Equilibria
Acid and base equilibria calculations

37. Phosphoric acid, H3PO4, is a polyprotic acid. If 0.30 mol H3PO4 and 0.60
mol KOH are reacted in aqueous solution, which one of the following ions will
have the highest concentration at equilibrium?
A. H3O+
B. OH-
C. H2PO4-
D. PO43-
E. HPO42-

ET note: (1) Strong bases bring the reaction to completion. (2)The Ka’s become much, much smaller in going from K1 to K2 to K3. K3 is essentially zero.

1st reaction: Bring to completion; H3PO4 is the limiting reactant.

H3PO4 + OH- → H2PO4- + H2O
Initial 0.30 0.60 0 0
Change -0.30 -0.30 +0.30
Equilibrium 0 0.30 0.30

2nd reaction:
H2PO4- + OH- → HPO42- + H2O
Initial 0.30 0.30 0 0
Change -0.30 -0.30 +0.30
Equilibrium 0 0 0.30

3rd reaction:
HPO42- + H2O → H3O+ + PO43-
Initial 0.30 0 0
Change -X +X +X
Equilibrium 0.30-X +X +X
([H3O+][PO43-])/[HPO42-] = K3
([X][X])/[0.30-X] = K3
In the third reaction, K3 is so small due to the formation of a triply charged substance (i.e., unstable), that
essentially nothing happens. Hence, X is very, very small

A. No. H3O+ only forms in the third step, but since K3 is so small virtually no H3O+ will form.
B. No. The OH- gets completely used up in the first and second steps.
C. No. The H2PO4- that is formed in the first step is completely used up in the second step.
D. No. The PO43- forms only in the third step, but since third step Ka’s of polyprotic acids are soooo
small, there is virtually no PO43- formed.
E. Yes. The HPO42- that is formed in the second step is virtually untouched in the third step because 3rd
Ka’s are very, very small.

Chem 162-2012 Final exam review from 2010 final exam 13

 RELATIONSHIPS BETWEEN STRUCTURE AND STRENGTHS
OF ACIDS AND BASES

• Vertical group binary acids: Acid strength increases as period

number (proton-halogen bond distance) increases.
• All other acids: Acid strength increases as electronegativity
increases.

Chem 162-2012 Final exam review from 2010 final exam 14

CHEM 162-2010 FINAL EXAM
CHAPTERS 16 & 17 - ACID AND BASE EQUILIBRIA
RELATIONSHIP BETWEEN ACID AND BASE STRUCTURE AND STRENGTH

26. Arrange the following acids in order of increasing acid strength.

HBrO HClO3 HClO2 HClO HIO

A. HClO < HBrO < HIO < HClO2 < HClO3

B. HClO3 < HClO2 < HClO < HIO < HBrO
C. HIO < HBrO < HClO < HClO2 < HClO3
D. HClO < HClO2 < HClO3 < HBrO < HIO
E. HClO3 < HClO2 < HClO < HBrO < HIO
ET note: All oxyacids

All five are oxyacids, so the strength depends on the relative weakness of the
bonds, which is caused by differences in electronegativity.
Electronegativity ranking: F > O > Cl > Br > I
HIO is the weakest acid.
HBrO is a little stronger than HIO because Br is stronger in electronegativity
than I.
HClO is a little stronger than HBrO because Cl is stronger in
electronegativity than Br.
HClO2 is a little stronger than HClO because it contains two electronegative
oxygens.
HClO3 is a little stronger than HClO2 because it contains three
electronegative oxygens.

Chem 162-2012 Final exam review from 2010 final exam 15

Chem 162-2010 Final Exam + Answers
Chapters 16 & 17 - Applications of Aqueous Equilibria (of Acids and Bases)
Buffers (including Henderson-Hasselbalch equation) Concepts

18. A buffer is formed by adding 1.0 mol of CH3COOH and 1.0 mol CH3COO-
in a 1.0 L container. The pH of the buffer is 4.74. Which of the following
would make the smallest change in the pH?

A. Add 0.50 mol of NaOH to 1.0L of the buffer

B. Add 0.50 mol of HCl to 1.0L of the buffer
C. Add 49L of water to 1.0L of the buffer
D. Add 0.50 mol of CH3COOH to 1.0 L of the buffer.
E. Add 0.50 mol of CH3COO- to 1.0L of the buffer.
ET: Addition of any acid or base will change the pH, some more than others. But, based on the HH equation, addition of H2O dilutes the [A-] and [HA]
equally, so the log term will still drop out.

Henderson-Hasselbalch equation: pH = pKa + log([A-]/[HA])

A. False. Addition of a strong base will react with the HA, resulting in a
small increase in pH.
B. False. Addition of a strong acid will react with the A-, resulting in a
small decrease in pH.
C. True. In the Henderson-Hasselbalch equation, 1.0 mol of CH3COOH and
1.0 mol CH3COO- in 1.0L results in the following: pH = pKa +
log([1]/[1]). In this case, since the log of 1/1 drops out, the pH = the pKa
of the acetic acid. If the buffer were diluted 50 fold, then the equation
would be pH = pKa + log([0.02]/[0.02]). The log of 0.02/0.02 drops out
again, and the pH still equals the pKa, i.e., the pH doesn’t change at all
upon dilution of the buffer. (Only the buffer capacity changes.)
D. False. Addition of a weak acid will react with the A-, resulting in a very
small decrease in pH.
E. False. Addition of a weak base will react with the HA, resulting in a very
small increase in pH.

Chem 162-2012 Final exam review from 2010 final exam 16

 A titration is a procedure where a base is added to an acid, or an acid is added to a
base until the stoichiometric amount of base or acid is added This is called the
TITATION CURVE OF WEAK ACID
-
WITH
-
STRONG BASE
HA + OH → H2O + A
14 ←
Strong
base
Strong base

12
Weak base
Completion
or
10 Red
End Point
HIn + In- or 9 for SB & WA
Phenolphthalein -
A Equivalence Point 7 for SB & SA
Indicator
or 5 for WB & SA
pH

8
Colorless Stoichiometric Point
or
Neutralization Point
6 1:1
HA:A-

Half-way Point
4 or
Half-equivalency Point
Weak acid HA pH = pKa + log([A-]/[HA])
pH = pKa + log([X]/[X])
pH = pKa
2 5 = pKa
Ka = 10-pH = 1 x 10-5
Strong acid

0
0 10 20 30 40
Volume of Titrant (mL)
Henderson-Hasselbalch equation
pH = pKa + log([B]/[A])
At half-way point pH = pKa
[H+162-2012
Chem ] = KFinal
a (=exam
-pH
10review
) from 2010 final exam 17
CHAPTERS 16 & 17
CHEM 162-2010 Final exam
Chapters 16 & 17B - Applic. of Acid & Base Equilibria (Buffers & Titrations)
Titrations and Indicators

1. Aniline, one of the first synthetic dyes, has a Kb of 7.4 x 10-10. A student is
planning to titrate a solution containing aniline to determine its concentration.
In picking an indicator, what should the student consider (aside from the color
of the dye)?

A. The choice of indicator will depend on the initial concentration.

B. The indicator should change color at or near pH 9.
C. The indicator should change color at or near pH 3.
D. The indicator should change color at or near pH 7.
E. The indicator should change color at or near pH 6.
ET note: Problem can be done quantitatively or qualitatively. Quantitatively involves bringing the reaction to completion and then back again. Qualitatively
involves realizing that 10-10 is a very,very weak base, and estimating that the equivalence point would be at ~ pH 3 on the titration diagram.

Weak bases are generally titrated with strong acids. When a strong acid titrates
a strong base the stoichiometric point is approximately 7. When a strong acid
titrates a weak base, e.g., NH3 (Kb = 1.8 x 10-5), the stoichiometric point is
approximately 5. Aniline is a very weak base (Kb = 7.4 x 10-10). Hence the
stoichiometric point should be well below 5. The only option is 3.

Chem 162-2012 Final exam review from 2010 final exam 18

 CHAPTER 16
PRECIPITATION REACTIONS
(HEAVY METAL IONS FORMING
PRECIPITATES)

1A 2A 3A 4A 5A 6A 7A 8A

He

Li+ Be B C N O F Ne

Na+ Mg 3B 4B 5B 6B 7B 8B 8B 8B 1B 2B Al Si P S2- Cl- Ar

K+ Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br- Kr

Rb+ Sr Y Zr Nb Mo Te Ru Rh Pd Ag+ Cd In Sn Sb Te I- Xe
?

Cs+ Ba2+ La Hf Ta W Re Os Ir Pt Au Hg22+ Tl Pb2+ Bi Po At- Rn

Chem 162-2012 Final exam review from 2010 final exam 19

 PRECIPITATION REACTIONS
Concept:
Soluble salts:
All group IA metal ions and NH4+
All nitrates (NO3-), acetates (CH3CO2-),
perchlorates (ClO4-)
All Cl-, Br-, I-* (except Ag+, Pb2+, Hg22+)
All IO3- and IO4- (except Pb2+, Hg22+, Ba2+)
HIGH PRIORITY
LOW PRIORITY

All SO42- (except Pb2+, Hg22+, Ba2+, Ca2+)

*Note absence of F-

Insoluble salts:
Ag+, Pb2+, Hg22+, Ba2+
Hydroxides (OH-)
Sulfides (S2-)
Carbonates (CO32-)
Chromates (CrO42-)
Phosphates (PO43-)

Chem 162-2012 Final exam review from 2010 final exam 20

CHEM 162-2001 HOURLY EXAM III
Chapter 16
SOLUBILITY PRODUCT

5. What is the pH of an aqueous solution that is saturated with Mn(OH)2 (Ksp =

1.9 x 10-13)?
A. 9.86
B. 8.53
C. 10.23
D. 11.20
E. 7.56
ET: Begin with Ksp equilibrium equation. Solve as usual.

Mn(OH)2(s) →
← Mn2+(aq) + 2 OH-(aq)
Initial Y 0 0
Change -X +X +2X
Equilibrium Y-X +X +2X
[Mn2+][OH-]2 = Ksp
X x (2X)2 = 1.9 x 10-13
4X3 = 1.9 x 10-13
X = 3.625 x 10-5
2X = 7.251 x 10-5
pOH = -log[OH-]
pOH = -log[7.251 x 10-5]
pOH = 4.14
pH = 14 - 4.14 = 9.86

Chem 162-2012 Final exam review from 2010 final exam 21

CHEM-2010 FINAL EXAM + ANSWERS
CHAPTER 16 - EQUILIBRIA
SOLUBILITY PRODUCT
29. A solution is initially 0.10M in Mg2+(aq) and 0.10M in Fe2+(aq). Solid NaOH is slowly added. What
is the concentration of Fe2+ when Mg(OH)2 first precipitates?
Ksp(Mg(OH)2 = 6.0 x 10-10; Ksp(Fe(OH)2) = 7.9 x 10-16

A. 4.1 x 10-6
B. 2.6 x 10-9
C. 3.8 x 10-11
D. 1.3 x 10-7
E. 6.7 x 10-5
ET: Selective precipitation problem. Note that selective precipitation is the main factor in the Qualitative Inorganic Analysis Scheme at the end of chapter 16.
→ Mg2+ + 2OH-
Mg(OH)2(s) ←
→ Fe2+ + 2OH-
Fe(OH)2(s) ←

→
Mg(OH)2(s) ← Mg2+ + 2OH-

Initial Y 0 0
Change -X +X +2X
Equilibrium 0.10 2X
[Mg2+][OH-]2 = Ksp
0.10 x (2X)2 = 6.0 x 10-10
X = 3.872 x 10-5
2X = 7.744 x 10-5 = [OH-] to just begin precipitation of Mg(OH)2

→
Fe(OH)2(s) ← Fe2+ + 2OH-

Initial Y 0 0
Change
Equilibrium 0.10 +2X
2+ - 2
[Fe ][OH ] = Ksp
0.10 x (2X)2 = 7.9 x 10-16
X = 4.44 x 10-8
2X = 8.88 x 10-8 = [OH-] to just begin precipitation of Fe(OH)2

So Fe(OH)2 begins to precipitate first.

Stop the titration when [OH-] just reaches 7.744 x 10-5.

Determine the concentration of Fe2+ in solution when [OH-] just reaches 7.744 x 10-5M
[Fe2+][OH-]2 = Ksp
[Y] x ((7.744 x 10-5)2) = (7.9 x 10-16)
Y = [Fe2+] = 1.317 x 10-7

Chem 162-2012 Final exam review from 2010 final exam 22

CHEM 162-2010 Final exam
Chapter 16 - Transition Metals and Coordination Chemistry
Complex Ion Equilibria
28. 0.40 moles of AgNO3 and 2.5 moles of S2O32- are dissolved in 1.00L of aqueous solution. A
coordination complex forms.

→ [Ag(S2O3)2]3-(aq)
Ag+(aq) + 2S2O32- ← Kf = 1.7 x 1013

Calculate [Ag+] in this solution.

A. 8.1 x 10-15M
B. 5.3 x 10-15M
C. 1.7 x 10-13M
D. 2.0 x 10-12M
E. 1.7 x 10-13M
ET: Typical complex ion problem using small K rule (because of large K) and then right-to-left rule.

Ag+(aq) + 2S2O32-(aq) → [Ag(S2O3)2]3-(aq)

←
Initial 0.40 2.5 0
Change -X -2X +X
Equilibrium 0.40-X 2.5-2X +X

This is going to give a quadratic equation. Use the large K rule. Bring the reaction to
completion, and then back to equilibrium. Ag+ is the limiting reactant.

Ag+(aq) + 2S2O32-(aq) → [Ag(S2O3)2]3-(aq)

←
Initial 0.40 2.5 0
Change -0.40 -0.80 +0.40
Equilibrium 0 1.70 +0.40

Now go back to equilibrium. Since it’s more convenient for the student to go from left to right,
reverse the equation, and invert K.
→
[Ag(S2O3)2]3- ← Ag+ (aq) + 2S2O32-(aq)
New initial 0.40 0 1.70
Change -X +X +2X
Equilibrium 0.40-X +X 1.70 + 2X
+ 2- 2 3-
([Ag ][S2O3 ] )/[Ag(S2O3)2] = 1/Kf
([X][1.70+2X]2)/[0.40-X] = 1/(1.7x1013) = 5.88 x 10-14
To avoid a quadratic equation, use the small K rule.
([X][1.70]2)/[0.40] = 5.88 x 10-14
X = 8.14 x 10-15 = [Ag+]

Chem 162-2012 Final exam review from 2010 final exam 23

 CHAPTER 19
BALANCING REDOX EQUATIONS
(Follow rules in descending order of priority)

(1) Write net reaction.

(2) Identify pairs of substances involved in oxidation (OXLEA) and pairs of
substances involved in reduction half-reactions.
(3) Balance (in the following order)
-- the atoms (not O or H);
-- O, using H2O;
-- H, using H+;
-- charge, using electrons;
-- electrons of each half-cell reaction, using half-equation coefficients.
(4) Add the two half-cell equations.
(5) Get rid of spectator ions/spectator molecules/spectator electrons.
(6) Adjust H+ with OH- if basic solution is requested.
(7) Verify that all atoms and charges are balanced.

Chem 162-2012 Final exam review from 2010 final exam 24

 for lecture 20CHAPTER 19 - ELECTROCHEMISTRY
ELECTRODE REDUCTION POTENTIALS
Some Selected Standard Electrode Reduction Potentials
ET: In this table all reactions are written as reductions.Eo, volt (red’n)
F2 + 2 e- → 2 F- +2.87
+ -
H2O2 + 2 H + 2 e → 2 H2O +1.78*
- + - 2+
MnO4 + 8H + 5e → Mn + 4H2O +1.51
3+ -
Au + 3e → Au +1.50
+ - 2+
PbO2 + 4 H + 2 e → Pb + 2 H2O +1.46
- -
Cl2 + 2 e → 2 Cl +1.36
2- + - 3+
Cr2O7 + 14 H + 6 e → 2 Cr + 7 H2O +1.33
O2 + 4 H+ + 4 e- → 2 H2O +1.23*
Br2 + 2e- → 2Br- +1.09
+ -
Ag + e → Ag +0.80
3+ - 2+
Fe + e → Fe +0.77
- - -
MnO4 + 2 H2O + 3 e → MnO2 + 4 OH +0.60
- -
I2 + 2 e → 2 I +0.54
2+ -
Cu + 2 e → Cu +0.34
2+ - +
Cu + e → Cu Ref. electrode: +0.16
REDUCTION

+ -
2H + 2 e → H2 1M H+ & 1atm H2 0.00
OXIDATION

Fe3+ + 3e- → Fe -0.036

2+ -
Pb + 2 e → Pb -0.13
2+ -
Ni + 2 e → Ni -0.23
Cd2+ + 2e- → Cd -0.40
3+ - 2+
Cr + e → Cr -0.50
2+ -
Zn + 2 e ----> Zn -0.76
- -
2 H2O + 2 e → H2 + 2 OH -0.83*
Al3+ + 3e- → Al -1.66
2+ -
Mg + 2 e → Mg -2.37
+ -
Na + e → Na -2.71
2+ -
Ba + 2e → Ba -2.91
+ -
Cs + e → Cs -3.03
* H2O half-cell reactions

Chem 162-2012 Final exam review from 2010 final exam 25

 ELECTROCHEMISTRY FORMULAS

Eocell = Eoredn + Eooxidn

Ecell = Eocell -(RT/nF)ln(Q) = Nernst equation
(Ecell = Eocell – ((8.314 x 298.15)/(n x 96485)) x (2.303 x log(Q))
Ecell = Eocell -(0.0592/n)log(Q) = Nernst equation
At equilibrium: 0 = Eocell -(0.0592/n)log(K)
Eocell = (0.0592/n)log(K)

∆G = ∆Go + RT ln(Q)
At equilibrium: 0 = ∆Go + RTln(K)
∆Go = -RTln(K)

∆Go = -nFEocell
∆G = -nFEcell
wmax = ΔG

Definitions:
1 ampere = 1 coulomb of charge/second
1 mole of electrons caries a charge of 1 Faraday = 96485 coulombs

Calculations :
(1) Amperes x ((Coulombs/sec)/Ampere) x sec
x (1 mol e-/96485 coulomb) x (mol subst./mol e-) = mol substance
or
(2) (amperes x seconds)/(96485 x electrons) = mol substance

Chem 162-2012 Final exam review from 2010 final exam 26

 LINE NOTATION

• Salt bridge, represented by a double vertical line, in middle.

• Anode components on left; cathode components on right
o Anode and cathode electrode substance on far left and far right,
respectively.
o All species of each half-cell reaction listed between its
electrode and the salt bridge.
- If species are in same phase, separate by commas.
- If species are in different phases, separate by single
vertical lines.

Chem 162-2012 Final exam review from 2010 final exam 27

LINES OF DEFENSE AGAINST RUST
- Paint the iron to exclude air.
- Coat with a less active material, e.g., Sn
- Galvanizing: Coat with a more active material, e.g., Zn
(galvanized iron)
Forms a thin, hard ZnO coating, impervious to air.
- Stainless steel: Stainless steel is an alloy of iron with small
amounts of chromium and nickel, which form oxide coatings
which protect the iron.
- Sacrificial anode: Fe connected to a chunk of more active material,
e.g., Zn, Mg, Al, directly or with a wire.

Chem 162-2012 Final exam review from 2010 final exam 28

 LINE NOTATION

• Salt bridge, represented by a double vertical line, in middle.

• Anode components on left; cathode components on right
o Anode and cathode electrode substance on far left and far right,
respectively.
o All species of each half-cell reaction listed between its
electrode and the salt bridge.
- If species are in same phase, separate by commas.
- If species are in different phases, separate by single
vertical lines.

Chem 162-2012 Final exam review from 2010 final exam 29

CHEM 162-2010 FINAL EXAM
CHAPTER 19 - ELECTROCHEMISTRY
GALVANIC CELLS & REDUCTION-POTENTIAL CONCEPTS

4. In the cell diagram

Pt(s)│Br2(l)│Br-(aq)║Cl-(aq)│Cl2(g)│Pt(s)
(1) The cathode reaction is Br2(l) + 2e- → 2Br-(aq).
(2) Platinum is part of the cell as an inert conductor.
(3) The cell potential will change as the concentration of Cl-(aq) changes.

A. Only (1) is true.

B. Only (1) and (3) are true.
C. Only (2) is true.
D. All three are true.
E. Only (2) and (3) are true.
ET: Explain line diagram as anode on the left and cathode on the right.

(1) False. In a line diagram, the cathode is on the right side. It is the reaction
of Cl2(l) + 2e- → 2Cl-(aq).
(2) True. Platinum is part of the cell as an inert conductor.
(3) True. In all voltaic cells, the cell potential decreases as the reaction goes
forward. The reaction going forward means that the Br- concentration
decreases, while the Cl- concentration increases. Eventually the cell potential
becomes zero, and the reaction stops. This can be demonstrated
mathematically by plugging numbers into the Nernst equation for this reaction.
At first, the value of E is the difference between the voltages of the two half-
cells. But as the concentration of Cl- increases (and correspondingly the
concentration of Br- decreases), the value of E becomes smaller.
E = 0.29 – ((0.0592/1) x log ([Cl-]/[Br-]))

Chem 162-2012 Final exam review from 2010 final exam 30

CHEM 162-2010 FINAL EXAM
CHAPTER 19 - ELECTROCHEMISTRY
REDUCTION POTENTIAL CALCULATIONS
15. Given the following data:

AgCl(s) + e- → Ag(s) + Cl- Eo = 0.22 volts

Zn2+(aq) + 2e- → Zn(s) Eo = -0.76 volts
The voltaic cell represented by: Zn(s)│Zn2+(0.0010M)║Cl-(?M)│AgCl(s)│Ag(s)
has a measured cell potential of 1.17 volts.
What is the molarity of Cl- in this cell?

A. 0.0010M
B. 0.0050M
C. 0.0190M
D. 0.0500M
E. 1.00M
ET: Need to understand line diagrams. Straightforward filling in Nernst equation with one unknown, the [Cl-].

The left side of line diagrams is the anode, and the right side is the cathode.

Eo
Zn → Zn2+ + 2e- +0.76
2(AgCl + 1e- → Ag + Cl-) +0.22
Zn + 2AgCl → Zn2+ + 2Ag + 2Cl- +0.98V

Zn(s) + 2AgCl(s) → Zn2+ + 2Ag(s) + 2Cl-

0.0010M XM

Ecell = Eocell – (0.0592/n)logQ

Ecell = Eocell – (0.0592/n)log([Zn2+][Cl-]2)
1.17 = 0.98 – (0.0592/2) x log([0.0010][X2])
X = 0.0195 = [Cl-]

Chem 162-2012 Final exam review from 2010 final exam 31

 BALANCING REDOX EQUATIONS
(Follow rules in descending order of priority)

(1) Write net reaction.

(2) Identify pairs of substances involved in oxidation (OXLEA) and pairs of
substances involved in reduction half-reactions.
(3) Balance (in the following order)
-- the atoms (not O or H);
-- O, using H2O;
-- H, using H+;
-- charge, using electrons;
-- electrons of each half-cell reaction, using half-equation coefficients.
(4) Add the two half-cell equations.
(5) Get rid of spectator ions/spectator molecules/spectator electrons.
(6) Adjust H+ with OH- if basic solution is requested.
(7) Verify that all atoms and charges are balanced.

Chem 162-2012 Final exam review from 2010 final exam 32

CHEM 162-2010 FINAL EXAM
CHAPTER 19 - ELECTROCHEMISTRY
OXIDATION-REDUCTION REACTION CONCEPTS
7. Consider the unbalanced half reaction:
S2O32- +OH- → SO42- + H2O + e-
When the above half reaction is balanced with whole number coefficients,
which of the following are the correct coefficients for OH- and SO42-?

OH- SO42-
A. 8 3
B. 5 5
C. 4 6
D. 10 2
E. 3 7
ET: Balancing a half-cell equation in basic solution

S2O32- → SO42-
Balance the S’s.
S2O32- → 2(SO42-)
Balance the oxygens with H2O.
S2O32- + 5H2O → 2(SO42-)
Balance the hydrogens with H+.
S2O32- + 5H2O → 2(SO42-) + 10H+
Balance the charge with electrons.
S2O32- + 5H2O → 2(SO42-) + 10H+ + 8e-
Make it basic by adding OH- to both sides.
S2O32- + 5H2O + 10OH-→ 2(SO42-) + 10H+ + 8e- + 10OH-
Simplify the equation.
S2O32- + 5H2O + 10OH-→ 2(SO42-) + 10H2O + 8e-
Get rid of spectators.
S2O32- + 10OH-→ 2(SO42-) + 5H2O + 8e-

Chem 162-2012 Final exam review from 2010 final exam 33

Chem 162-2010 Final Exam + Answers
Chapter 19 - Electrochemistry
Free energy and cell potential calculations/Nernst equation, concentration cell

9. The Eo for the reaction

Cr2O72-(aq) + 6Fe2+(aq) + 14H+(aq) → 2Cr3+(aq) + 6Fe3+(aq) + 7H2O(l)
is +0.56V at 25oC. Calculate the equilibrium constant for the reaction.
A. 7.1x1056
B. 1.4x103
C. 2.9 x 109
D. 37.8
E. 2.5x1028

Eocell = +(0.0592/n)log(K)
ET note: We know Eocell. We just need to calculate “n” to find “K”.

We need to find the value of n, the number of electrons transferred.

Cr2O72- → Cr3+
Cr2O72- → 2Cr3+
Cr2O72- → 2Cr3+ + 7H2O
Cr2O72- + 14H+ → 2Cr3+ + 7H2O
Cr2O72- + 14H+ + 6e- → 2Cr3+ + 7H2O

Fe2+ → Fe3+
Fe2+ → Fe3+ + 1e-
6(Fe2+ → Fe3+ + 1e-)

Cr2O72- + 14H+ + 6e- → 2Cr3+ + 7H2O

6(Fe2+ → Fe3+ + 1e-)
Cr2O72- + 14H+ + 6Fe2+ → 2Cr3+ + 6Fe3+ + 7H2O
n=6

0.56 = +(0.0592/6) x log(K)

K = 7.125 x 1056

Chem 162-2012 Final exam review from 2010 final exam 34

CHEM 162-2010 EXAM III + ANSWERS
CHAPTER 19
ELECTROCHEMISTRY
FREE ENERGY AND CELL POTENTIAL CALCULATIONS/NERNST EQUATION
ET: Very similar to previous problem except that here we have to calculate Eo.

11. Given
Eo(V)
Co2+ + 2e- → Co(s) -0.28
Cd2+ + 2e- → Cd(s) -0.40

What is the equilibrium constant for

Cd(s) + Co2+(aq) ←→ Cd2+(aq) + Co(s)

A. 2.1 x 105
B. 1.1 x 104
C. 3.3 x 10-4
D. 4.5 x 10-6
E. 3.1 x 104
ET: Straightforward; calculate Eocell, n, and then find K

Cd(s) → Cd2+(aq) + 2e- ℰ° = +0.40V

Co2+(aq) + 2e- → Co(s) ℰ° = -0.28V
Cd(s) + Co2+(aq) ←
→ Cd2+(aq) + Co(s) ℰ°cell = 0.12V

Eocell = (0.0592/n)log(K)
0.12 = (0.0592/2) x log(K)
K = 1.13x104

Chem 162-2012 Final exam review from 2010 final exam 35

Chem 162-2010 Final Exam + Answers
Chapter 19 - Electrochemistry
Galvanic cells, line notation & reduction potential

16. If the standard reduction potentials for the couples Cu2+/Cu, Ag+/Ag and
Fe2+/Fe are +0.34V, +0.80V and -0.44V respectively, which is the strongest
reducing agent?

A. Cu
B. Ag
C. Ag+
D. Fe2+
E. Fe
ET: Discuss “Standard Reduction Potential” table as being for reductions, which means “oxidizing agents”, but “reducing agents” is for oxidations.

Standard reduction potential table:

Ag+ + e- → Ag Eo = +0.80V
Cu2+ + 2e- → Cu Eo = +0.34V
Fe2+ + 2e- → Fe Eo = -0.44V

A strong reducing agent means that the substance is easily oxidized.

So change the table to a standard oxidation potential table.
Fe → Fe2+ + 2e-. Eo = +0.44V
Cu → Cu2+ + 2e- Eo = -0.34V
Ag → Ag+ + e- Eo = -0.80V

Fe is the most easily oxidized and therefore the strongest reducing agent.

Chem 162-2012 Final exam review from 2010 final exam 36

 anions
cations
cations
anions

Chem 162-2012 Final exam review from 2010 final exam 37

Chem 162-2010 Final exam + answers
Chapter 19- Electrochemistry
Galvanic cells, line notation & reduction potential concepts

17. Which one of the following statements is false in a galvanic cell?

A. Sustained electron flow cannot occur without the salt bridge or a porous
disk.
B. Electrons flow from the anode to the cathode through an external wire.
C. The electrode compartment in which oxidation occurs is called the anode.
D. Cations flow from the salt bridge to the anode compartment.
E. It is a device for converting chemical energy to electrical energy.
ET: Students need to be familiar with the galvanic and electrolytic cells and their differences.

A. True. The salt bridge contains ions to neutralize the buildup of charges at
the electrodes. If there is no salt bridge, then the charges at the electrodes
will build up, making the system thermodynamically unstable, resulting in
the reaction stopping.
B. True. Oxidation is loss of electrons at the anode. The electrons flow from
the anode to the cathode through an external wire.
C. True. Oxidation is loss of electrons at the anode.
D. False. Negative charge is built up at he cathode. Therefore, cations flow
from the salt bridge to the cathode compartment in order to neutralize the
build up of this negative charge
E. True. The chemicals change spontaneously, by way of the electrons going
through an external wire. On the other hand, an electrochemical cell is one
which converts electrical energy (from a battery) into chemical energy
(increasing the Gibbs free energy of the products).

Chem 162-2012 Final exam review from 2010 final exam 38

Chem 162-2010 Final exam + answers
Chapter 19- Electrochemistry
Free energy and cell potential calculations/Nernst equation, concentration cell calculations

19. Given
Br2(l) + 2e- → 2Br-(aq) Eo = 1.065V
O2(g) + 4H+(aq) + 4e- → 2H2O(l) Eo = 1.229 V
Calculate ∆Go for the reaction below:
2Br2(l) + 2H2O(l) → 4Br-(aq) + O2(g) + 4H+(aq)

A. +31.7 kJ
B. -31.7 kJ
C. -15.8 kJ
D. -42.2 kJ
E. +63.3 kJ
ET note: Straightforward. Use equation “ΔGo = -nFEocell”; calculate n and Eocell, then find ΔGo.

ΔGo = -nFEocell

Eo(V)
2(Br2(l) + 2e- -> 2Br-(aq)) 1.065
+ -
2H2O(l)→ O2(g) + 4H (aq) + 4e -1.229
- +
→ 4Br (aq) + O2(g) + 4H (aq) -0.164
2Br2(l) + 2H2O(l) ←

ΔGo = -4 x 96485 x (-0.164) = 6.33x104 J = 63.3 kJ

Chem 162-2012 Final exam review from 2010 final exam 39

Chem 162-2010 Final Exam + Answers
Chapter 19 – Electrochemistry
Electric work/amperes

31. What mass of copper will be deposited at the cathode if a current of 0.15A
is passed through a solution of CuSO4 for 45 seconds?

A. 2.22 x 10-3g
B. 1.03 x 107g
C. 2.07 x 107g
D. 1.11 x 10-3g
E. 3.50 x 10-5g

Cu2+ + 2e- → Cu
ET note: Straightforward; calculate mol and then convert to mass.

(amperes x seconds)/(96485 x electrons) = mol substance

(0.15 x 45)/(96485 x 2) = mol Cu
= 3.498 x 10-5 mol Cu
3.498 x 10-5 x 63.546g/mol = 2.22 x 10-3 g Cu

Chem 162-2012 Final exam review from 2010 final exam 40

 CHAPTER 14 FORMULAS
ET: Rate = speed. Using a diagram with Y being 100 lbs and 110 lbs, and days 0 to 5, show that the increase in weight = slope = (Y2 – Y1)/(X2 – X1) = +2lb/day.
Decrease in weight = -increase in weight = -slope = -(Y2 – Y1)/(X2 – X1) = -2lb/day.

ET: Point out that table in middle of page contains the key formulas in kinetics. Discuss these formulas at beginning of recitation, focusing on 1o reaction.

C12H22O11(sucrose) + H2O → 2 C6H12O6(glucose)

Rate of sucrose disappearance = -(∆ [sucrose])/(∆ time) = -([sucrosef] - [sucrosei])/(tf - ti)
Rate of glucose appearance = 2 x Rate of sucrose disappearance
aA + bB → cC + dD
General rate of reaction = -(1/a)(∆[A]/∆t) = -(1/b)(∆[B]/∆t) = (1/c)(∆[C]/∆t) = (1/d)(∆[D]/∆t)
Determination of order of reaction through method of initial rates:
For a single reactant:
Rate 1 = k[A1]m
Rate 2 = k[A2]m
(Rate 1/Rate 2) = (k[A1]m)/(k[A2]m) = ([A1]/[A2])m
For two reactants:
Rate1 = k[A1]m[B1]n
Rate2 = k[A2]m[B1]n
(Rate1/Rate2) = (k[A1]m[B1]n)/(k[A2]m[B1]n) = (A1/A2)m

Integrated
Reaction Differentiated rate law k
Order Reaction Rate** RATE LAW*** (y = mx + b) Half-life* units
o
0 AvgRate = -(C2-C1)/(t2-t1) InstRate = k[C] =k [C]t = -kt + [C]o t1/2 = [C]o/2k M1s-1
1 AvgRate = -(C2-C1)/(t2-t1) InstRate = k[C]1 ln[C]t = -kt + ln[C]o t1/2 = 0.693/k Mos-1
2 AvgRate = -(C2-C1)/(t2-t1) InstRate = k[C]2 1/[C]t = kt + 1/[C]o t1/2 = 1/(k[C]o) M-1s-1
** Rate of appearance = +slope; rate of disappearance = -rate of appearance = -slope.
*** Differentiated Rate Law may be for more than one component, e.g., Rate = k[C]1[D]2

*Half-lives:
For a zero order reaction, each successive half-life is ½ the time of the preceding one.
For a first order reaction, each successive half-life is equal in time to the preceding one.
For a second order reaction, each successive half-life is double time of the preceding one.

Arrhenius equation:
k = Ae(-Ea/RT)
ln k = -Ea/RT + ln A; ln k = ((-Ea/R) x (1/T)) + ln A
A = frequency factor = combination of steric factor and collisional frequency
Ea = energy of activation
ln k2 - ln k1 = (-Ea/RT2) - (-Ea/RT1)
ln (k2/k1) = -(Ea/R)[(1/T2) - (1/T1)]
Chem 162-2012 Final exam review from 2010 final exam 41
 C12H22O11 + H2O → 2C6H12O6 (hypothetical example)
Hypothetically: Reaction is 2nd order with respect to C12H22O11 and zero order with
Rate Plot C (M) Time (s)
ET: Discuss formation of plot from data; then discuss definitions 1.0 0
X1,Y1 0.9 0.1
1 0.8 0.3
Rate = -(Y2 - Y1)/(X2 - X1) Note 1,2,3,4 0.7 0.4
Rate = -(0.8-1.0)/(0.25-0) = +0.80M/s Note2 0.6 0.7
0.5 1.0
0.9 0.4 1.5
0.3 2.3
0.2 4.0
Rate = k[C]2
k=1
X2,Y2
0.8
SUCROSE CONCENTRATION (M)

Note1Rate: Change in concentration of a reactant or product per change in time.

2 Average rate: Rate calculated between two points. Note rate faster at
0.7 beginning than end due to the concentration of C12H22O11 being greater at the
beginning.
3 Instantaneous rate: Rate calculated at one point.

4 Initial rate: Instantaneous rate at time close to zero, to avoid the complication

of reverse reactions.
0.6
5 Rate law: Relationship between rate of reaction and concentration of

reactants

X1,Y1
0.5
Rate = -(Y2 - Y1)/(X2 - X1)
Rate = -(0.3- 0.5)/(2.33-1.0) = 0.15M/s

0.4

0.3 X2,Y2

0.2
0 1 2 3 4 5

Chem 162-2012 Final exam review from 2010 final exam TIME (s) 42
PRIORITIES IN SOLVING KINETICS PROBLEMS

FIND REACTION ORDER

• Use method of initial rates
- If initial rates are available*
*If initial rates are not available they can be calculated, but that is probably not worth the time on an exam.

• Evaluation of half-life data

• Identifying integrated rate law straight line graph
- From actual graph
- From description of graph
• Recognizing k units
• Plugging numbers into equations to get a constant “k”.
(the “constant-constant” method)
- Integrated rate law equation
- Differentiated rate law equation
- Half-life equation

FIND THE RATE CONSTANT

• After identifying reaction order, plug numbers into
- Differentiated rate law equation or
- Integrated rate law equation or
- Half-life equation
• Slope or negative slope of integrated rate law graph

Note: Diff. rate law equation contains conc. and rate terms.
Integ. rate law and t1/2 equations contain conc. and time terms.

EVERYTHING ELSE
• Use table of formulas for everything else.

Chem 162-2012 Final exam review from 2010 final exam 43

 COLLISION THEORY, INCLUDING ARRHENIUS EQUATION
Collision theory is a model that explains reaction rates.
o Molecules must collide to react.
o Frequency of molecular collisions is important
o Molecules must have the correct steric orientation.
o Molecules must have a minimum energy (≥activation energy)
o Rate of reactions increase with temperature
ET: Possible way to discuss Activation Energy is with molecular models, e.g., I- + CH3Br → CH3I + Br-

Arrhenius equation: k = Ae(-Ea/RT)

ln k = -Ea/RT + ln A

Rate = k[A]m[B]n

The “k” in the Arrhenius equation is the same as the “k” in the rate equ.

Chem 162-2012 Final exam review from 2010 final exam 44

 REQUIREMENTS FOR HYPOTHETICAL MECHANISMS

1. The sum of the calculated elementary stoichiometry steps must be

equal to the experimentally determined stoichiometric equation.
2. The calculated rate law must be consistent with the experimentally
determined rate law.
3. No elementary step can have a molecularity greater than three (even
three is rare).

Chem 162-2012 Final exam review from 2010 final exam 45

CHEM 162-2010 FINAL EXAM
CHAPTER 14 - KINETICS
RATES,RATE CONSTANTS, REACTION ORDERS, HALF-LIVES CALCULATIONS
REACTION RATE

41. The instantaneous rate of the second-order decomposition of A is 2.70x10-3M/s

when [A] = 0.60M. What is the instantaneous rate of this reaction when [A] =
0.20M?

A. 6.0x10-4M/s
B. 4.5x10-4M/s
C. 3.0x10-4M/s
D. 8.0x10-4M/s
E. 1.2x10-3M/s
ET: First thing to do is to find k. Go from differentiated rate law to k to differentiated rate law.

If you are provided with the rate and concentration then use the “Differentiated
Rate Law”. The Differentiated Rate Law for a second order reaction is: Rate =
k[C]2.
Rate = k[C]2
2.7 x 10-3 = k[0.60]2
k = 0.0075
The rate constant doesn’t change no matter what the rate is or no matter what
the concentration is. Hence, use the same equation to determine the rate:
Rate = k[C]2
Rate = 0.0075 x [0.20]2
Rate = 3.0 x 10-4

Chem 162-2012 Final exam review from 2010 final exam 46

 CHEM-2010 FINAL EXAM + ANSWERS
CHAPTER 14 - KINETICS
RATES,RATE CONSTANTS, REACTION ORDERS, HALF-LIVES CONCEPTS
INTEGRATED RATE LAW

ET: First order plot (ln[A]t on y-axis, vs. t on x-axis) can be used to find the rate constant.

If a plot of ln[A] vs time gives a straight line, then the reaction is first order.
ln[A]t = -kt + ln[A]o
Y = mx + b
k = -the slope
X1 = 0
Y1 = -1.47
X2 = 1195
Y2 = -3.60

slope = (Y2-Y1)/(X2-X1) = (-3.60 –(-1.47))/(1195-0) = -1.78 x 10-3s-1

-slope = k = 1.78 x 10-3s-1
B = Answer
Chem 162-2012 Final exam review from 2010 final exam 47
Very complex problem
Chem 162-2010 final exam
Chapter 14A - Kinetics
Rates,rate constants, reaction orders, half-lives calculations
10. Consider the reaction N2(g) + 3H2(g) → 2NH3(g). This reaction proceeds by the rate law
-(∆P(N2))/∆t = kP(N2), where k = 1.25x10-3s-1.
Starting with 0.45 atm of N2 and 1.55 atm of H2 and no NH3, what will the total pressure be after 145s
have elapsed? [Hint: total pressure is the sum of all the partial pressures at that time.]
A. 0.375 atm
B. 1.85 atm
C. 1.33 atm
D. 0.075 atm
E. 0.650 atm

ET: The reaction is first order. We have the value of k. We have the initial pressure and the time, so use
the integrated rate law to find the final pressure. The difficult part of this problem is realizing that the
integrated rate law should be dealing with the limiting reactant, which is N2 in this case.

N2 + 3H2 → 2NH3
Initial 0.45 atm 1.55 atm 0 atm
Change -X -3X +2X
145 second pressures 0.45-X 1.55-3X 2X

ln[C]t = -kt + ln[C]o

ln[C]t = (-1.25x10-3 x 145s) + ln[0.45atm]
[C]t = 0.375M

0.45 – X = 0.375
X = 0.075 atm

N2 + 3H2 → 2NH3
Initial 0.45 atm 1.55 atm 0 atm
Change 0.075 atm 3 x 0.075 = 0.225 atm 2 x 0.075 = 0.150 atm
145 second pressures 0.375 atm

N2 + 3H2 → 2NH3
Initial 0.45 atm 1.55 atm 0 atm
Change 0.075 atm 0.225 atm 0.150 atm
145 second pressures 0.375 atm 1.325 atm 0.150 atm

Total pressure after 145 seconds = 0.375 + 1.325 + 0.150 = 1.85 atm

Chem 162-2012 Final exam review from 2010 final exam 48

CHEM 162-2010 FINAL EXAM
Chapter 14A - Kinetics
Rates,rate constants, reaction orders, half-lives calculations
43. Consider the reaction 2A + B → 3C + D. The rate of reaction was measured as a function of concentration.
From the data below, calculate the rate law.
Exp. [A] M [B] M Initial rate M/s
1 0.300 0.100 1.23 x 10-4
2 0.400 0.100 2.91 x 10-4
3 0.300 0.300 1.11 x 10-3

A. 4.09x10-3[A][B]
B. 1.37x10-2[A]2[B]
C. 0.455[A]3[B]2
D. 1.37[A]2[B]2
E. 0.0409[A][B]2

Use initial rate method to find rate law. Use simultaneous equations to cancel unknowns.
Rewrite table to line up initial rates.
Experiment [A] (M) [B] (M) Initial rate (M/s)
1 0.300 0.100 1.23 x 10-4
2 0.400 0.100 2.91 x 10-4
3 0.300 0.300 11.1 x 10-4

Rate = k[A]m[B]n
Use the initial rate method.
We can proceed by getting rid of “A” in order to calculate “n”.
Divide experiment 3 by experiment 1:
11.1 x 10-4 = k[0.300]m[0.300]n
1.23 x 10-4 = k[0.300]m[0.100]n
9.02 = 3n
n = 2.0

We can proceed by getting rid of “B” in order to calculate “m”.

Divide experiment 2 by experiment 1:
2.91 x 10-4 = k[0.400]m[0.100]n
1.23 x 10-4 = k[0.300]m[0.100]n
2.37 = 1.33m
m = 3.0

Rate = k[A]3[B]2
This must be “C”, but we can go further to calculate “k”
Plug any set of numbers into the rate equation to find k.
Exp. 1:
1.23x10-4 = k[0.300]3[0.100]2
k = 0.456
Rate = 0.456[A]3[B]2

Chem 162-2012 Final exam review from 2010 final exam 49

Chem 162-2010 Final Exam + Answers
Chapter 14 – Kinetics
Reaction mechanisms, activation energy & catalysts calculations
Mechanisms
30. Given the following mechanism, what is the expected rate law?

→ B
2A ← fast equilibrium
A+B→C slow
C→D fast

A. rate = k[A][B]
B. rate = k[A]3
C. rate = k[B]1/2
D. rate = k[A]3[C]
E. rate = k[A]2[B]1

Rate always dependent only on the slow step; this is a typical rate law for a
component in the slow step being a reactive intermediate.
Rate = k[A][B]
But B is an unstable intermediate. Therefore, replace it using the fast
equilibrium equation.
Rate of forward reaction = kf[A]2
Rate of reverse reaction = kr[B]
Rate of forward reaction = Rate of reverse reaction
kf[A]2 = kr[B]
[B] = ((kf/kr)[A]2)
Rate = k[A][B]
Rate = k[A]((kf/kr)[A]2)
Rate = k[((kf/kr)[A])][A]2
Rate = k’[A]3

Chem 162-2012 Final exam review from 2010 final exam 50

CHEM 162-2010 EXAM I
CHAPTER 14 - KINETICS
REACTION MECH., ACTIVATION ENERGY & CATALYSTS CALCULATIONS

13. The rate constant for the reaction CO(CH2COOH)2(aq) → CO(CH3)2(aq) +

2CO2(g) is 4.75 x 10-4s-1 at 20.0oC and 1.63 x 10-3s-1 at 30.0oC. Find Ea for this
reaction.

A. 1.32 kJ
B. 615 kJ
C. 91.0 kJ
D. 898 kJ
E. 10.9 kJ

Using the Arrhenius equation:

k1 = 4.75 x 10-4s-1 T1 = 20oC = 293K
k2 = 1.63 x 10-3s-1 T2 = 30oC = 303K
ln (k2/k1) = -(Ea/R)[(1/T2) - (1/T1)]
ln ((1.63x10-3)/(4.75 x 10-4)) = -(Ea/8.314)[(1/303) - (1/293)]
Ea = 9.10x104 J = 91.0 kJ/mol

Chem 162-2012 Final exam review from 2010 final exam 51

 CHEM 162-2010 FINAL EXAM

Chem 162-2012 Final exam review from 2010 final exam 52

CHEM 162-2010 FINAL EXAM
CHAPTER 14 - KINETICS
REACTION MECH., ACTIVATION ENERGY & CATALYSTS CONCEPTS
REACTION MECHANISMS

The addition of a catalyst to a chemical reaction

34. The addition of a catalyst to a chemical reaction.

A. Increases the concentration of products at equilibrium.

B. Increases the fraction of reactant molecules with a given kinetic energy
C. Provides an alternate mechanism with a lower activation energy.
D. Lowers the enthalpy change of the overall reaction.
E. Lowers the activation energy of the forward reaction without affecting the
activation energy of the reverse reaction.

ET: Use catalysis diagram to answer most of these questions. Point out that the catalyst also changes the frequency factpr in the Arrhenius equation. The
frequency factor, “A” should really be called the frequecy-steric factor. How the molecules interact changes when using a catalyst. The rate of the reaction
can speed up due to a change in the molecules orientations.

A. False. A catalyst has no effect on the concentration of reactants or

products, i.e., it doesn’t change the equilibrium constant. It just serves to
speed up the reaction.
B. False. Only an increase in temperature increases the fraction of reactant
molecules with a given kinetic energy.
C. True. A catalyst provides an alternate mechanism with a lower activation
energy. It is as if a person walked through a tunnel in the mountain (low
activation energy) as opposed to climbing over the mountain (high
activation energy) to get to the other side.
D. False. A catalyst does not affect the enthalpy of the reactants or the
products. If it did, then the equilibrium constant would change, but the
equilibrium constant doesn’t change due to using a catalyst.
E. False. It lowers the activation energy of the forward and reverse reactions.

Chem 162-2012 Final exam review from 2010 final exam 53

 CHAPTER 20 - SELECTED EQUATIONS FOR NUCLEAR CHEMISTRY
Radioactivity, or radioactive decay, is the spontaneous change of the nuclei of certain atoms, accompanied by the emission of subatomic particles and/or high-frequency
electromeagnetic radiation.

CAPTURED OR EMITTED PARTICLES/RAYS

4 4
Alpha particles 2α = 2He Sum of protons and neutrons = mass number (neutrons and protons are nucleons)
*** - 0 0
Beta particles β = -1β = -1e Number of protons (or charge) = atomic number
** 0
Gamma ray 0γ
Positron particle β+= 01e
1
Neutron 0n
1
Proton 1H
**Nuclei have energy levels just as electrons do. When a nucleus in an excited state drops to a lower energy level, the energy is released in the form of a gamma ray.
Atoms that emit gamma rays are high energy and are identified with an asterisk.
***An electron can be emitted or captured. Capture: An inner core electron can “fall” into the nucleus to combine with a proton and form a neutron. 0-1e + 11H → 10n. An
outer shell electron then drops to fill the vacancy, releasing an X-ray. 12553I + 0-1e → 12552Te + 00γ

RADIOACTIVE DECAY RATE Units in 1o reactions

Reaction Differential Integrated cancel, so are irrelevant.
Order Rate Law rate law Half-life*
1 Rate = λN ln(Nt/No) = -λt t1/2 = 0.693/λ**
ln(Nt) = -λt + ln(No)
Rate = rate of radioactive decay = activity (“A”) = disappearance of atoms/sample
per second = disintegrations of atoms/sample per second = disintegrations per
second = decays per second
λ = the decay constant
N = concentration in molarity, number of atoms/sample, molecules/sample, moles/sample,
g/sample, %, % of a sample, emission counts/sample, disintegrations/sample, rate of
decay/sample
Note similarity to equations from KINETICS chapter:
KINETICS
Reaction Differential Integrated
Order Rate Law rate law Half-life*
1 Rate = k[A] ln(At) = -kt + ln(Ao) t1/2 = 0.693/k
* For a first order reaction, each successive half-life is equal to the preceding one.
**Unlike chemical reactions, k is not dependent on T, or anything else.
MASS DEFECT
Calc. nuclear mass (= nucleon mass) = Actual nuclear mass + mass defect
(Calc’d mass of neutrons + protons) (actual mass of nucleus) (binding energy)

E = mc2 J = kg x (3.00 x 108 ms-1)2

or 931.5 MeV/u
Chem 162-2012 Final exam review from 2010 final exam 54
 Effects of Radiation
Somatic Damage: damage to organism itself: sickness or death
Genetic Damage: damage to genetic machinery: affects offspring

Biological effects depend on:

(1) Energy of Radiation Measured in rad = 10-2J/kg tissue
(2) Penetrating effect of Radiation
Gamma: Highly penetrating
Beta: penetrates about 1 cm
Alpha: stopped by skin
(3) Ionizing ability of radiation. This describes the ability of the
radiation to remove electrons from biological molecules, forming ions.
Generally detrimental to health.

Gamma: penetrates well, but cause only occasional ionization

Alpha particles: not very penetrating, but very effective at causing
ionization if inside the body.
Beta particles: penetrating; not as likely to ionize
Gamma rays: Very penetrating; not very ionizing

Chem 162-2012 Final exam review from 2010 final exam 55

CHEM 162-2010 FINAL EXAM
CHAPTER 20 - THE NUCLEUS
RADIOACTIVE DECAY PARTICLES AND RAYS
20. What is the product of the following nuclear reaction?
236 1 136
92U → 4 0n + 53I + ?
96
A. 38Sr
B. 9039Y
C. 9640Zr
D. 9841Nb
E. 9639Y
ET: Simple math

236
92U → 4 10n + 13653I + 9639?
236
92U → 4 10n + 13653I + 9639Y

Chem 162-2012 Final exam review from 2010 final exam 56

 BELT OF STABILITY
- The narrow band of stable isotopes (dark blue and light blue circles) is sometimes called the peninsula of stability in a sea of instability. Any nuclide in the sea
of instability (pink circles) will decay in such a way that the nucleus can come ashore onto the peninsula. Only 279 of the ~2000 known nuclides are stable.
- In three “Belt of Stability” slides is a discussion of the decay of a uranium nuclide and two cerium nuclides. Relative to a stable reference atom, the uranium
nuclide has too many protons, which makes it unstable. Relative to a stable cerium nuclide, the cerium nuclides either have too high or too low a ratio of
neutrons to protons, which make them unstable. Too high a ratio is unstable because neutrons, by themselves, are unstable, having only a 12.6 minute half-life.
Too low a ratio is unstable because of the proton-proton interaction. The perfect ratio is when the neutrons form a stable complex with the protons, without
any extra protons or any extra neutrons. The modes of decay are presented. These modes are typical of corresponding nuclides that contain either too many
protons, or a non-optimum ratio of neutrons to protons.

Instability due to too many protons.

Mode of decay to decrease number of protons:
alpha decay
Reference point: 209 (126 neutrons)83 protonsBi.
e.g., 23892U → 42α + 23490Th
238
92 U Result: Going in correct direction (90 is approaching 83 protons).

209
83 Bi
Too many protons and
neutrons
Unstable nuclide due to high neutron to proton ratio relative in this region;
to stable nuclide. Protons > 83
Reference 140 (82 neutrons)58 protonsCe is approx. the average therefore, decay by alpha
of the 4 stable cerium nuclides.
Rewrite: 82n58pCe; neutron:proton ratio = 1.41 emission
Example of unstable isotope: 148 (90 neutrons58 protonsCe Lose protons and
148
Rewrite: 90n58pCe; neutron:proton ratio = 1.55 58 Ce (unstable high n:p ratio) neutrons
Mode of decay to approach reference (i.e., to
decrease neutron to proton ratio) is electron emission. 140
58Ce
concurrently
Unstable nuclide due to low neutron to proton ratio relative to
148 0
58Ce → -1e +
148
59La (stable) stable nuclide.
Rewrite: 90n58pCe → 0-1e + 8959Pr; neutron:proton ratio = 1.51 Reference 140 (82 neutrons)58 protonsCe is approx. the average of the 4
stable cerium nuclides.
Rewrite: 82n58pCe; neutron:proton ratio = 1.41
Example of unstable isotope: 130 (72 neutrons)58 protonsCe
Rewrite: 72n58pCe; neutron:proton ratio = 1.24
Mode of decay to approach reference (i.e., to increase neutron
to proton ratio) is beta emission or electron capture.
130 Beta emission: 13058Ce → 0+1e + 13057La
58Ce (unstable low
n:p ratio) Rewrite: 72n58pCe → 0+1e + 7357La; neutron:proton ratio = 1.28
Result: Going in correct direction
Electron capture: 13058Ce + 0-1e → 13057La
Rewrite: 72n58pCe + 0-1e → 7357La; neutron:proton ratio = 1.28
Result: Going in correct direction

Neutron to proton ratio

too high in this region;
therefore, becomes Neutron to proton ratio too low in
stable through decay by this region; therefore, decay by
beta emission positron emission and/or electron
capture

Chem 162-2012 Final exam review from 2010 final exam 57

CHEM-2001 FINAL EXAM + ANSWERS
CHAPTER 20 - NUCLEAR CHEMISTRY
RADIOACTIVE DECAY KINETICS

24. Which of the following statements regarding nuclear reactions is false.

A. Nuclear reactions involve substantially greater energy changes than
ordinary chemical reactions.
B. Nuclear decay follows first order kinetics.
C. Nuclear reactions do not require conservation of mass.
D. Nuclear reactions are typically the same for different isotopes of the same
element.
E. The rate of nuclear decay is not temperature dependent.
ET: Show “Belt of stability” diagram to discuss “D”. Also, mention that nothing affects the rate of nuclear decay.

A. True. I don’t know if all nuclear reactions involve substantially greater

energy changes than ordinary chemical reactions, but the nuclear reactions
involving splitting or fusion of nuclei provide much greater energy than
ordinary chemical reactions.
B. True. Nuclear decay always follows first order kinetics.
C. True. Virtually all nuclear reactions involve going from a higher energy
state into a lower energy state, losing mass and releasing energy.
D. False. Typically one isotope is stable while another one is not. The
unstable ones radiate particles or energy, while changing into another
nuclide.
E. True. I don’t know why, but temperature cannot change the rate of nuclear
decay. One would think that, based on collision theory, the number of
atoms that can reach the energy of activation would increase with
increasing temperature, but apparently this isn’t so.

Chem 162-2012 Final exam review from 2010 final exam 58

 ET: Show stability of 56-Fe vs reactants with typical simple elementary step curve .

FISSION & FUSION BINDING ENERGY

10 56
26Fe (atom most stable per nucleon)

8
Fission
e.g., 92U + 0n → 56Ba + 9236Kr + 3 10n
235 1 141
Binding energy per nucleon (MeV)

7 (capable of chain reaction due to extra neutrons formed)

Critical mass: Mass of reactant needed to achieve the
critical state to have a chain reaction.
In an atomic bomb resulting from the explosive fission of U-235, a supercritical mass is achieved
suddenly when two sub-critical pieces are brought together.
6
Nuclear reactor: Binding energy creates electricity
Control rods: Absorbs excess neutrons
5

Fusion
e.g., 21H + 31H → 42He + 10n
3 (requires a temperature > 40,000,000K for
the positively charged nuclei to move fast
enough to overcome the plus plus
2 repulsion. A fusion bomb (“hydrogen
bomb”) uses a fission explosion (uranium
or plutonium) to provide the high
temperature needed to initiate fusion.)
1 H-H fusion occurs in the sun.

0
0 50 100 150 200 250 300
Mass Number

Chem 162-2012 Final exam review from 2010 final exam 59

Chem 162-2010 Final Exam + Answers
Chapter 20 - The Nucleus
Radioactive decay particles and rays

6. The stable isotopes of lead are Pb-204, Pb-206, and Pb-208. The unstable
isotope Pb-214 is most likely to undergo

A. electron capture
B. neutron emission
C. α particle emission
D. β particle emission
E. positron emission
ET: Unstable isotopes decay in a way that will make them more stable. Pb-214 tries to become more like Pb-204, -206 and -208, with regard to the neutron to
proton ratio.
ET: Discuss fission, fusion and critical mass in above Fe-56 slide.

Except for hydrogen (11H), which has 0 neutrons and 1 proton, stable isotopes
have a ratio of approximately 1 neutron:1proton, to 1.5 neutrons:1 proton.

Pb-204 has a ratio of (122/82=) 1.49 neutrons to 1 proton.

Pb-206 has a ratio of (124/82=) 1.51 neutrons to 1 proton.
Pb-208 has a ratio of (126/82=) 1.54 neutrons to 1 proton
Pb-214 has a ratio of (132/82=) 1.61 neutrons to 1 proton

Clearly, Pb-214 is the least stable, with a high neutron:proton ratio.

214
A. 82 + 0-1e → 21481Tl neutron:proton = 133/81 = 1.64. This ratio is going
in the wrong direction.
214 1 213
B. 82Pb → 0n + 82Pb neutron:proton = 131/82 = 1.60. This ratio is going
in the correct direction.
214 4 210
C. 82Pb → 2He + 80Tl neutron:proton = 130/80 = 1.63. This ratio is
going in the wrong direction.
214 0 214
D. 82Pb → -1e + 83Hg neutron:proton = 131/83 = 1.58. This ratio is going
in the correct direction.
214 0 214
E. 82Pb → +1e + 81Tl neutron:proton = 133/81 = 1.64. This ratio is going
in the wrong direction.

Neutron emission and beta particle emission are both going in the correct direction, but
beta particle emission, not neutron emission, is what actually happens.

Chem 162-2012 Final exam review from 2010 final exam 60

CHEM-2010 FINAL EXAM + ANSWERS
CHAPTER 20 - NUCLEAR CHEMISTRY
NUCLEAR BINDING ENERGY
2. What is the binding energy for 23793Np? 1p = 1.0073u, 1n = 1.0087u, 1e- = 5.49x10-4u, the atomic mass of 23793Np =
237.0481u; 1.66 x 10-24g = 1u
(The problem should have said binding enery of 23793Np per atom.)

A. 2.89 x 10-10J
B.
C.
D.
E.

ET: Calculated nuclear mass = Actual nuclear mass + Mass defect. Mass defect can be converted into binding energy (E=mc2).
ET: “u” is atomic mass units, amu’s, or “Daltons” or grams/mol. Note that sometimes mass defect or binding energy is asked per mole, per atom, or per nucleon.

Calculated Np nuclear mass = Actual nuclear mass + Mass defect

93 11H + 144 10n = 23793Np + mass defect

Calculated nuclear mass = (93 x 1.0073) + (144 x 1.0087) = 238.932u

Actual nuclear** mass = actual atomic mass – mass of electrons
= 237.0481u – (93 x (5.49x10-4)) = 236.997u
**Nuclear mass is the mass of the atom without its electrons.

Calculated nuclear mass = Actual nuclear mass + Mass defect

238.932u = 236.997u + mass defect
mass defect = 1.935u

1.66 x 10-24g = 1u

1.935u x (1.66 x 10-24g/u) x (1 kg/1000g) = 3.212 x 10-27 kg

E = mc2
E = 3.212 x 10-27 kg x (3 x 108m/s)2 = 2.891 x 10-10 kgm2/s2 x (1J/((kgm2/s2))
= 2.89 x 10-10J

Chem 162-2012 Final exam review from 2010 final exam 61

CHEM 162-2010 FINAL EXAM
CHAPTER 20 - THE NUCLEUS
RADIOACTIVE DECAY KINETICS

40. The specific rate constant, λ, for the radioactive decay of 11B is 0.0490s-1. What
mass of a 0.500g sample of 11B will remain after 28.0s?

A. 0.250g
B. 0.127g
C. 0.305g
D. 0.404g
E. 0.0625g
ET: The order and rate constant are already determined. Given time, k and initial concentration, find final concentration with the integrated rate law.

[No] = 0.500g
[Nt] = ?
t = 28s
k = 0.0490s-1
ln(Nt) = -kt + ln(No)
ln(Xg/sample) = (-0.0490 x 28) + ln(0.500g/sample)
X = 0.1268g

Chem 162-2012 Final exam review from 2010 final exam 62

CHEM-2001 FINAL EXAM + ANSWERS
CHAPTER 20 - NUCLEAR CHEMISTRY
RADIOACTIVE DECAY KINETICS

47. A sample of wood from an Egyptian tomb has a 14C activity of 7.07 dpm
(disintegrations per minute) per gram of C, while a sample of freshly cut wood has
an activity of 15.3 dpm per gram of C. Calculate the age of the wood. The half life
of 14C is 5730 years.

A. 5100 years
B. 3600 years
C. 6400 years
D. 7200 years
E. 9200 years
ET: Carbon-14 dating to determine length of time the wood is dead. Solve problem qualitatively, then quantitatively first finding k, then using the integrated rate law with
initial and final concentrations and k to find t.

Qualitative approach:
The half-life of the 14C is 5730 years. Since going from a concentration of 15.3 dpm
to 7.7 dpm is one half-life, and the concentration is 7.07 dpm, then we have gone to
slightly more than one half-life. Hence, the age of the wood should be slightly
greater than 5730 years. 6400 years is a reasonable guesstimate.

Quantitative approach:
t1/2 = 0.693/λ
5730 = 0.693/λ
λ = 0.00012094

Use the Integrated Rate Law, ln(At/Ao) = -λt

ln(Nt) = -λt + ln(No)
ln(7.07) = -0.00012094 x t + ln(15.3)
t = 6383 years

Chem 162-2012 Final exam review from 2010 final exam 63

 Effects of Radiation
Somatic Damage: damage to organism itself: sickness or death
Genetic Damage: damage to genetic machinery: affects offspring

Biological effects depend on:

(1) Energy of Radiation Measured in rad = 10-2J/kg tissue
(2) Penetrating effect of Radiation
Gamma: Highly penetrating
Beta: penetrates about 1 cm
Alpha: stopped by skin
(3) Ionizing ability of radiation. This describes the ability of the
radiation to remove electrons from biological molecules, forming ions.
Generally detrimental to health.

Gamma: penetrates well, but cause only occasional ionization

Alpha particles: not very penetrating, but very effective at causing
ionization if inside the body.
Beta particles: penetrating; not as likely to ionize
Gamma rays: Very penetrating; not very ionizing

Chem 162-2012 Final exam review from 2010 final exam 64

CHEM 162-2010 FINAL EXAM
CHAPTER 20 - THE NUCLEUS
MISCELLANEOUS
14. The most dangerous feature of radioactivity is

A. the amount of gamma radiation emitted.

B. the solubility of most isotopes.
C. the long half-lives of radioisotopes.
D. the ionizing of important biological compounds.
E. the penetrating power making it hard to contain.
ET: Discuss reference table.

A. Rarely, if ever, does a radioactive nuclei emit gamma radiation.

B. Although the isotope might be soluble, it is not necessarily dangerous.
C. Long half-lives contribute to danger, but if the emitted particle or ray is not
dangerous, then the radioactivity is not dangerous.
D. Radiation can ionize molecules in living matter. Even slight exposure can
damage DNA and cause birth defects, leukemia, bone cancer, and other
forms of cancer.
E. Highly penetrating radioactive isotopes can be contained in containers such
as Pb.

Chem 162-2012 Final exam review from 2010 final exam 65

CHAPTER 18 - SPONTANEITY, ENTROPY AND FREE ENERGY
First law of thermodynamics: Energy can neither be created nor destroyed.
Second law of thermodynamics: The entropy of the universe always increases in a
spontaneous process.
Third law of thermodynamics: The entropy of a perfectly ordered crystalline substance at 0
K is zero.

Entropy describes the number of arrangements (positions and/or energy levels) available to
a system.
Entropy is (officially called chaos, disorder, randomness) positional freedom, or
positional availability, or disorder, the number of microstates or number of energy levels
or being unconfined positionally
or escape from positional confinement
or freedom from positional confinement

ΔGo = ΣnpΔGof(products) - ΣnrΔGof(reactants)

ΔHo = ΣnpΔHof(products) - ΣnrΔHof(reactants)
ΔSosystem = ΣnpSoproducts - ΣnrSoreactants

ΔSsystem = ΣnpSproducts - ΣnrSreactants (used for ΔSsystem anytime)

ΔSsystem = ΔHsystem/T (used for ΔSsystem only when at equilibrium)
Trouton’s rule: At normal B.P., ΔSvaprization ≈ 87J mol-1K-1
ΔSsurr = ΔHsurr/T = -ΔHsystem/T (used for ΔSsurr anytime)
ΔSuniv = ΔSsys + ΔSsurr = ΔSsys – (ΔHsys/T)

Four ways to find ΔGo:

(1) ΔGo = ΔHo - TΔSo (or ΔG = ΔH - TΔS)
(2) ΔGo = ΣnpΔGof(products) - ΣnrΔGof(reactants)
(3) ΔGTo = ΔG1o + ΔG2o (i.e., adding equations [Hess’s law])
(4) ΔGo = -RT ln(K)
ΔG = ΔGo + RT ln(Q) (Q can be any pressure or concentration)

wmax = ΔG
lnKeq = ((-∆Ho/R) x 1/T) + ∆So/R
Plot straight line: Y = mX + b
ln(K2/K1) = -(∆Ho/R)((1/T2) – (1/T1)): van’t Hoff equation
ln(P2/P1) = -(∆Hvapno/R)((1/T2) – (1/T1)): Clausius-Clapeyron equation

Chem 162-2012 Final exam review from 2010 final exam 66

Chem 162-2010 Final Exam + Answers
Chapter 18 – Thermodynamics
Free energy concepts

8. What is the physical significance of ∆G?

A. The amount of heat transferred at constant temperature.
B. The maximum work that a system can do.
C. The temperature dependence of ∆H.
D. The degree of disorder of the system.
E. The temperature dependence of ∆S.
ET: ∆G and work are both energy. When ∆G does work, the energy isn’t all converted into work.

This is a conceptually difficult question.

A. False. Heat transferred is ΔH, not ΔG.
B. True. ΔG = workmax
C. False. Not related. ∆G is highly temperature dependent; ∆H is only
slightly temperature dependent.
D. False. The degree of disorder is ΔS, not ΔG.
E. False. Not related. ∆G is highly temperature dependent; ∆S is only
slightly temperature dependent.

Chem 162-2012 Final exam review from 2010 final exam 67

Chem 162-2010 Final Exam
Chapter 18-Thermodynamics
Free energy and equilibria concepts

12. Under standard conditions, calcium reacts readily with chlorine gas. What
conclusions may be drawn from this fact?

A. Keq > 1 and ∆Go < 0

B. Keq < 1 and ∆Go > 0
C. Keq > 1 and ∆Go = 0
D. Keq < 1 and ∆Go < 0
E. Keq > 1 and ∆Go > 0
ET: If the reaction goes to the right from standard conditions, then ∆Go < 0, and the [Ca2+] and [Cl-] concentration increases.

Ca + Cl2 ←→ Ca2+ + 2Cl-

1M 1atm 1M 1M
If the reaction goes to the right spontaneously under standard state conditions,
then the concentration of products will increase from the initial 1M, and the
reactants will decrease, and therefore, Keq >1. If the reaction goes to the right
spontaneously under standard state conditions then ∆Go < 0.

Chem 162-2012 Final exam review from 2010 final exam 68

CHEM 162-2010 HOURLY EXAM III + ANSWERS
CHAPTER 18: THERMODYNAMICS
FREE ENERGY AND EQUILIBRIA CALCULATIONS

22. Calculate ∆G for the following reaction at 400K when the pressures of
NH3(g) and CO2(g) are 1.00 atm and 2.00 atm, respectively

→ 2NH3(g) + CO2(g)
NH2CONH2(s) + H2O(l) ← ∆Go = 27.6 kJ

A. 31.3 kJ
B. 27.6 kJ
C. 34.9 kJ
D. 25.3 kJ
E. 29.9 kJ
ET: Increasing concentration on the right makes the reaction less spontaneous.

NH2CONH2(s) + H2O(l) ← → 2NH3(g) + CO2(g) ∆G = ?

1.00atm 2.00atm
o
ΔG = ΔG + RTln(Q)
ΔG = 27600 + (8.314 x 400 x (ln(2/(1)2)))
ΔG = 2.99 x 104 J = 29.9 kJ

Chem 162-2012 Final exam review from 2010 final exam 69

CHEM 162-2010 HOURLY EXAM III + ANSWERS
CHAPTER 18: THERMODYNAMICS
FREE ENERGY AND EQUILIBRIA CALCULATIONS

27. Given the data below, what is the equilibrium constant at 500K for the
following reaction?

→ PCl5(g)
PCl3(g) + Cl2(g) ←
Compound ∆Hfo(kJ/mol) So(Jmol-1K-1)
PCl3 -287.0 311.7
PCl5 -374.9 364.5
Cl2 0 223.0

A. 2.8
B. 2800
C. 1.96
D. 0.51
E. 1.00
ET: Use ΔHo - TΔSo to find ΔGo; then use ΔGo = -RT ln(K) to find K.

PCl3(g) + Cl2(g) → PCl5(g)

←
∆Ho -287000 0 -374900
So 311.7 223.0 364.5

∆Go = ∆Ho - T∆So

∆Ho = -374900 – (-287000 + 0) = -8.79x104
∆So = 364.5 – (311.7 + 223.0) = -170.2
∆Go = (-8.79x104) – (500 x -170.2) = -2.8 x 103

∆Go = -RTln(K)
(-2.8 x 103) = ((-8.314) x 500 x (ln(K)))
K = 1.96

Chem 162-2012 Final exam review from 2010 final exam 70

CHEM 162-2010 FINAL EXAM + ANSWERS
CHAPTER 18
THERMODYNAMICS
FREE ENERGY AND EQUILIBRIA CALCULATIONS 33.
→ 2SO3(g) is 910 at 900K and
33. The Keq for the reaction 2SO2(g) + O2(g) ←
0.38 at 1170K. What is ∆Ho for this reaction?

A. 252 kJ
B. -252 kJ
C. -0.252 kJ
D. -7.57x105 kJ
E. 75.7 kJ
ET: The van’t Hoff equation is the quantitative counterpart to LeChatelier’s principle for the effect on K after raising the temperatue of an
endothermic/exothermic reaction.

K1 = 910
T1 = 900K
K2 = 0.38
T2 = 1170K

van’t Hoff equation: ln(K2/K1) = (∆Ho/R)(1/T1 – 1/T2)

ln(0.38/910) = (∆Ho/8.314)(1/900 – 1/1170)
∆Ho = -2.52 x 105 J/mol = -2.52 x 102 kJ/mol

Chem 162-2012 Final exam review from 2010 final exam 71

CHEM 162-2010 FINAL EXAM
Chapter 18 - Thermodynamics
Entropy concepts

39. All of the following processes would be expected to have positive ∆So, except
A. C6H12O6(s) → 2C2H5OH(l) + 2CO2(g)
B. N2H4(l) → N2(g) + 2H2(g)
C. CaCO3(s) → CaO(s) + CO2(g)
D. (NH4)2SO4(s) → 2NH4+(aq) + SO42-(aq)
E. 2NH3(g) + CO2(g) → NH2CONH2(aq) + H2O(l)
ET: Entropy is positional freedom. “E” isn’t positional freedom; it is positional confinement.

A. Going from a solid to a liquid and gas is positive ∆So.

B. Going from a liquid to gases is positive ∆So.
C. Going from a solid to a solid and gas is positive ∆So.
D. Going from a solid to a solution is positive ∆So.
E. Going from a gas to a solution and liquid is negative ∆So.

Chem 162-2012 Final exam review from 2010 final exam 72

 CHAPTER 15 - CHEMICAL EQUILIBRIUM

A+B← → C+D (gases or solutes, only)

Law of mass action (or molar interaction):
Kc = ([C][D])/([A][B])

2A + 3B ←→ 4C + 1D

A+A+B+B+B← → C+C+C+C+D

Kc = ([C] • [C] • [C] • [C] • [D])/( [A] • [A] • [B] • [B] • [B])
Kc = ([C]4[D])/([A]2[B]3)

eA + fB ← → gC + hD
Kc = ([C]g[D]h)/([A]e[B]f)

e.g., 2NO + O2 2NO2

2 2
Kc = ([NO2] )/([NO] [O2])

K
A B [B]/[A] = K1

C D [D]/[C] = K2
A+C B+D ([B][D])/([A][C]) = K
Addition of ([B]/[A]) + ([D]/[C]) = (([B][C] + [A][D]))/([A][C])

Equations K(s)
Add Multiply
Reverse Invert
Double Square
Halve Square root

Kp inatm = Kc (RT)∆ngas
inM

Chem 162-2012 Final exam review from 2010 final exam 73

 UNDERSTANDING EQUILIBRIA
DYNAMIC* EQUILIBRIUM
(*not static equilibrium)
ET: At equilibrium, the forward and reverse reactions proceed at equal rates and the concentrations of reactants and products remain constant.
Mountain
INITIALLY
Slum sad
k1 = 0.01/s k-1 = 0.10/s town with
Palacial happy 0 sad
town with people/mi2
1100 happy
people/mi2

Forward rate pre-equilibrium = k1 x reactant conc. = 0.01s-1 x 1100 = 11 people/mi2s-1

Reverse rate pre-equilibrium = k-1 x reactant conc. = 0.10s-1 x 0 = 0 people/mi2s-1

Mountain

AT EQUILIBRIUM Slum sad

k1 = 0.01/s k-1 = 0.10/s town with
Palacial happy 100 sad
town with people/mi2
1000 happy
people/mi2

Equilibrium reached
Macroscopically: You continuously see 1000 happy people on the left and 100 sad
people on the right.
Microscopically: You also see a constant equal exchange of sad people and happy
people going across the bridge, a “dynamic equilibrium”. That is, the rate forward
equals the rate reverse.
Rate forward = k1 x [reactant] = 0.01s-1 x 1000 = 10 people/mi2s-1
Rate reverse = k-1 x [product] = 0.10s-1 x 100 = 10 people/mi2s-1

Also note:
K = [Products]/[Reactants] = 100/1000 = 0.1
K = k1/k-1 = 0.01/0.10 = 0.1

Chem 162-2012 Final exam review from 2010 final exam 74

Le Chatelier’s Principle:
H&P: “When any change in concentration, temperature, pressure, or
volume is imposed on a system at equilibrium, the system responds by
attaining a new equilibrium condition that minimizes the impact of the
imposed change.”

Le Chatelier’s Concept - Relieve stress

ET: If a stress (change) is placed on a system at equilibrium, the
position of equilibrium will shift in a direction to counteract reduce
the applied stress.

Chem 162-2012 Final exam review from 2010 final exam 75

CHEM162-2010 HOURLY EXAM II + ANSWERS
CHAPTER 15 - NON ACID-BASE CHEMICAL EQUILIBRIUM
NON-ACID-BASE EQUILIBRIUM CALCULATIONS
35. Solid ammonium chloride decomposes when heated according to the following reaction:

NH4Cl(s) ←→ NH3(g) + HCl(g)

A sample of ammonium chloride is heated in an evacuated container. At equilibrium, the total pressure in
the container is 1.5x 10-4 atm. Calculate Kp for this reaction.
A. 7.8x10-5
B. 2.3x10-8
C. 3.5x10-6
D. 1.5x10-4
E. 5.6x10-9

→ NH3(g) + HCl(g)
NH4Cl(s) ←

→
NH4Cl(s) ← NH3(g) HCl(g)

Initial Y 0 0
Change -X +X +X
Equilibrium Y-X +X +X
[NH3][HCl] = Kp
[X][X] = Kp
But what is the value of X?

X + X = 0.00015
2X = 0.00015
X = 0.000075
Kp = X2 = [0.000075]2 = 5.6 x 10-9

Chem 162-2012 Final exam review from 2010 final exam 76

CHEM-2010 FINAL EXAM + ANSWERS
CHAPTER 15 - NON ACID AND BASE CHEMICAL EQUILIBRIUM
NON ACID-BASE EQUILIBRIUM CALCULATIONS 21.

For the reaction

→ Br2(g) + Cl2(g)
21. 2BrCl(g) ← Kc = 32 at 500K
What would happen if a 1.0L bulb were filled with 0.10mol BrCl(g), 0.50mol Br2(g), and 0.50mol Cl2(g)?

A. Some BrCl will react spontaneously to form additional Br2 and Cl2.
B. Some of the Br2 and Cl2 will react spontaneously to form additional BrCl.
C. Nothing will happen because the initial concentrations correspond to equilibrium concentrations.
D. All of the BrCl will be consumed.
E. All of the Br2 will be consumed.

2 BrCl(g) → Br2(g) + Cl2(g)

←
0.10 0.50 0.50

Kc = ([Br2][Cl2])/([BrCl]2)
([0.50][0.50])/([0.10]2) = 25 = Q
When Q is less than Kc, then the numerator is too small, so the reaction will go to the right to make the
numerator larger and to reach equilibrium.

A. True
B. False. The reaction will shift to the right, not to the left.
C. False. The initial concentrations do not correspond to equilibrium concentrations.
D. False. The reaction will shift to the right, but no component is ever totally consumed.
E. False. The concentration of Br2 will increase, not decrease.

Chem 162-2012 Final exam review from 2010 final exam 77

CHEM 162-2010 FINAL EXAM
CHAPTER 15 - NON ACID/BASE CHEMICAL EQUILIBRIUM
NON ACID-BASE EQUILIBRIUM CALCULATIONS
46. Given:
→ CH4(g)
C(s) + 2H2(g) ← Kp = 0.262 at 1270K
What is Kc for the above reaction?

A. 20.5
B. 19.6
C. 12.9
D. 27.3
E. 16.3

Kp = Kc(RT)∆ngas
0.262 = Kc(0.08214 x 1270)-1
Kc = 27.3

Chem 162-2012 Final exam review from 2010 final exam 78

 CHAPTER 22
Coordination Compound Fundamentals

Ligand (L: ligo, to bind):

A substance (neutral or anionic) having a lone electron pair that
bonds to a transition metal cation (i.e., Lewis base-Lewis acid
interaction).
Usually a transition metal

Complex ion:
Transition metal cation + ligands
Complex ion is sometimes called a complex.
Complex ion is usually a cation, but could be neutral or anionic.
The metal is usually, but not always, a transition metal;.

Coordination compound
(Transition) metal cation + ligands + counterions
Complex ion (in brackets)
The complex ion may be positively or negatively charged or uncharged; the counterions have the opposite charge; the purpose of the counterions is to
make a zero charge overall; if the complex ion isn’t charged then there are no counterions.

Coordination compound dissociation in aqueous solution:

[Co(NH3)5Cl]Cl2 → [Co(NH3)5Cl]2+ + 2Cl-
Alfred Werner (1893) theorized two types of Cl bonding in a single
molecule to explain why AgNO3 formed a precipitate with only two of the
three chlorine atoms. This was the beginning of Coordination Chemistry.
Ligands are much more tightly attached to the metal cation than are the
counterions. The ligands are tightly attached to the metal cation through
covalent bonds (actually coordinate covalent bonds [both electrons of the
bond coming from one atom]), whereas the counterions move freely
around the solution (weaker ion-dipole bonds with the solvent).
- AgNO3 will not react with the covalently bonded Cl; it will only
react with the above two chloride counterions.

Coordination number:
The number of bonds between the metal ion and the ligands
(6 in the above case; therefore, octahedral structure)
Chem 162-2012 Final exam review from 2010 final exam 79
 Ligand Types
Unidentate
–
Bonds to metal ion using only “one tooth” (even if it has
several teeth)
–
Include: NH3, Cl-, NO2-, CN-, OH-, H2O
: C ≡ N:
cyano-N or cyano-O, depending on which atom is bonded to the metal ion
.. ..
[ : O ― N = O:]-
. . . .

nitrito-N or nitrito-O, depending on which atom is bonded to the metal ion

ET: Note that NO2- and CN- have a choice of two binding sites, but they are still both monodentate because they can only bond with one site at a time.

– Bidentate - e.g., ethylenediamine (“en”), H NCH CH NH

- -
2 2 2 2
oxalato, O2CCO2
binds with two teeth onto a metal cation to form a
chelate
The ligand must be large enough (4 or 5 atoms long) to
form a 5 or 6 atom ring with the metal cation.
– Polydentate – binds with more than one tooth onto a metal
cation to form a chelate
The ligand must be large enough (4 or 5 atoms long) to
form a 5 or 6 atom ring with the metal cation.
e.g., 2-(O2C)2NCH2CH2N(CO2)22- EDTA
(ethylenediaminetetraacetato)

Chelating (<Gk. “claw”), forming a ring

Chem 162-2012 Final exam review from 2010 final exam 80

 SOME COMMON LIGANDS

Formula Name as Ligand Abbreviation

Neutral Molecules
NH3 Ammine
CH3NH2 Methylamine
NO Nitrosyl
CO Carbonyl

Anions
F- Fluoro
Cl- Chloro
Br- Bromo
I- Iodo
OH- Hydroxo
NO2- Nitrito-N
ONO- Nitrito-O
CN- Cyano
SCN- Thiocyanato-S
NCS- Thiocyanato-N

Polydentate
H2NCH2CH2NH2 Ethylenediamine en
[OOCCOO]2- Oxalato ox
[(OOCCH2)2NCH2CH2N(CH2COO)2]4- Ethylenediaminetetraacetato EDTA

Chem 162-2012 Final exam review from 2010 final exam 81

 RULES FOR NAMING COORDINATION COMPOUNDS
(1) Name cation before anion.
(2) Name ligands before metal ion.
(3) Name ligands alphabetically. Ignore prefixes.
(Note: When writing a formula from a name, place anionic ligands before neutral ones.)

- For neutral ligands use name of molecule

Exceptions: H2O, NH3, CO, and NO (see table I below).
(4) Anionic ligands (AL)
- Add “o” to root name of anionic ligands (see table I below)
(5) Anionic complex ions (ACI)
- Use Latin name of metal if possible, with “ate” (see Table II).
(6) Prefixes to ligands
- Use di-, tri-, tetra-, etc. for the number of monodentate ligands, not mono.
- Use bis-, tris-, tetrakis-, etc. for the number of polydentate ligands.
(7) Roman numeral of metal
- Indicate oxidation state of metal
Table I - Names of Some Common Unidentate Ligands
Neutral Molecules
H2O Aqua
NH3 Ammine
CH3NH2 Methylamine
CO Carbonyl
NO Nitrosyl
Anions
F- Fluoro
-
Cl Chloro
-
Br Bromo
-
I Iodo
-
OH Hydroxo
-
CN Cyano
-
NO2 Nitrito
Table II - Latin Names Used for Some Metal Ions in Anionic Complex ions
Fe Ferrate
Cu Cuprate
Pb Plumbate
Ag Argentate
Au Aurate
Sn Stannate

Chem 162-2012 Final exam review from 2010 final exam 82

 FORMAT OF ISOMER SLIDES

• Structural isomers
Coordination isomers
Linkage isomers

• Stereoisomers
Geometrical isomerism
Double-bonded structures (for Orgo)
Square planar structures
Tetrahedral structures (not possible)
Octahedral structures
Optical isomerism
Square planar structures (not possible)
Tetrahedral structures
Octahedral structures
- Monodentate ligands

Chem 162-2012 Final exam review from 2010 final exam 83

Chapter 22
25. In the reaction CaO(s) + CO2(g) ←→ CaCO3(s),
A. CaO is acting as a Lewis acid because the resulting salt is basic.
B. CaO is acting as a Lewis base because it donates an electron pair.
C. CO2 is acting as a Lewis acid because it donates an electron pair.
D. CO2 is acting as a Lewis base because it accepts an electron pair.
E. CO2 is acting as a Lewis acid because CaO is a Bronsted-Lowry base.

O O
║ │
Ca2+ O2- + C → Ca2+ O—C
║ ║
O O

CO2 is acting as a Lewis acid.

CaO is acting as a Lewis base.
A. False, because CaO is acting as a Lewis base.
B. True. CaO is acting as a Lewis base because the oxide donates an electron pair.
C. False. Although CO2 is acting as a Lewis acid, the suggested mechanism is incorrect. Lewis acids
don’t donate electron pairs. They receive electron pairs.
D. False. CO2 is acting as a Lewis acid.
E. False. Although CO2 is acting as a Lewis acid, CaO is not acting as a Bronsted-Lowry base. A
Bronsed-Lowry base is a proton acceptor. The CaO is not accepting protons in this reaction.

CHAPTER 22
38. Which of the following pairs are not structural isomers?

A. [Co(NO2)(NH3)5]2+ [Co(ONO)(NH3)5]]2+
B. [Cr(SO4)(NH3)5]Cl [CrCl(NH3)5]SO4
C. [Co(NH3)6][CrCl6] [Cr(NH3)6[CoCl6]
D. [CoCl2(NH3)4]Br [CoBrCl(NH3)4]Cl
E. [Co(en)(H2O)4]3+ [Co(en)2(H2O)2]3+

A. are structural isomers. They are linkage isomers.

B. are structural isomers. They are coordination isomers.
C. are structural isomers. They are coordination isomers.
D. are structural isomers. They are coordination isomers.
E. are not structural isomers. They are not isomers.

Chem 162-2012 Final exam review from 2010 final exam 84

CHAPTER 22
48. What is the correct name for the compound [Co(NO2)2(en)2]NO3?
[en = ethylenediamine]
A. Cobaltodinitro-N-diethylenediamine nitrate
B. diethylenediaminedinitrocobalt(III)nitrate
C. bi(ethylenediamine)bisnitrocobaltate(III)nitrate
D. diethylenediaminedinitrito-N-cobalt(I) nitrate
E. bis(ethylenediamine)dinitrito-N-cobalt(III)nitrate

A. False. The metal is always listed at the end of the cation; also, more than one ethylenediamine is always
preceded by bis, tris, tetrakis, etc, not di, tri, tetra, etc. Also, the term for NO2 in complex ions is nitrito, not
nitro.
B. False. More than one ethylenediamine is always preceded by bis, tris, tetrakis, etc, not di, tri, tetra, etc. Also,
the term for NO2 in complex ions is nitrito, not nitro. Also, the nitrito group needs a description of whether it is
connected at the N or O.
C. False. More than one ethylenediamine is always preceded by bis, tris, tetrakis, etc, not “bi”. Nitro is
preceded by “di”, not “bis”. Also, the term for NO2 in complex ions is nitrito, not nitro. Also, the Co group in a
cationic complex ion is called “cobalt”, not “cobaltate”; “Cobaltate” is used in an anionic complex ion.
D. False. More than one ethylenediamine is always preceded by bis, tris, tetrakis, etc, not di, tri, tetra, etc.
E. True

CHAPTER 22
49. The correct formula of triamminediaquachlorocobalt(III) iodide is

A. [CoCl(NH3)2(H2O)3]I
B. [CoCl(NH3)3(H2O)3]I
C. [CoCl(NH3)3(H2O)2]I3
D. [CoCl(NH3)3(H2O)2]I2
E. [Co3Cl(NH3)3(H2O)2]I

(+3) + (-1) = +2
The molecule needs two iodides to balance the +2 charge in the complex ion.

Chem 162-2012 Final exam review from 2010 final exam 85

 CHAPTER 12 FORMULAS
ET note: Not everything goes through moles, e.g., volume to grams, grams to volume, atoms to molecules, molecules to atoms.
CHAPTER 5 - STOICHIOMETRY

MOLES ARE AT THE CENTER

(FOR CONVERSIONS, WORK THROUGH MOLES)

VA
(D = g/V) %A
gA or MWA MA or VA

MWA or AWA = gA/moleA molA = MALA

molesA = gA/MWA moles = PAVA/RTA for gases

(molecules x (moles x Avog.

atoms/molecule No. = molecules
(or atoms)) (molesA = gA/MWA)
= atoms)
moles A
atoms molecules
(or atoms if
↕ MW

particle is an moles B
atom) Empirical
formula (MW/EW) x
Emp form =
Molecula
r
molA = MALA (molesB = gB/MWB) f l
moles = PAVA/RTA for
gases
gB or MWB
MB or VB (D = g/V)
%B
VB
moles = g/MW PV = nRT

moles = M x V P1V1/n1T1=P2V2/n2T2

g/MW = M x V 6.022x1023molecule/mole

D = g/L
Chem 162-2012 Final exam review from 2010 final exam 86
 FORMULAS
gsolute + gsolvent = gsolution mLsolute + mLsolvent ≠ mLsolution

Mass percent = grams of solute/100 g solution

Mole percent = moles of solute/100 moles solution

Molarity = moles of solute/L of solution

ET: Molarity is temperature dependent, but molality is not. Difficult but important
interconversion
Molality = moles of solute/kilogram of solvent

PPM = grams of solute/1,000,000 grams solution

Volume percent = volume of solute/100 mL of solution

Proof = 2 x Vol. %; e.g., 2 x 40 mL/100 mL solution = 80 proof

Mole fraction: XA = nA/(nA + nB) XA + XB = 1

Particle fraction: PXA = inA/(inA + inB) PXA + PXB = 1

Raoult’s law: Don’t use: Psoln = XsolventPosolvent

Use: Psoln = PXsolventPosolvent
For two volatile components: Psoln = PXsolventAPosolventA + PXsolventBPosolventB
PXsolvent = insolvent/(insolvent + insolute)
PXA + PXB = 1

van’t Hoff factor, “i”; i = moles of particles in solution/moles of solute dissolved

Boiling-point elevation: ΔT = Tf - Ti = Kbimsolute

Note that H&P uses: ΔT = Tf(solution) – Tf(solvent) = Kbimsolute; my formula and H&P’s formula are identical.

Freezing-point depression: ΔT = Tf - Ti = -Kfimsolute

Note that H&P uses: ΔT = Tf(solution) – Tf(solvent) = -Kfimsolute; my formula and H&P’s formula are identical.

Osmotic pressure: πV = inRT*

* Begin problem with this formula, not the equivalent π = iMsoluteRT

ΔHsoln = ΔHsolute-solutebondbreaking + ΔHsolvent-solventbondbreaking + ΔHsolute-solventbondforming

Henry’s Law: SA=kPA; MA = Solubility of dissolved gas in solution
“S” may be any unit of concentration (depending on the units of “k”), e.g., X, M, %.
ET note: Not everything goes through moles, e.g., volume to grams, grams to volume, atoms to molecules, molecules to atoms.
Chem 162-2012 Final exam review from 2010 final exam 87
 ENERGETICS OF SOLUTIONS AND
SOLUBILITIES
Relative
Strength
• Electrostatic interaction (ions) 1000
(= charge-charge interaction (“strong”)
= ionic interaction)
Coulomb’s Law: F = k(Q1 x Q2)/r2

Relatively
• Ion-dipole interaction 100-500(?)
strong
bonds
• Hydrogen bonding 30
Y = N, O or F (“moderate”)
Y―H Y

• Dipole-dipole interaction 10
(polar molec. & polar molec.) (“moderate”)

• London forces (with all molecules) 1*

Relatively
(non-polar molecules (“weak”)
weak
bonds & non-polar molec.)

Chem 162-2012 Final exam review from 2010 final exam 88

 COLLOIDS
A colloid is a dispersion in which the dispersed matter has one or more dimensions (length, width, or thickness) in the
range from about 1nm to 1000 nm. The particles don’t settle out (suspension) but they aren’t dissolved into individual
molecules either (solution).

Particle Fluid Tyndall

Example Phase Precipitation Size appearance Effect**
Solution NaCl in H2O Homogen No <1nm Clear No

Colloid* Starch in H2O, milk, Varies No 1nm to 1000 nm Usually cloudy Yes
gelatin, fog, steam,
hair spray

Suspension Sand in H2O Heterogen Yes >1000 nm Cloudy Yes

*Also called “colloidal suspension” or “colloidal dispersion”.

**The Tyndall effect is the scattering of light by colloidal particles, which makes a colloidal dispersion distinguishable
from a true solution.

Colloids occur in any phase.

Gas phase: aerosol
Liquid phase: emulsion
Solid phase: sol

Chem 162-2012 Final exam review from 2010 final exam 89

CHEM 162-2010 FINAL EXAM
Chapter 12 - Properties of Solutions
Energetics of solutions and solubility concepts
23. Which compound below would be expected to be the least soluble in water?
A. CH3CH2CH2I
B. CH3CH2CH2NH2
C. CH3CH2-O-CH3
D. CH3CH2COOH
E. CH3CH2COOCH3

The molecule that would be the most soluble would be the one that forms the strongest bonds with water.
B, C, D and E can all form hydrogen bonds with water. However, A is not capable of forming hydrogen
bonds with water. It forms a slightly weaker dipole-dipole bond with water, and is therefore the least
soluble.

Chem 162-2010 Final Exam + Answers

Chapter 12 – Physical Properties of Solutions
Solution concentrations calculations
42. What is the molality of 2.158M C6H12O6(aq) whose density is 1.1434g/cm3?
A. 1.777m
B. 2.860m
C. 2.158m
D. 1.887m
E. 2.467m

2.158 mol C6H12O6/Lsoln → ?mol C6H12O6/kgsolv

First do numerator, then denominator.

Numerator is already done: 2.158 mol → 2.158 mol

Denominator:
Plan: Lsoln → gsoln → gsolv → kgsolv
1L solution x 1.1434g/0.001L = 1143.4g solution
gsolute + gsolvent = gsolution
gsolute = 2.158mol x 180.18g/mol = 388.83 g
388.83gsolute + gsolvent = 1143.4gsolution
gsolvent = 754.57g = 0.75457kg

Combine numerator with denonimator:

2.158mol/0.75457kg = 2.86 molsolute/kgsolvent = 2.86molal

Chem 162-2012 Final exam review from 2010 final exam 90

CHEM 162-2010 FINAL EXAM
CHAPTER 14 - PROPERTIES OF SOLUTIONS
COLLIGATIVE PROPERTIES (BOILING POINT, FREEZING POINT, OSMOTIC PRESSURE CHANGES) CALCULATIONS
32. When 0.64g of the heart stimulant epinephrine was dissolved in 36.00g of benzene, the normal
freezing point of the resulting solution was found to be 5.03oC. What is the approximate molar mass of
epinephrine? Tf of benzene = 5.53oC; Kf for benzene = 5.12oC-kg/mol

A. 180 g/mol
B. 970 g/mol
C. 510 g/mol
D. 390 g/mol
E. 96 g/mol

Freezing-point depression: ΔT = Tf - Ti = -Kfimsolute

Tf - Ti = -Kfimolsolute/kgsolvent
Tf - Ti = -Kfi((masssolute)/(MWsolute))/kgsolvent
5.03 – 5.53 = -5.12 x 1 x ((0.64/MW)/0.036)
MW = 182g/mol

51. What color is your exam booklet?

A. white
B. yellow
C. blue
D. pink

Chem 162-2012 Final exam review from 2010 final exam 91