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

Dr. Ed Tavss
CHAPTER

TITLE

REQUESTS

High Priority
16
17
19
14
20

Acids and Bases


Acid-Base/Solubility Equilibria
Electrochemistry
Chemical Kinetics
Nuclear Chemistry

59
71
49
29
41

Low Priority
18
15
22
13

Thermochemistry
Chemical Equilibrium
Coordination Chemistry
Physical Properties of Solutions

18
25
22
13

Chem 162-2012 Final exam review from 2010 final exam

CHAPTERS 16 & 17

pH
14

H2O + H2O

Basic

[H+]
1x10-14

7 Neutral (e.g. H2O) 1x10-7

-14
+
H3O + OH Kw = 1x10
+
-

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

Acidic

1x10o

pH units of 1 to 13 is what is commonly used, but pHs as low as


-1 or as high as 15 are possible. No acids in existence for <-1 or
bases for >+15.

pH = -log[H ]

pOH

[OH-] = 10-pOH
-

pOH = -log[OH ]

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

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

pH + pOH = 14

pH
pH + pOH = 14

pH = -log[H+]
[H+] = 10-pH
pOH = -log[OH-]
[OH-] = 10-pOH

[H+] = 10-pH

[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

SEVEN STRONG ACIDS


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

Ka
~106
~108
~109

Acid
HCl + H2O
HBr + H2O
HI + H2O
H2SO4 + H2O
HNO3 + H2O
HClO4 + H2O
HClO3 + H2O

H 3O +
H 3O +
H 3O +
H 3O +
H 3O +
H 3O +
H 3O +

*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

Very weak base


(i.e., not a base;
spectator ion)**
+ Cl+ Br+ I+ HSO4-***
+ NO3+ ClO4+ ClO3-)*

2 +
H3O + SO4

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, CO32Lewis Base: Anything that has available non-bonding electrons, e.g., NaOH, RNH2, CO32Chem 162-2012 Final exam review from 2010 final exam

Chem 162-2012 Final exam review from 2010 final exam

RELATIONSHIP BETWEEN STRUCTURE


AND STRENGTH OF ACID, H-Z
ET: Impossible to understand this topic based on H&Ps 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 H+Z- 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 (+ -) interaction of the two partial charges is the dominant factor when the atoms are close to each other
(according to Coulombs 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

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

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

Write the equil. equations and identify Ks for the following reactions:
Weak acid + water (e.g., acetic acid + H O):

HA + H2O

H3O+ + A-

Assume Ka = ~1 x 10-5

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


2

HA + OH-

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


K = 1/Ka = 1/(1 x 10-5) = 1 x 105
3

(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 + A4

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)
RNH3+ + OHRNH2 + H2O
Assume Kb = ~1 x 10-5

Weak base + water (e.g., NH + H O):


3

RNH2 + H3O+
Conjugate acid + water (e.g., sodium acetate + H O): RNH3+ + H2O
Kca = Kw/Kb = (1 x 10-14)/(1 x 10-5) = (1 x 10-9)
2

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
K = 1/(Kw/Kb) = Kb/Kw = (1 x 10-5)/(1 x 10-14) = 1 x 109
3

(or bring to completion; then solve either using HH or

reverse + Kb)
Chem 162-2012 Final exam review from 2010 final exam

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

14

H2O + A

Strong
base

Strong base

12
Weak base

Red

10

HIn + In-

pH

Phenolphthalein
Indicator

9 for SB & WA

Equivalence Point 7 for SB & SA


or
Stoichiometric Point
or
Neutralization Point

Colorless

5 for WB & SA

1:1
HA:A-

Half-way Point
or
Half-equivalency Point

4
Weak acid

Completion
or
End Point
or

HA

pH = pKa + log([A-]/[HA])
pH = pKa + log([X]/[X])
pH = pKa
5 = pKa
Ka = 10-pH = 1 x 10-5

Weak
acid

2
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
-pH
[H+162-2012
] = KFinal
10review
) from 2010 final exam
Chem
a (=exam

SIX STRONG ACIDS


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

Ka
~106
~108
~109

Acid
HCl + H2O
HBr + H2O
HI + H2O
H2SO4 + H2O
HNO3 + H2O
HClO4 + H2O
(HClO3 + H2O

H 3O +
H 3O +
H 3O +
H 3O +
H 3O +
H 3O +
H 3O +

*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

Very weak base


(i.e., not a base;
spectator ion)**
+ Cl+ Br+ I+ HSO4-***
+ NO3+ ClO4+ ClO3-)*

2 +
H3O + SO4

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, CO32Lewis Base: Anything that has available non-bonding electrons, e.g., NaOH, RNH2, CO32Chem 162-2012 Final exam review from 2010 final exam

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.
X.
Y.
Z.

A.
B.
C.
D.
E.

NH4I
BaCl2
KNO3
NaF

Z only
Xand Y
Y and Z
W only
W and X

ET: Get rid of schmutz ions and determine pH of whats remaining.

NH4I NH4+ + II- is such a weak base that it doesnt act basic.
I- + H2O NR
But NH4+ is a weak acid.
NH3 + H3O+
NH4+ + H2O
Therefore, solution is acidic.
BaCl2 Ba2+ + 2ClGroup 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+ + NO3Group 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+ + FGroup I and II cations are not acidic.
Na+ + H2O NR
F- is a weak conjugate base.
HF + OHF- + H2O
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?
CH3NH3+(aq)
CH3NH2(aq) + H+(aq)
A.
B.
C.
D.
E.

2.8x1011
3.6x1010
1.7x108
3.6x103
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)
CH3NH3+(aq) + H2O
CH3NH2(aq) + H3O+(aq)
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.
B.
C.
D.
E.

2.3 mol
1.6 mol
0.75 mol
0.43 mol
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)
Initial
Change
Equilibrium

H2O

0.950

NH4+(aq)

OH-(aq)
0
4.0 x 10-5

NH3(aq)
Initial
Change
Equilibrium

H2O

0.950
-X
0.950-X
NH3(aq)

NH4+(aq)

Y
+X
Y+X
+

H2O

Initial
0.950
-4.0 x 10-5
Change
0.950-(4.0 x 10-5)
Equilibrium
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

NH4+(aq)

OH-(aq)
0
+X
4.0 x 10-5

Y
+4.0 x 10-5
Y + (4.0 x 10-5)

OH-(aq)
0
+4.0 x 10-5
4.0 x 10-5

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.
B.
C.
D.
E.

H3O+
OHH2PO4PO43HPO42-

ET note: (1) Strong bases bring the reaction to completion. (2)The Kas 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
Initial
0.30
0.60
Change
-0.30
-0.30
Equilibrium
0
0.30
2nd reaction:
Initial
Change
Equilibrium

H2PO40.30
-0.30
0

OH0.30
-0.30
0

H2PO40
+0.30
0.30

H2O
0

HPO420
+0.30
0.30

H2O
0

3rd reaction:

+
H2O

H3O+
+
PO43HPO42Initial
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 Kas 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
Kas 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.
B.
C.
D.
E.

HClO < HBrO < HIO < HClO2 < HClO3


HClO3 < HClO2 < HClO < HIO < HBrO
HIO < HBrO < HClO < HClO2 < HClO3
HClO < HClO2 < HClO3 < HBrO < HIO
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 CH3COOin 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.
B.
C.
D.
E.

Add 0.50 mol of NaOH to 1.0L of the buffer


Add 0.50 mol of HCl to 1.0L of the buffer
Add 49L of water to 1.0L of the buffer
Add 0.50 mol of CH3COOH to 1.0 L of the buffer.
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 doesnt 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

14

H2O + A

Strong
base

Strong base

12
Weak base

Red

10

HIn + In-

pH

Phenolphthalein
Indicator

9 for SB & WA

Equivalence Point 7 for SB & SA


or
Stoichiometric Point
or
Neutralization Point

Colorless

5 for WB & SA

1:1
HA:A-

Half-way Point
or
Half-equivalency Point

4
Weak acid

Completion
or
End Point
or

HA

pH = pKa + log([A-]/[HA])
pH = pKa + log([X]/[X])
pH = pKa
5 = pKa
Ka = 10-pH = 1 x 10-5

2
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
-pH
[H+162-2012
] = KFinal
10review
) from 2010 final exam
Chem
a (=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.
B.
C.
D.
E.

The choice of indicator will depend on the initial concentration.


The indicator should change color at or near pH 9.
The indicator should change color at or near pH 3.
The indicator should change color at or near pH 7.
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

2B

Al

Si

S2-

Cl- Ar

Zn

Ga Ge

As

Se

Br- Kr

In

Sb

Te

I-

Pb2+ Bi

Po

At- Rn

Na+ Mg

3B 4B 5B 6B

7B

K+

Ca

Sc

Ti

Mn Fe

Rb+ Sr

Zr

Nb Mo Te

Ru Rh Pd

Ag+ Cd
?

Hf

Ta

Os Ir

Au

Cs+

Ba2+ La

Cr

Re

8B 8B 8B 1B

Co Ni

Chem 162-2012 Final exam review from 2010 final exam

Pt

Cu

Hg22+ Tl

Sn

Ne

Xe

19

LOW PRIORITY

HIGH PRIORITY

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+)
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-)

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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)
Y
-X
Y-X

Initial
Change
Equilibrium
[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

Mn2+(aq)
0
+X
+X

2 OH-(aq)
0
+2X
+2X

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
1.3 x 10-7
E. 6.7 x 10-5

D.

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+ + 2OHMg(OH)2(s)
Fe2+ + 2OHFe(OH)2(s)

Mg(OH)2(s)
Y
-X

Mg2+ +

Fe(OH)2(s)

Fe2+ +

Initial
0
Change
+X
Equilibrium
0.10
[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

Initial
Y
0
Change
Equilibrium
0.10
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

2OH0
+2X
2X

2OH0
+2X

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
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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.
B.
C.
D.
E.

8.1 x 10-15M
5.3 x 10-15M
1.7 x 10-13M
2.0 x 10-12M
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)
Initial
Change
Equilibrium

0.40
-X
0.40-X

2S2O32-(aq)

2.5
-2X
2.5-2X

[Ag(S2O3)2]3-(aq)
0
+X
+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)
Initial
Change
Equilibrium

0.40
-0.40
0

2S2O32-(aq)
2.5
-0.80
1.70

[Ag(S2O3)2]3-(aq)
0
+0.40
+0.40

Now go back to equilibrium. Since its more convenient for the student to go from left to right,
reverse the equation, and invert K.
Ag+ (aq)
+
2S2O32-(aq)

[Ag(S2O3)2]3-
New initial
0.40
0
Change
-X
+X
Equilibrium
0.40-X
+X
+
32- 2
([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

1.70
+2X
1.70 + 2X

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.

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for lecture 20CHAPTER 19 - ELECTROCHEMISTRY

ELECTRODE REDUCTION POTENTIALS


Some Selected Standard Electrode Reduction Potentials
Eo, volt (redn)
F2 + 2 e- 2 F+2.87
+
+1.78*
H2O2 + 2 H + 2 e 2 H2O
+
2+
MnO4 + 8H + 5e Mn + 4H2O
+1.51
3+
Au + 3e Au
+1.50
+
2+
+1.46
PbO2 + 4 H + 2 e Pb + 2 H2O
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
+0.54
I2 + 2 e 2 I
2+
Cu + 2 e Cu
+0.34
2+
+
Cu + e Cu
Ref. electrode: +0.16
+
1M H+ & 1atm H2 0.00
2H + 2 e H2
Fe3+ + 3e- Fe
-0.036
2+
Pb + 2 e Pb
-0.13
2+
-0.23
Ni + 2 e Ni
Cd2+ + 2e- Cd
-0.40
3+
2+
Cr + e Cr
-0.50
2+
-0.76
Zn + 2 e ----> Zn
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

OXIDATION

REDUCTION

ET: In this table all reactions are written as reductions.

* H2O half-cell reactions

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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 = G
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

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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.

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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.
B.
C.
D.
E.

Only (1) is true.


Only (1) and (3) are true.
Only (2) is true.
All three are true.
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 halfcells. 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-]))

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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.
B.
C.
D.
E.

0.0010M
0.0050M
0.0190M
0.0500M
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.
Zn Zn2+ + 2e2(AgCl + 1e- Ag + Cl-)
Zn + 2AgCl Zn2+ + 2Ag + 2Cl-

Eo
+0.76
+0.22
+0.98V

Zn(s) + 2AgCl(s) Zn2+ + 2Ag(s) + 2Cl0.0010M


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-]

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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.

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32

CHEM 162-2010 FINAL EXAM


CHAPTER 19 - ELECTROCHEMISTRY
OXIDATION-REDUCTION REACTION CONCEPTS

7. Consider the unbalanced half reaction:


S2O32- +OH- SO42- + H2O + eWhen the above half reaction is balanced with whole number coefficients,
which of the following are the correct coefficients for OH- and SO42-?
A.
B.
C.
D.
E.

OH8
5
4
10
3

SO423
5
6
2
7

ET: Balancing a half-cell equation in basic solution

S2O32- SO42Balance the Ss.


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+ + 8eMake it basic by adding OH- to both sides.
S2O32- + 5H2O + 10OH- 2(SO42-) + 10H+ + 8e- + 10OHSimplify the equation.
S2O32- + 5H2O + 10OH- 2(SO42-) + 10H2O + 8eGet rid of spectators.
S2O32- + 10OH- 2(SO42-) + 5H2O + 8e-

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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+ + 1e6(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

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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
Cd2+(aq) + Co(s)
Cd(s) + Co2+(aq)
A.
B.
C.
D.
E.

2.1 x 105
1.1 x 104
3.3 x 10-4
4.5 x 10-6
3.1 x 104

ET: Straightforward; calculate Eocell, n, and then find K

Cd(s) Cd2+(aq) + 2e-

= +0.40V

Co2+(aq) + 2e- Co(s)

= -0.28V

Cd2+(aq) + Co(s)
Cd(s) + Co2+(aq)

cell = 0.12V

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

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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.
B.
C.
D.
E.

Cu
Ag
Ag+
Fe2+
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
Eo = +0.34V
Cu2+ + 2e- Cu
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.
Eo = +0.44V
Fe Fe2+ + 2e-.
Cu Cu2+ + 2eEo = -0.34V
Ag Ag+ + eEo = -0.80V
Fe is the most easily oxidized and therefore the strongest reducing agent.

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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).

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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
Eo = 1.229 V
O2(g) + 4H+(aq) + 4e- 2H2O(l)
Calculate Go for the reaction below:
2Br2(l) + 2H2O(l) 4Br-(aq) + O2(g) + 4H+(aq)
A.
B.
C.
D.
E.

+31.7 kJ
-31.7 kJ
-15.8 kJ
-42.2 kJ
+63.3 kJ

ET note: Straightforward. Use equation Go = -nFEocell; calculate n and Eocell, then find Go.

Go = -nFEocell
Eo(V)
1.065
2(Br2(l) + 2e- -> 2Br-(aq))
+
2H2O(l) O2(g) + 4H (aq) + 4e
-1.229
+
4Br (aq) + O2(g) + 4H (aq) -0.164
2Br2(l) + 2H2O(l)
Go = -4 x 96485 x (-0.164) = 6.33x104 J = 63.3 kJ

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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.
B.
C.
D.
E.

2.22 x 10-3g
1.03 x 107g
2.07 x 107g
1.11 x 10-3g
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

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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
Order Reaction Rate**
RATE LAW*** (y = mx + b)
Half-life*
o
0 AvgRate = -(C2-C1)/(t2-t1) InstRate = k[C] =k [C]t = -kt + [C]o t1/2 = [C]o/2k

k
units
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 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)]

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C12H22O11 + H2O 2C6H12O6 (hypothetical example)


C (M)
Rate Plot

Hypothetically: Reaction is 2nd order with respect to C12H22O11 and zero order with
ET: Discuss formation of plot from data; then discuss definitions

X1,Y1

Rate = -(Y2 - Y1)/(X2 - X1) Note 1,2,3,4


Rate = -(0.8-1.0)/(0.25-0) = +0.80M/s Note2

0.9

X2,Y2

SUCROSE CONCENTRATION (M)

0.8

1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
Rate = k[C]2
k=1

Time (s)
0
0.1
0.3
0.4
0.7
1.0
1.5
2.3
4.0

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


2 Average rate: Rate calculated between two points. Note rate faster at
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.
5 Rate law: Relationship between rate of reaction and concentration of
reactants
Note1

0.7

0.6

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

TIME (s)

Chem 162-2012 Final exam review from 2010 final exam

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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.

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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

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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).

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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.
B.
C.
D.
E.

6.0x10-4M/s
4.5x10-4M/s
3.0x10-4M/s
8.0x10-4M/s
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 doesnt 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

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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

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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.
Initial
Change
145 second pressures

N2 +
0.45 atm
-X
0.45-X

3H2
1.55 atm
-3X
1.55-3X

2NH3
0 atm
+2X
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
Initial
Change
145 second pressures

N2 +
0.45 atm
0.075 atm
0.375 atm

3H2
1.55 atm
3 x 0.075 = 0.225 atm

2NH3
0 atm
2 x 0.075 = 0.150 atm

Initial
Change
145 second pressures

N2 +
0.45 atm
0.075 atm
0.375 atm

3H2
1.55 atm
0.225 atm
1.325 atm

2NH3
0 atm
0.150 atm
0.150 atm

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

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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]
0.455[A]3[B]2
D. 1.37[A]2[B]2
E. 0.0409[A][B]2

C.

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

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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
fast equilibrium
2A
A+BC
slow
CD
fast

A.
B.
C.
D.
E.

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

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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.
B.
C.
D.
E.

1.32 kJ
615 kJ
91.0 kJ
898 kJ
10.9 kJ

Using the Arrhenius equation:


k1 = 4.75 x 10-4s-1
T1 = 20oC = 293K
T2 = 30oC = 303K
k2 = 1.63 x 10-3s-1
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

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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 doesnt 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 doesnt change due to using a catalyst.
E. False. It lowers the activation energy of the forward and reverse reactions.

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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
Sum of protons and neutrons = mass number (neutrons and protons are nucleons)
Alpha particles
2 = 2He
***
- 0
0
Beta particles
= -1 = -1e Number of protons (or charge) = atomic number
**
0
Gamma ray
0
Positron particle
+= 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 + 00

RADIOACTIVE DECAY RATE


Reaction Differential
Rate Law
Order
1
Rate = N

Units in 1o reactions
cancel, so are irrelevant.

Integrated
rate law
ln(Nt/No) = -t
ln(Nt) = -t + ln(No)

Half-life*
t1/2 = 0.693/**

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

= 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
Order
Rate Law
1
Rate = k[A]

Integrated
rate law
ln(At) = -kt + ln(Ao)

Half-life*
t1/2 = 0.693/k

Actual nuclear mass


+
(actual mass of nucleus)

mass defect
(binding energy)

* 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)
(Calcd mass of neutrons + protons)

E = mc2
J = kg x (3.00 x 108 ms-1)2
or 931.5 MeV/u
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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

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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

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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.

238

209

83

92

Bi

Unstable nuclide due to high neutron to proton ratio relative


to stable nuclide.

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: 148 (90 neutrons58 protonsCe
Rewrite: 90n58pCe; neutron:proton ratio = 1.55
Mode of decay to approach reference (i.e., to
decrease neutron to proton ratio) is electron emission.
148
0
148
58Ce -1e +
59La
Rewrite: 90n58pCe 0-1e + 8959Pr; neutron:proton ratio = 1.51

148

58

Ce (unstable high n:p ratio)


140

58Ce
(stable)

130

58Ce (unstable low


n:p ratio)

Neutron to proton ratio


too high in this region;
therefore, becomes
stable through decay by
beta emission

Chem 162-2012 Final exam review from 2010 final exam

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 42 + 23490Th
Result: Going in correct direction (90 is approaching 83 protons).

Too many protons and


neutrons
in this region;
Protons > 83
therefore, decay by alpha
emission
Lose protons and
neutrons
concurrently
Unstable
nuclide due to low neutron to proton ratio relative to
stable nuclide.
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.
Beta emission: 13058Ce 0+1e + 13057La
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 low in


this region; therefore, decay by
positron emission and/or electron
capture

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 dont 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 dont 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 isnt so.

Chem 162-2012 Final exam review from 2010 final exam

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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)

Binding energy per nucleon (MeV)

235

141

Fission

e.g., 92U + 0n 56Ba + 9236Kr + 3 10n


(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.

Nuclear reactor: Binding energy creates electricity


Control rods: Absorbs excess neutrons

Fusion

e.g., 21H + 31H 42He + 10n


(requires a temperature > 40,000,000K for
the positively charged nuclei to move fast
enough to overcome the plus plus
repulsion. A fusion bomb (hydrogen
bomb) uses a fission explosion (uranium
or plutonium) to provide the high
temperature needed to initiate fusion.)
H-H fusion occurs in the sun.

0
0

50

100

150

200

250

300

Mass Number
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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.
B.
C.
D.
E.

electron capture
neutron emission
particle emission
particle emission
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.
A.
B.
C.
D.
E.

214
82

+ 0-1e 21481Tl neutron:proton = 133/81 = 1.64. This ratio is going


in the wrong direction.
214
1
213
82Pb 0n +
82Pb neutron:proton = 131/82 = 1.60. This ratio is going
in the correct direction.
214
4
210
neutron:proton = 130/80 = 1.63. This ratio is
82Pb 2He +
80Tl
going in the wrong direction.
214
0
214
82Pb -1e +
83Hg neutron:proton = 131/83 = 1.58. This ratio is going
in the correct direction.
214
0
214
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.
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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, amus, 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

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CHEM 162-2010 FINAL EXAM


CHAPTER 20 - THE NUCLEUS
RADIOACTIVE DECAY KINETICS

40. The specific rate constant, , 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.
B.
C.
D.
E.

0.250g
0.127g
0.305g
0.404g
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

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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.
B.
C.
D.
E.

5100 years
3600 years
6400 years
7200 years
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/
5730 = 0.693/
= 0.00012094
Use the Integrated Rate Law, ln(At/Ao) = -t
ln(Nt) = -t + ln(No)
ln(7.07) = -0.00012094 x t + ln(15.3)
t = 6383 years

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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

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CHEM 162-2010 FINAL EXAM


CHAPTER 20 - THE NUCLEUS
MISCELLANEOUS

14. The most dangerous feature of radioactivity is


A.
B.
C.
D.
E.

the amount of gamma radiation emitted.


the solubility of most isotopes.
the long half-lives of radioisotopes.
the ionizing of important biological compounds.
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.

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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
Go = npGof(products) - nrGof(reactants)
Ho = npHof(products) - nrHof(reactants)
Sosystem = npSoproducts - nrSoreactants
Ssystem = npSproducts - nrSreactants (used for Ssystem anytime)
Ssystem = Hsystem/T (used for Ssystem only when at equilibrium)
Troutons rule: At normal B.P., Svaprization 87J mol-1K-1
Ssurr = Hsurr/T = -Hsystem/T (used for Ssurr anytime)
Suniv = Ssys + Ssurr = Ssys (Hsys/T)
Four ways to find Go:
(1) Go = Ho - TSo (or G = H - TS)
(2) Go = npGof(products) - nrGof(reactants)
(3) GTo = G1o + G2o (i.e., adding equations [Hesss law])
(4) Go = -RT ln(K)
G = Go + RT ln(Q) (Q can be any pressure or concentration)
wmax = G
lnKeq = ((-Ho/R) x 1/T) + So/R
Plot straight line: Y = mX + b
ln(K2/K1) = -(Ho/R)((1/T2) (1/T1)): vant Hoff equation
ln(P2/P1) = -(Hvapno/R)((1/T2) (1/T1)): Clausius-Clapeyron equation

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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 isnt all converted into work.

This is a conceptually difficult question.


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

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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.
B.
C.
D.
E.

Keq > 1 and Go < 0


Keq < 1 and Go > 0
Keq > 1 and Go = 0
Keq < 1 and Go < 0
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+ +
2Cl1M
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.

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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)

A.
B.
C.
D.
E.

Go = 27.6 kJ

31.3 kJ
27.6 kJ
34.9 kJ
25.3 kJ
29.9 kJ

ET: Increasing concentration on the right makes the reaction less spontaneous.

2NH3(g) + CO2(g)
NH2CONH2(s) + H2O(l)
1.00atm 2.00atm
o
G = G + RTln(Q)
G = 27600 + (8.314 x 400 x (ln(2/(1)2)))
G = 2.99 x 104 J = 29.9 kJ

Chem 162-2012 Final exam review from 2010 final exam

G = ?

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)
PCl3
-287.0
PCl5
-374.9
Cl2
0

A.
B.
C.
D.
E.

So(Jmol-1K-1)
311.7
364.5
223.0

2.8
2800
1.96
0.51
1.00

ET: Use Ho - TSo to find Go; then use Go = -RT ln(K) to find K.

PCl3(g)
Ho -287000
So 311.7

Cl2(g)
0
223.0

PCl5(g)
-374900
364.5

Go = Ho - TSo
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

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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.
B.
C.
D.
E.

252 kJ
-252 kJ
-0.252 kJ
-7.57x105 kJ
75.7 kJ

ET: The vant Hoff equation is the quantitative counterpart to LeChateliers principle for the effect on K after raising the temperatue of an
endothermic/exothermic reaction.

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

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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 isnt positional freedom; it is positional confinement.

A.
B.
C.
D.
E.

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


Going from a liquid to gases is positive So.
Going from a solid to a solid and gas is positive So.
Going from a solid to a solution is positive So.
Going from a gas to a solution and liquid is negative So.

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CHAPTER 15 - CHEMICAL EQUILIBRIUM


C+D
A+B
(gases or solutes, only)
Law of mass action (or molar interaction):
Kc = ([C][D])/([A][B])
4C + 1D
2A + 3B
C+C+C+C+D
A+A+B+B+B
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])
A

K
[B]/[A] = K1

C
D
A+C

B+D

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

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

Equations
Add
Reverse
Double
Halve
Kp

inatm

K(s)
Multiply
Invert
Square
Square root

= Kc (RT)ngas
inM

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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
Palacial happy
town with
1100 happy
people/mi2

k1 = 0.01/s

k-1 = 0.10/s

Slum sad
town with
0 sad
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
Palacial happy
town with
1000 happy
people/mi2

k1 = 0.01/s

k-1 = 0.10/s

Slum sad
town with
100 sad
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
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Le Chateliers 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 Chateliers 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.

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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:
NH3(g) + HCl(g)
NH4Cl(s)
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)
Y
-X
Y-X

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

NH3(g)

HCl(g)

0
+X
+X

0
+X
+X

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

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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.
B.
C.
D.
E.

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

2 BrCl(g)
0.10

Br2(g) +

Cl2(g)

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.
B.
C.
D.
E.

True
False.
False.
False.
False.

The reaction will shift to the right, not to the left.


The initial concentrations do not correspond to equilibrium concentrations.
The reaction will shift to the right, but no component is ever totally consumed.
The concentration of Br2 will increase, not decrease.

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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

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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 isnt 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)
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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


-

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

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SOME COMMON LIGANDS


Formula
Neutral Molecules
NH3
CH3NH2
NO
CO

Name as Ligand
Ammine
Methylamine
Nitrosyl
Carbonyl

Anions
FClBrIOHNO2ONOCNSCNNCS-

Fluoro
Chloro
Bromo
Iodo
Hydroxo
Nitrito-N
Nitrito-O
Cyano
Thiocyanato-S
Thiocyanato-N

Polydentate
H2NCH2CH2NH2
[OOCCOO]2-

Ethylenediamine
Oxalato

[(OOCCH2)2NCH2CH2N(CH2COO)2]4-

Ethylenediaminetetraacetato

Chem 162-2012 Final exam review from 2010 final exam

Abbreviation

en
ox
EDTA

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
FFluoro
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
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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

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Chapter 22
CaCO3(s),
25. In the reaction CaO(s) + CO2(g)
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+ OC

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
dont 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.
B.
C.
D.

[Co(NO2)(NH3)5]2+
[Cr(SO4)(NH3)5]Cl
[Co(NH3)6][CrCl6]
[CoCl2(NH3)4]Br

E.

[Co(en)(H2O)4]3+

[Co(ONO)(NH3)5]]2+
[CrCl(NH3)5]SO4
[Cr(NH3)6[CoCl6]
[CoBrCl(NH3)4]Cl
[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.

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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.

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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
molA = MALA
moles = PAVA/RTA for gases

MWA or AWA = gA/moleA


molesA = gA/MWA
(moles x Avog.
No. = molecules
(or atoms))

(molecules x
atoms/molecule
= atoms)
atoms

(molesA = gA/MWA)
moles A

molecules
(or atoms if
particle is an
atom)

MW

moles B
Empirical
formula

(MW/EW) x
Emp form =
Molecula
r
l
(molesB = gB/MWB) f

molA = MALA
moles = PAVA/RTA for
gases

gB or MWB
(D = g/V)

MB or VB
%B

moles = g/MW

PV = nRT

moles = M x V

P1V1/n1T1=P2V2/n2T2

g/MW = M x V

6.022x1023molecule/mole

VB

D = g/L
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gsolute + gsolvent = gsolution

FORMULAS
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
Difficult but important

ET: Molarity is temperature dependent, but molality is not.

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

Raoults law: Dont use: Psoln = XsolventPosolvent


Use: Psoln = PXsolventPosolvent
For two volatile components: Psoln = PXsolventAPosolventA + PXsolventBPosolventB
PXsolvent = insolvent/(insolvent + insolute)
PXA + PXB = 1
vant Hoff factor, i; i = moles of particles in solution/moles of solute dissolved
Boiling-point elevation: T = Tf - Ti = Kbimsolute

Note that H&P uses: T = Tf(solution) Tf(solvent) = Kbimsolute; my formula and H&Ps formula are identical.

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

Note that H&P uses: T = Tf(solution) Tf(solvent) = -Kfimsolute; my formula and H&Ps formula are identical.

Osmotic pressure: V = inRT*


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

Hsoln = Hsolute-solutebondbreaking + Hsolvent-solventbondbreaking + Hsolute-solventbondforming


Henrys 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.

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ENERGETICS OF SOLUTIONS AND


SOLUBILITIES

Relatively
strong
bonds

Relatively
weak
bonds

Relative
Strength
1000
(strong)

Electrostatic interaction (ions)


(= charge-charge interaction
= ionic interaction)
Coulombs Law: F = k(Q1 x Q2)/r2

Ion-dipole interaction

100-500(?)

Hydrogen bonding
Y = N, O or F
YH

30
(moderate)
Y

Dipole-dipole interaction
(polar molec. & polar molec.)

London forces (with all molecules)


(non-polar molecules
& non-polar molec.)

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10
(moderate)
1*
(weak)

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 dont settle out (suspension) but they arent dissolved into individual
molecules either (solution).

Solution
Colloid*

Example
NaCl in H2O

Phase
Homogen

Particle
Precipitation Size
No
<1nm

Starch in H2O, milk,


gelatin, fog, steam,
hair spray

Varies

No

1nm to 1000 nm

Usually cloudy

Yes

Heterogen

Yes

>1000 nm

Cloudy

Yes

Suspension Sand in H2O

Fluid
appearance
Clear

Tyndall
Effect**
No

*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

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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.
B.
C.
D.
E.

CH3CH2CH2I
CH3CH2CH2NH2
CH3CH2-O-CH3
CH3CH2COOH
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

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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.
B.
C.
D.
E.

180 g/mol
970 g/mol
510 g/mol
390 g/mol
96 g/mol

Freezing-point depression: T = 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

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