Introductory Chemistry

AS.030.102 Section 2 Spring 2015

Instructor: Dr. Thyagarajan

Calendar
First Class: January 26 2015
Class meets MWF 10:00 a.m. to 10:50 a.m. in Remsen 1
Office hours: M,F: 2:00 3:30 p.m. or by appointment
In-class exams: February 23, March 30 and April 27
Final Exam: May 11th - 9:00 a.m. to noon

Syllabus
Required text
Oxtoby, Gillis, and Campion, Principles of Modern
Chemistry (7th edition)
OWL (on-line web-based learning system)
Optional
Student Solutions Manual

Syllabus
Three Units:
Electrochemistry and Kinetics
Chapters 17, 18
Quantum Mechanics
Chapters 4 6
Organic, Inorganic, Spectroscopy Chapters 7, 8, 20
Homework - Due wednesdays using OWL

Syllabus
Help Sessions:
TA help sessions
Learning Den
Problem Solving
PILOT
Grading and exams:
No scores will be dropped.
You will be able to bring ONE sheet (one side filled) with
equations/formulas/constants etc.
Equations will NOT be provided.
You WILL be given a periodic table.
5

Syllabus
To Study for the Tests
Look at the course objectives posted on the schedule.
Know how to do problems
Examples done in class
End-of-chapter homework problems
Optional tutorials and practice problems.
Understand all vocabulary words / concepts.
Try test questions from previous tests.

Syllabus
Required math skills
Algebra, including solving quadratic equations and
solving two equations with two unknowns.
Arithmetic, including exponents and logs
Metric System Prefixes
nano through kilo
Scientific Notation
Small amount of calculus
Bring to class each day
A calculator
Your periodic table
7

Syllabus
Grades
Homework
20 %
Mid-term Exams (3) 50 %
Final Exam
30 %
Clickers (class use)
10 points
Ethics Policy
Violations:
Homework, Tests
Penalties: Class failure through expulsion

Syllabus
Blackboard
Syllabus
Schedule
Discussion section
Lecture slides
Course help information
Log in to My JH
https://login.johnshopkins.edu
login: JHED ID
Password: your JHU password

How to Get Access to OWL

How to Get an OWL Access Code

Three ways to purchase:
Card packaged with new text from bookstore
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Instant access purchased online
Access codes are 25 characters long and look like
this:
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Cards look like this:

Questions?

12

Chapter 17 - Electrochemistry

Oxidation numbers and balancing equations

lectrochemical cells and cell parts

nergetics

13

Oxidation Numbers (Review)

14

Oxidation Numbers (Review)

+1

+2

0
+3

+4

-3

-2

-1

Oxidation Numbers (Review)

Transition Metals

Determine the oxidation number of

each atom
a) iron(III)chloride
b) nitrogen dioxide
c) sulfuric acid
d) potassium dichromate (K2Cr2O7)
17

Oxidation Reduction (Redox)

Reactions
A reaction where the oxidation number
of one or more atoms changes
(transfer of electrons).
Not+1a redox
-1 +1 reaction:
-2 +1

+1

-1

+1

-2

HCl(aq) + NaOH(aq) NaCl(aq) +

H2O(l)
0

Redox reaction:

+1

-2
18

Redox Reactions
VERBS:
OXIDATIONloss of electron(s) by a
species; increase in oxidation number.
REDUCTIONgain of electron(s);
decrease in oxidation number.
NOUNS:
OXIDIZING AGENTelectron
acceptor; species is reduced.
REDUCING AGENTelectron donor;
species is oxidized.
19

Balance Redox Reactions

Half-Reaction Method
+2-2

Step 1

+5 -2

+2

+6 -2

+2 -2

Determine which atoms change oxidation numbe

te: All electrochemical reactions in this course are in water.

20

Balance Redox Reactions

Half-Reaction Method

Step 2

Write out the half-reactions

(not balanced, but with key compounds or ions present)

21

Balance Redox Reactions

Half-Reaction Method

Step 3

Balance charges by adding electrons to the

right side for oxidation and to the left side for reduction.

CuS(s)

Cu2+(aq)

SO42-(aq)

8 e-

+6

-2
NO3-(aq) +
+5

3 e-

NO(g)
+2
22

Balance Redox Reactions

Half-Reaction Method

uS(s)
NO3-(aq) +

Cu2+(aq)
3 e-

+ SO42-(aq)
NO(g)

8 e-

For acidic media (solutions):

Step 4

Balance atoms (mass) by adding H2O to

balance oxygen and then H+ to balance hydrogen.

O(l) + CuS(s)

Cu2+(aq) + SO42-(aq) + 8 H+(aq)

H+(aq) + NO3-(aq) +

3 e-

NO(g) + 2 H2O(
23

Balance Redox Reactions

Half-Reaction Method

For acidic media (solutions):

Step 5

Multiply each half-reaction by an integer

the number of electrons in each is the same (so they cancel

x 34 H2O(l) + CuS(s)

x8

Cu2+(aq) + SO42-(aq)

+ 8 H+(aq) + 8 e-

4 H+(aq) + NO3-(aq) + 3 e+ 3CuS

2 H2O(l)
2+
2(g)
12NO
H2O
+
3Cu
+
3SO
(l)
(s)
(aq)
4 (aq) +
24 H+(aq) + 24 e32 H

+ 8 NO

24 e

24

Balance Redox Reactions

Half-Reaction Method

For acidic media (solutions):

Step 6

Cancel and add the two half-reactions.

12 H2O(l) + 3CuS(s)
+
24
H
+
24
e
(aq)
8

3Cu2+(aq) + 3SO42-(aq) +

32 H+(aq) + 8 NO3-(aq) + 24 eNO(g) + 16 H2O(l)3 CuS(s) + 8 NO3 (aq) + 8 H+(aq)

4
8

3 Cu2+(aq) + 3 SO42-(aq) + 8 NO(g) + 4

H2O(l)

25

Balance Redox Reactions

Half-Reaction Method

3 CuS + 8 NO3- + 8 H+
8 NO
+ 4(solutions):
H2O
For+basic
media

3 Cu2+ + 3 SO42-

Solve for acidic media first.

Step 7 Add OH- to both sides for every H+.
H+ + OH- becomes H2O. Cancel water.

4 3CuS + 8NO3 + 8H2O

8NO + 4H2O + 8OH3 CuS + 8 NO3- + 4 H2O
8 NO + 8 OH-

3Cu2+ + 3SO42- +
3 Cu2+ + 3 SO42- +
26

Examples for Practice

Acid Solution:
VO2+ + Zn

>
Zn2+

VO2+ +

27

Electrochemistry

Oxidation numbers and balancing equations

Electrochemical cells and cell parts

Energetics

28

Redox Reactions
Classifications:
Direct No external circuit
Indirect external circuit
Galvanic / voltaic cell - Produces
electrical
energy
Electrolytic cell Requires
electrical energy

29

Direct Redox Reactions

Oxidizing and reducing agents in direct
contact.
Cu(s) + 2 Ag+(aq) > Cu2+(aq) + 2 Ag(s)

Check
Oxidati
on
States
and
their
change
s

30

Direct Redox Reactions

With time, Cu plates out
onto Zn metal strip, and Zn
strip disappears.
Electrons
Electrons are
are transferred
transferred
2+
from
from Zn
Zn to
to Cu
Cu2+,, but
but there
there is
is
no
no useful
useful electric
electric current.
current.

Oxidation:
Zn(s)
Zn2+(aq) + 2e
Reduction: Cu2+(aq) + 2e Cu(s)
-------------------------------------------------------Cu2+(aq) + Zn(s) Zn2+(aq) + Cu(s)
31

Indirect Redox Reactions

To obtain a useful current,
we separate the oxidizing
and reducing agents.
- No direct contact.
- Electron transfer occurs
thru an external wire.
Electrochemical Cell
An apparatus that allows a redox reaction to
occur by transferring electrons through an
external connector (circuit).

Electrochemical Cells
Galvanic / voltaic cell

Electrolytic cell

Chemical change produces

electric current

electric current used to cause

chemical change in a nonspontaneous reaction

GRxn < 0

GRxn > 0

Product favored reaction

Reactant favored reaction
Batteries are
voltaic /
galvanic cells

Chrome plate car bumpers

Gold / silver plate jewelry, etc.
33

Galvanic Cell Parts

Anode:

Cathode:

Zn2+(aq) + 2 e

Zn(s)

Cu2+(aq) + 2e Cu(s)

Cu2+(aq)+ Zn(s) Zn2+(aq)+ Cu(s)

-hand solution

Convention

Zn(s) Zn2+(aq) + 2 e
Anode: Oxidation occurs
at this electrode

Right-hand solut
Cu2+(aq) + 2e Cu(s)

Cathode: Reduction occurs

at this electrode

Electrons flow in the wire from anode to cathode.

Galvanic Cell Parts

35

Galvanic Cell Parts

36

Galvanic Cell Parts

37

Galvanic Cell Parts

Ammeter:
measures
current

Solutions [Cu(NO3)2 and

AgNO3] are connected by a
salt bridge, containing
NaNO3.
Porous plugs at ends of
bridge prevent solutions
from mixing but allows ions
to pass through.
Left:
Cu(s) is oxidized
- Cu2+ dissolves
- pos. charge
builds up
- ions move
Right:
Ag+ is reduced
- Ag precipitates
- neg. charge
builds up
38

Writing Galvanic Cells

node on the left

athode on the right.
ectrons flow left to right.

Cation in solutionCation in solution

at the anode
at the cathode

Cu|Cu2+||Ag+|Ag

Anode

Salt Bridge

Cathode
39

Diagram the following galvanic cell, indicating the

direction of flow of electrons in the external circuit

and the motion of ions in the salt bridge:

Sn|Sn2+(aq)||Cl(aq)|Hg2Cl2(s)|Hg(l)

Write the half-reactions at each electrode and a

balanced equation for the overall reaction in this cel

40

2NaCl(l)

Electrolytic Cell Parts

Anode, cathode, electrolyte solution

All in one container, no salt bridge

2 H2O(l)

2 H2(g) + O2(g)

2Na(l) + Cl2(g)
41

Electrochemistry

Oxidation numbers and balancing equations

Electrochemical cells and cell parts

Energetics

42

Energetics
Mechanics
Electrostatics m m
F ma G

Force

r2

G 6.67 x 10 11

m3
kg s 2

mearth
PE m g h m G 2 h
r

Potential PE w m g h
Energy
m gh

q1 q 2
F k 2
r
1
10 C
k
1.113 x 10
4 0
V

Potential

mearth
gh G
r

q1 q 2
PE k
r

q1
PE w q 2 k
r

q1
k
r
E

43

Energetics
Cu2+(aq)+ Zn(s) Zn2+(aq)+ Cu(s)
If the only change is the transfer of electrons, the
change in energy of the reaction is the same as the
change in energy of the electrons.
Energy = w = Q * V
voltage

Q is charge

Q=1C
V = 1 volt
= 1J
Q = 1 electron (1.602 x 10-19 C) V = 1 volt
Energy = 1 eV
1 eV = 1.602 x 10-19 J

V is
Energy

44

Energetics
Cu2+(aq)+ Zn(s) Zn2+(aq)+ Cu(s)
w P.E. Q V

Q is charge

V is voltage

Q it

i = current (C/s)
t = time (s)
Q is the number of electrons that went through the
circuit
If we measure the voltage (voltmeter), current
(ammeter) and time
then we can calculate
- number of electrons passed through the
electrodes
- amount of product produced (mass, moles,
concentration)

45

Cell
Potential
voltmeter
lead

+1.10 V

voltmeter
lead

Zn and Zn2+,
anode

Cu and Cu2+,
cathode

1.0 M

1.0 M

Electrons are driven from anode to cathode by an

electromotive force or emf (change in potential).
For Zn/Cu cell, this is indicated by a voltage of 1.10
at 25 C and when [Zn2+] and [Cu2+] = 1.0 M.

Cu2+ + Zn

Cu +

Zn2+

46

Cell Potential

For Zn/Cu cell, potential is +1.10 V at 25 C and

when [Zn2+] and [Cu2+] = 1.0 M.

STANDARD CELL POTENTIAL, E

A quantitative measure of the tendency of reactants

to proceed to products when all are in their
standard states, 1 atm (gases) and 1 M (solutions).
47

Cell Potential
Instead of tabulating the potential for every possible
electrochemical cell, half-reaction potentials are
tabulated.
Balanced half-reactions can be added together to
get overall, balanced equation.
2+
Zn(s)

Zn
Zn(s) Zn2+(aq)
(aq) +
+ 2e2e2+
Cu
Cu2+(aq)
(aq) +
+ 2e2e- Cu(s)
Cu(s)
--------------------------------------------------------------------------------------2+
2+
Cu
Cu2+(aq)
(aq) +
+ Zn(s)
Zn(s) Zn
Zn2+(aq)
(aq) +
+
Cu(s)
Cu(s)
If we know Eo for each half-

reaction, we could get Eo for net

reaction.

48

Cell Potential
Cant measure 1/2 reaction Eo directly.
Therefore, measure it relative to a
STANDARD HYDROGEN ELECTRODE, SHE. Also NHE

2 H++ ((aq
+
2e
H22 ((gg,, 11 atm)
aq,, 1
1 M)
M)
atm)

Eo = 0.0 V
49

Zn/Zn2+ half-cell hooked to a SHE.

Eo measured for the cell = + 0.76 V
Negative
electrod
e

Positiv
e
electro
de

Supplie
Accepto
r of
r of
electron
electron
s Zn Zn2+ + 2e- 2 H+ + 2e- H2 s
Oxidation
Reduction
Reduction
Anode
Cathode
of H+
Net Reaction: Zn(s) + 2H+ Zn2+ + 50H2(g
by Zn

Zn2+/Zn and 2H+/H2 Cell

Overall reaction is sum of two
half-reactions:
Cathode:
Anode:

2 H+

(aq)

Zn(s) Zn2+(aq) + 2 e-

Overall potential is:

o
E
Zn2+ (anode)
(aq) + 2e-

Zn

2+

+ 2 e- H2(g)

(aq) + 2e-

is

(cell)

= E

(cathode)

- 0.76
V
Half-Reaction
Potential

+ 0.76 V = 0.00 V - E

Zn

isStandard Reduction Potential

51

Cu2+/Cu and 2H+/H2 Cell

Eo(cell) = + 0.34 V

Positive
Accepto
r of
electron
s
Cu

+ 2e- Cu
Reduction
Cathode

2+

Negative
Supplie
r of
electron
s
+ 2e-

H2 2 H +
Oxidation
Anode

his Electrochemical Cell runs right-to-left

52

Cu2+/Cu and 2H+/H2 Cell

Overall reaction is sum of two
half-reactions:
Cathode:
Anode:

Cu2+

(aq)

+ 2 e- Cu(s)

H2(g) 2 H+(aq) + 2 e-

Overall potential is: E

o

(cell)

= E

(cathode)

-E

(anode)

Cu2+ + 2e- Cu

is

+ 0.34 V = E

(cathode)

- 0.00

+ 0.34Half-Reaction
V
Potential

Standard Reduction Potential

53

Zn2+/Zn and Cu2+/Cu Cell

+

Anode,
negative
, source
of
electrons
Anode:

Zn2+(aq) + 2e-

Zn(s)

Cathode,
positive,
sink for
electrons

Eo = - 0.76 V

Cathode: Cu2+(aq) + 2e- Cu(s) Eo = + 0.34 V

------------------------------------------------------------------------Cu2+(aq) + Zn(s) Zn2+(aq) + Cu(s)
Overall potential is:

(cell)

= E

o
(cathode)

-E

(anode)

= + 0.34 V - ( -0.76 V) = + 1.10 V

54

Table of Standard
Reduction Potentials

Organize half-reactions
by relative ability to
act as oxidizing agents

ndard Reduction Potentials

book (7th ed.) Appendix E

Handbook Pages 8-20 thru 8-31

55

Best
oxidizin
g
agents

Potential Ladder for Reduction

Best
reducin
g
agents
56
Half-Reactions

Table of Standard Reduction

Potentials
Any substance on the right will
reduce any substance higher
than it on the left.
Zn can reduce H+ and Cu2+.
H2 can reduce Cu2+ but not
Zn2+
Cu cannot reduce H+ or Zn2+.

57

Standard Redox Potentials, Eo

Ox. agentCu2+ + 2e- > Cu
+

2 H + 2e- >

H2

Zn2+ + 2e- > Zn

+0.34
0.00

-0.76Red. agent

Any substance on the right will reduce

any substance higher than it on the left.

Northwest-southeast rule: productfavored reactions occur between

reducing agent at southeast corner
oxidizing agent at northwest corner
58

Standard Redox Potentials, Eo

Ox. agentCu2+ + 2e- > Cu
+

2 H + 2e- >

H2

Zn2+ + 2e- > Zn

+0.34
0.00

-0.76Red. agent

e REDUCING AGENT gets OXIDIZED at the ANODE

Zn Zn2+ + 2 e-

e OXIDIZING AGENT gets REDUCED at the CATHO

Cu2+ + 2 e- Cu
59

Using Standard Redox

Potentials

In which direction do the following reactions go?

Cu(s) + 2 Ag+(aq)

2+

Cu2+(aq) + 2 Ag(s)

+ 2e > Cu
+ e- > Ag

E
E

2 Fe2+(aq) + Sn2+(aq)
+
+

e
>
2 e >

Fe
Sn(s)

What is E

2+

(cell)

o
o

= + 0.340 V
= + 0.800 V

Goes right
as written

2 Fe3+(aq) + Sn(s)
Goes left,
E = + 0.770 V
reverse of
o
E = 0.136 V
direction written
o

for the overall reaction?

60

Uses of E

Values

Use Standard Reduction Potentials to

predict:
- Direction of redox reactions
(anode and cathode)
- Cell potentials
61

Using Standard Redox

Potentials
2 Fe3+(aq) + Sn(s)

2 Fe2+(aq) + Sn2+(aq)

>

Fe2+

2 e

>

Sn(s) E

What is E

(cell)

=E

(cell)
o

E
o

= + 0.770
V
CATHODE

= 0.136 VANODE

for the overall reaction?

(cathode)

-E

(anode)

= 0.770 (-0.136) = + 0.906 V

Do NOT multiply by 2 or
E o is an INTENSIVE property.

62

Using Standard Redox

Potentials
What is the reducing
agent?
Fe

Which is the anode?

Fe
Which direction do the
electrons
flow?
d2+ + 2e > Cd E o = - 0.40
V
e2+ + 2e- > Fe E o = - 0.44
V the Fe electrode
From
to the Cd electrode.
What is the cell potential
E o(cell) = E o(cathode) - E o(anode) = -0.40 (-0.44) =
63
+ 0.04 V

Using Standard Redox

Potentials

Assume I ion can reduce water.

2 H22O + 2e > H22 + 2 OH

Cathode
2 I
>
I22 + 2e
Anode
------------------------------------------------2 I + 2 H22O > I22 + 2 OH + H22
O + 2 e- > H2 + 2 OH2 e- > 2 I-

E
E

= - 0.828 V
o
= + 0.535 V
o

E o(cell) = E o(cathode) - E o(anode) = -0.828 (0.535)

= - 1.363 V
Negative E o means reaction occurs in
opposite direction
64

Fe(s) | Fe2+(aq) || Al3+(aq) | Al(s)

Fe2+ + 2e- > Fe
Or
Fe > Fe2+ + 2 e-

Al > Al3+ + 3 eor

Al3+ + 3 e- > Al

Fe2+ + 2e- > Fe

Al3+ + 3 e- > Al

E o = - 0.44 V
E o = - 1.66 V

Al is the better reductant -- It will reduce Fe2+

Fe2+ is the better oxidant -- It will oxidize Al

65

Fe(s) | Fe2+(aq) || Al3+(aq) | Al(s)

Fe(s

Electrons
> or <
Al(s)

Fe

1M
Fe(NO3
)2

1M
Al(NO3)
3

+ 2e- > Fe
Or
Fe > Fe2+ + 2 e-

Al > Al3+ + 3 eor

Al3+ + 3 e- > Al

Fe2+ + 2e- > Fe

Al3+ + 3 e- > Al

E o = - 0.44 V
E o = - 1.66 V

2+

66

Fe(s) | Fe2+(aq) || Al3+(aq) | Al(s)

Fe2+ + 2e- > Fe

Al > Al3+ + 3 e-

Fe2+ + 2e- > Fe

Al3+ + 3 e- > Al

E o = - 0.44 V
E o = - 1.66 V

Al is the better reductant -- It will reduce Fe2+

Fe2+ is the better oxidant -- It will oxidize Al

Electrons flow FROM Al TO Fe2+

67

+ 1.22
V

Cathode
Positive
Fe(s

Electrons

Anode
Negative
Al(s)

Fe

2+

1M
Fe(NO3
)2

1M
Al(NO3)

+ 2e- > Fe

(cell)

Al > Al3+ + 3 e-

= + 1.22 V

Which electrode gains mass?

Which electrode loses mass?

68

Fe(s) | Fe2+(aq) || Al3+(aq) | Al(s)

Cathode
Positive
Fe(s

(cell)

+ 1.22
V

Anode
Negative
Al(s)

Electrons

Fe

2+

1M
Fe(NO3
)2

+ 2e- > Fe

1M
Al(NO3)
3

Al > Al3+ + 3 e-

Fe2+ + 2e- > Fe

E o = - 0.44 V
Al3+ + 3 e- > Al
E o = - 1.66 V
= E o(cathode) - E o(anode) = -0.44 (- 1.66) = +
1.2
69