CHAPTER 20: ELECTROCHEMISTRY
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Transcript CHAPTER 20: ELECTROCHEMISTRY
Study of the relationships
between electricity and
chemical reactions
Oxidation States
REVIEW: How do we determine the
oxidation state?
What is the oxidation state of the boldfaced
element:
○ P2O5
○ NaH
○ Cr2O7-2
○ SnBr4
Redox Reactions
How do we determine if a reaction is a
redox reaction?
How would we define the following
vocabulary words:
Oxidizing agent (oxidant): agent aquiring
electrons from another substance (reduced)
Reducing agent (reductant): agent giving up
electrons (oxidized)
Identifying Oxidizing and
Reducing Agents
Cd (s) + NiO2 (s) + 2 H2O (l) Cd(OH)2 (s) + Ni(OH)2 (s)
2 H2O (l) + Al (s) + MnO4-(aq) Al(OH)4- (aq) + MnO2 (s)
Balancing Redox Reactions
How is balancing a redox reaction
different than balancing a normal
equation?
How do we split a redox reaction?
Why would using half reactions make
the process easier?
Balancing equations: acidic
solutions
In balancing reactions, we use “skeleton”
ionic equation.
Predict why this is called the skeleton ionic
equation.
Step-by-step procedure:
STEP 1: BALANCE EQUATION
○ Balance elements other than H and O
○ Balance O atoms by adding H2O as needed
○ Balance H atoms by adding H+ as needed
○ Finally balance charge by adding e- as needed
Balancing equations: acidic
solution cont’
STEP 2: Multiply half-reactions by
integers as needed to make the number
of electrons lost in the oxidation halfreaction equal the number of electrons
gained in the reduction half-reaction
STEP 3: Add half reactions (simplify if
possible by canceling species found on
both sides)
STEP 4: Check to make sure atoms and
charges are balanced
ಅಭ್ಯಾಸ (Kannada)
Given the skeleton equation:
MnO4- (aq) + C2O42- (aq) Mn2+ (aq) + CO2 (g)
April 10th, 2013
DO NOW:
Predict how balancing a redox reaction in
a basic solution is different than in an
acidic solution.
Basic Solutions
For Basic solutions:
Follow same process except for after
balancing H+, add OH- to both reactants and
products side to “neutralize” the H+ ion.
행하다 (Korean)
See Worksheet
Voltaic Cells
Energy is released when using a voltaic
cell, how is it being used?
How can we define voltaic cell?
Draw a diagram of a voltaic cell in your
notebook.
Anodes and Cathodes!
How do we differentiate between an
anode and a cathode?
Predict how the voltaic cell conducts
electricity.
Why is using a salt bridge necessary?
Predict which direction the anions flow.
Describing a voltaic cell
Cr2O72- (aq) + 14 H+ (aq) + 6 I- (aq) 2 Cr3+ (aq) + 3 I2 (s) + 7 H2O (l)
Is a spontaneous reaction in a voltaic cell. A solution
containing K2Cr2O7 and a solution containing H2SO4 are
poured into 1 beaker and a solution containing KI is
poured into a separate beaker. 2 pieces of metal that
won’t react with either are suspended into both solutions.
Indicate the following:
○
○
○
○
○
Reaction at anode
Reaction at cathode
Direction of Electron flow
Direction of ion flow
Signs of electrodes
Electricity Flow
Describe the flow of water in a waterfall.
Why?
Why do electrons flow spontaneously
from an anode to a cathode?
How do we measure energy between
the two?
Potential Energy
Potential Energy difference between the
two electrodes is called cell potential.
Also known as: Electromotive force (EMF)
○ Pushes e- through circuit
Assume 25°C standard conditions
Standard Cell Potential: E°cell
Depends on particular anode and cathode
half cells
How might we measure E°cell
Reference Cell
Why is it necessary to have a reference
half reaction?
Allows for measure of other cell potentials
directly.
Reference cell: SHE (standard hydrogen
electrode)
Calculating E°cell
How do we calculate E°cell from the
SHE?
IE: oxidation of zinc and reduction of
hydrogen ion
How would we represent this standard
reduction potential?
Reactions
How do we determine how likely a
reaction is to occur?
Given that electrons must flow
spontaneously, what assumption can we
make about the values of the E°red of
both the anode and the cathode?
April 11th, 2013
Do Now:
Thermodyanmics Quiz.
○ Have out Calculator and Reference Sheet.
Spontaneity of Voltaic Cells
How can we use our equation for standard cell
potentials as a generalized equation?
Based on this equation and your knowledge of
thermodynamics, predict how we determine if
the reaction is spotaneous.
NOTE: E = EMF @ nonstandard conditions
E°= EMF @ standard conditions
Practice: Is this reaction spontaneous:
Cu (s) + 2 H+ (aq) Cu2+ (aq) + H2 (g)
Reactivity of Metals
How are the standard reduction
potentials related to the activity series of
metals?
Which is a stronger reducing agent:
silver or nickel? Why?
Gibbs Free Energy (it never
leaves you alone)
How can we related Gibbs free energy to
EMF?
Predict the sign of the Gibbs free energy if you
have a positive EMF. Why is this to be
expected?
Rewrite the equation for a reaction in
“standard conditions”
How can we relate E° to K?
April 12th, 2013
DO NOW:
Using standard reduction potentials,
calculate standard free energy change and
k @ 298K for:
4 Ag (s) + O2 (g) + 4H+ (aq) 4 Ag+ (aq) + 2 H2O (l)
Suppose the reaction is halved, calculate the
change in gibbs free energy at standard
conditions, EMF at standard conditions, and k.
Non standard Conditions
As a cell is discharged (released all
possible electricity) reactants are
consumed and products are generated
the concentration changes until EMF
drops to 0 (dead cell)
We want to answer: How is EMF
generated under non-standard
conditions
Concentration is a changin!
Walther Nernst (1864-1941)
Established many theoretical foundations of
electrochemistry
Effect of concentration on cell EMF can be
obtained from effect of concentration on
Gibbs Free Energy.
Which equation would we want to use to
relate effect of concentration on Gibbs Free
Energy. Why?
Practice… again.
Calculate the EMF @ 298K generated by the
voltaic cell in which the reaction is
Cr2O72- (aq) + 14H+ (aq) + 6 I- (aq) 2 Cr3+ (aq) + 3 I2 (s) + 7 H2O (l)
[Cr2O72-] = 2.0 M
[H+] = 1.0 M
[I-]= 1.0 M
[Cr3+ ] = 1.0 x 10-5 M
One More
If the potential of a Zn-H+ cell is at 0.45
V at 25°C when [Zn2+] = 1.0 M and PH2 =
1.0 atm, what is the H+ concentration?
Concentration cells
Voltaic cells constructed by the same
species in both half-cells with different
concentrations
Ni2+ - Ni reaction
Write the two half reactions and the overall
reaction.
How can we calculate the EMF of this cell?
Determine the EMF.
If E° is 0, what produces the driving force?
**NOTE: when concentrations become the
same: Q = 1, E = 0
pH meters
Generating a potential by a concentration
difference
Example: A voltaic cell with 2 hydrogen
electrodes: Electrode 1: PH2 = 1.0 atm and
unknown concentration of H+ ions.
Electrode 2 is a standard Hydrogen
electrode. At 298K, E° = 0.211 V, and the
electrical current is observed to flow from
electrode 2 to electrode 1. What is the pH
of the unknown solution?
Electrolysis (Electrolytic cells)
Non-spontaneous redox reactions driven
by outside electrical energy
IE: decomposition of molten NaCl to Na
and Cl2
2 electrodes immersed in either molten
salt of solution
Process still similar to voltaic cells
Battery acts as electron pump
Electroplating
How is electroplating
different than general
electrolysis?
Uses electrolysis to
deposit a thin layer of
metal on another metal
to improve beauty or
resistance to corrosion
Uses active electrodes
instead of inert
Quantitative Electrolysis
How many moles of electrons are needed to
create the following from their ions?
Sodium
Copper
Aluminum
Amount of substance reduced or oxidized in
electrolytic cell is proportional to number of
electrons passed through cell
Quantity of charge is measured in Coulombs
Charge on 1 mol = 96485 C.
○ Coulomb = quantity of charge passing a point in a
circuit in 1 s when the current is 1 A (ampere)
Coulombs = amperes x seconds
Practissimo!
Calculate the number of grams of
aluminum produced in 1.00 hour by the
electrolysis of molten AlCl3 if the
electrical current is 10.0 A.