Annjaneth Briones and Nathalie Dagmang

€an

electron is transferred from one reactant to another

Zn(s) +

2+ Cu

Cu(s) +

2+ Zn

€An

electron-exchange reaction/oxidation or reduction at an electrodeq €a spontaneous redox reaction produces energy or
€a

non-spontaneous redox reaction uses up energy

€ Direct

€ Electrochemical

Cell

No work done

Work done/needed

Voltaic/Galvanic Cell
€ Spontaneous

Electrolytic Cell
€ Non-spontaneous

reaction € Generates or stores energy € ex. batteries

reaction € Uses up electrical
€ ex. Metal

plating, recovery of metal from ores

Voltaic/Galvanic Cell
load energy

Electrolytic Cell
Power supply

energy

anode

+
cathode

+
anode

cathode

Work done by system to surroundings

Work done on system by surroundings

ANODE Rxn
Galvanic Cell Electrolytic cell
Ion moving towards it

CATHODE Sign _ + Rxn reduction reduction
Ion moving towards it

Sign + _

oxidation oxidation

anions anions

cations cations

difference b/w the anode and cathode of galvanic and electrolytic cells is their polarity

Flow of electrons: ANODE

CATHODE (ALWAYS)

Voltaic/Galvanic Cell
2

e-

Voltmeter
SO42Zn
Salt bridge

e-

1

2K+ + Cu CuSO4

3

ZnSO4
Zn(s) Zn2+ (aq) + 2e-

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

Anode = Oxidation

Cathode = Reduction

Zn|Zn2+||Cu2+|Cu

€ Has

infinite resistance = won·t consume electricity € Measures the potential difference of the 2 half cells (Voltage)
‡ parameter for the tendency of the reaction to

proceed to an equilibrium state (same Vs)
‡ potential continues to decrease until it reaches

0.00 V.
€ Measures

the Electromotive Force (EMF)

‡ Electric work it can do/ can be extracted

€ Prevents

the direct reaction but still maintains electrical contact b/w the half cells. € Provides ions to neutralize its charges € Negative ions positive half-cell (Zinc) € Positive ions negative half-cell (Copper)
€

Some SO42-ions (from the cathode vessel) and some Zn2+ ions (from the anode vessel) also migrate into the salt bridge.

€ Solid

conductor through which an electric current enters or leaves or emitter of electric charge

€ Collector

€ Oxidation

takes place

e-

Zn(s) Zn2+ (aq) + 2e€ Reducing

agent
Zn2+

e-

² causes the cathode to reduce ² less e- affinity

Zn(s) SO42ZnSO4 electrolyte

€ Reduction

takes place

e-

Cu2+ (aq) + 2e- Cu(s)
€ Oxidizing

agent
Cu2+ SO42-

e-

² causes the anode to oxidize ² more e- affinity

+
Cu(s) CuSO4 electrolyte

Cu2+ (aq) + 2e- Cu(s) Zn(s) Zn2+ (aq) + 2eZn(s) + Cu2+ Cu(s) + Zn2+

(reduction) (oxidation) (Over-all reaction)

€

Electric current - transfer of charge through electrolytic and metallic conduction Electrolytic or ionic conduction- charge is carried by ions: cations move toward the cathode and anions move toward the anode Metallic conduction- charge is carried by flow of electrons from the negative pole to the positive pole the electrical conductors in an electrochemical cell are the electrodes (via metallic conduction), and the electrolyte solution (via electrolytic conduction)

€

€ €

€ Potential

at standard conditions:

‡ 1.00 M ‡ 1 atm ‡ 25 C
€ Independent

on number of moles

‡ Cu2+ (aq) + 2e- Cu(s) E = 0.34 V ‡ 2Cu2+ (aq) + 4e- 2Cu(s) E = 0.34 V

€ Measure

of the tendency for a reduction

to occur (when SHE is the anode)
‡ (+) V = spontaneous ‡ (-) V = non-spontaneous ‡ When reaction is reversed (turned into

oxidation), V changes sign
€ Standard

reduction potential

‡ Potential when the SHE (Standard Hydrogen

Electrode) is the anode

€ Potential

assigned as 0.00 V

2H+ + 2e- H2 H2 2H+ + 2e-

E = 0.00 V E = 0.00 V

Cu2+ (aq) + 2e- Cu(s) Zn(s) Zn2+ (aq) + 2eZn(s) + Cu2+ Cu(s) + Zn2+

E E

cathode anode

= 0.340 V = -0.763 V = 1.103 V

E

cell

E

cathode

-E

anode

=E

cell

*reduction potentials are used

€ Factors

affecting cell potential:

‡ Concentration ‡ Temperature ‡ Nature of reactant

E = E - RT ln Q nF
where: R (gas constant) = 8.314 J/molK, T = temperature in Kelvin, n= number of moles e- in rxn F (Faraday ) = 96, 485 Coulombs Q = reaction quotient

E = E - 0.0592 log Q n
(Substituting the constants and assuming 25 C temperature)

€ At

equilibrium,
E cell ! E
cell

G = 0, Ecell = 0, and Q = Keq 0.0592 thus, o 

n

log Q

becomes
E o cell !

0.0592 log K eq n

€ Solving € Note

for Keq, we get:

« ( n)(Eocell) » ¼ Keq ! anti log¬ ¬ 0.0592 ¼ ­ ½

that Keq can be Ksp, Ka, Kb, Kf , etc.

(G ! nFE cell
€

Thus, the reaction is spontaneous only if G is negative and Ecell is positive Example: Calculate the 3 Sn4+ + 2 Cr Go in J/mol for 3 Sn2+ + 2 Cr3+
where F = 96485 C/mol e-, n = no. of e- transferred

€

Cathode: 3(Sn4+ + 2eSn2+) Anode: 2(Cr Cr3+ +3e-)

Eo = + 0.15 V Eo = - 0.74 V

Eocell = (+0.15 V) ²(-0.74 V) = + 0.89 V
Note: 1 J = 1 CV
¨ 6 mol e  ¸¨ 96,485 C ¸ ¹ ¹© (G o ! nFE o cell ! © © mol rxn ¹© mol e  ¹  0.89 V ! 515,230 J / mol º ª ºª

The very negative value of G indicates that the reaction is product-favored. This is consistent with the positive value of Ecell

€ Let

us now calculate for the Keq of the previous example = (+0.15 V) ²(-0.74 V) = + 0.89 V

€ Recall: Eocell € Thus,

« (6)(0.89) » ! 1.59 x1090 ! anti log ¬ eq 0.0592 ¼ ­ ½

the very large value of Keq reinforces our previous conclusion that the reaction is product-favored

€ the

mass of the product formed or the reactant used is proportional to the amount of electricity that passes through the system

C = At
Where C = amount of electricity passing A (ampere) = current T= seconds 1 F = 96,500 Coulomb/mole e-

1 Set-up the following half-cells:
Zn|Zn2+(1 M) Cu|Cu2+(1 M) Fe3+(1 M), Fe2+|Fe
Zn Cu C

1 M ZnSO4

1M CuSO4

2 M FeSO4 +2 M FeCl3

* Why graphite and not Iron nail? Desired reaction is Fe3+ Fe2+ not Fe3+ Fe
C

2 M FeSO4 +2 M FeCl2 

When iron nail is used: Fe3+ Fe2+ FeO
Fe3+ is oxidized to Fe2+ which will cause rusting

Fe3+(1 M), Fe2+|Fe Graphite = semi-conductor - inert; won·t participate, will only conduct

2 Connect the Cu2+/Cu half-cell with a
voltmeter and a KNO3 salt bridge
Voltmeter
Salt bridge

Cu CuSO4

X X-

3 Record Voltmeter reading
Voltmeter
Salt bridge

Cu CuSO4

X X-

1 Set-up the following half-cells:
Cl- (1 M), Cl2|C Br-(1 M), Br2|C
C C C C

I-(1 M), I2|C
C C

1 M KCl

1M KBr

1 M KI

Carbon = inert won·t participate in the rxn

2 Connect to 1.5 V dry cells for 1 min
to generate X2
Cl-(1 M), Cl2|C Br-(1 M), Br2|C
batt batt

I-(1 M), I2|C
batt

C

C

C

C

C

C

1 M KCl

1M KBr

1 M KX

* What happened:
I-(1 M), I2|C
batt

Bubbles formed from H2 0

C

C

Formed brownish substance (Iodine / I2)

KI + I2

2I- I2 + 2e-

* What happened:
Cl-(1 M), Cl2|C
batt Bubbles C C

Br-(1 M), Br2|C
batt

Bubbles C C

KCl + Cl2

KBr + Br2

Yell

ish

2Cl- Cl2 + 2e-

2Br- Br2 + 2e-

3 Connect the electrolyzed solutions to
the Cu half cell
Voltmeter
Salt bridge

Cu CuSO4

C KX, X2

X2 + 2e-

2X-

3 Record voltmeter reading
Voltmeter
Salt bridge

Cu CuSO4

C KX, X2

Cell Notation
Cu|Cu2+||Cu2+|Cu Zn|Zn2+||Cu2+|Cu Cu|Cu2+||Fe3+|Fe C|Cl-,Cl2||Cu2+|Cu C|Br-,Br2||Cu2+|Cu C|I-,I2||Cu2+|Cu

Volts
0.0896 1.08 0.414 0.468 0.269 0.121

€Finding

for Eanode:
2+||Cu2+|Cu Zn|Zn

Take second set-up:

Given:

Cu2+ (aq) + 2e- Cu(s) , E = 0.34

€Finding

for Eanode:

Take second set-up: Zn|Zn2+||Cu2+|Cu Manipulating the equation: E cathode - E anode = E 0.34 - E anode = E cell

cell

E

anode

= 0.34 - E

cell

€ Finding

for Eanode:

Take second set-up: Zn|Zn2+||Cu2+|Cu
Experimental E
cell

= 1.08 V

E

anode

= 0.34 - 1.08

E

anode

= - 0.74

Zn2+ (aq) + 2e- Zn(s) , E = 0.763 % error = [-0.763 ² (- 0.74)]/-0.763 = 3.01%

€Finding

for Ecathode:
2+|C Fe

Take third set-up:
2+||Fe3+, Cu|Cu
Given:

Cu2+ (aq) + 2e- Cu(s) , E = 0.34

€Finding

for Ecathode:

Take third set-up: Cu|Cu2+||Fe3+,
Manipulating the equation:

Fe2+|C

E E

-E cathode = E
cathode

anode

= E cell cell + 0.34
cell

E

cathode

= 0.34 + E

€ Finding

for Ecathode:

Take third set-up: Cu|Cu2+||Fe3+,
Experimental E
cell

Fe2+|C

= 0.414 V

E

cathode

= 0.414 + 0.34

E

cathode

= 0.754 V

Fe3+ + e- Fe2+ E = 0.771 % error = [0.771- 0.754)]/0.771 = 2.2 %

Voltage reading: E = 0.468 V

Ecathode = Ecell + 0.34
Ecathode = 0.468 + 0.34 = 0.808 V

€ Take

4th set-up:

C|Cl-, Cl2||Cu2+|Cu
Data:

Ampere = 0.065 A Time = 270 seconds Substituting: C = 0.065 x 270

= 17.55 Coulombs

€ Take

4th set-up:

C|Cl-, Cl2||Cu2+|Cu
17.55 C x(1 mole e-/96,500 C) = 1.818 x 10-4 2Cl- (aq) Cl2+ 2eFrom the equation,

2 mol e- = 2 mol Cl- transformed to Cl2
Hence,

1.818 x 10-4 mol e- = 1.818 x 10-4 mol Cl-

€ Take

4th set-up:

C|Cl-, Cl2||Cu2+|Cu
0.025 mol Cl- - 1.818 x 10-4 mol Cl- = 0.0248182 mol Cl- left 0.0248182 mol Cl-/0.025 L = 0.992728 M [Cl-] = 0.992728 M

2Cl- (aq) Cl2+ 2eCl2 is a gas, so the activity of Cl2 is taken as 1,

so

Q = __1__ [Cl-]2

Substituting E, n and Q in the equation

E = E - 0.0592 log Q n

0.808 = E - 0.0592 log (1.014704) 2
E = 0.808 + 0.0001876479346 = 0.8081876479 V

Cell Notation
Cu|Cu2+||Cu2+|Cu Zn|Zn2+||Cu2+|Cu Cu|Cu2+||Fe3+|Fe

Cathode Copper Copper Iron

Anode Copper Zinc Copper Chlorine Bromine Iodine

C|Cl-,Cl2||Cu2+|Cu Copper C|Br-,Br2||Cu2+|Cu Copper C|I-,I2||Cu2+|Cu Copper

Cell Notation
Cu(s)|Cu2+(aq) (1M)|| Cu2+(aq) (1M)|Cu(s) Zn(s)|Zn2+(aq) (1M)|| Cu2+(aq) (1M)|Cu(s) Cu(s)|Cu2+(aq) (1M) ||Fe3+(aq) (1M), Fe2+(aq) (1M)|C(graphite) C(graphite)| Cl2(g) |Cl-(aq) (1M)||Cu2+(aq) (1M)|Cu(s) C(graphite)| Br2(l),Br-(aq) (1M)||Cu2+(aq) (1M)|Cu(s) C(graphite)| I2(s),I-(aq) (1M)||Cu2+(aq) (1M)|Cu(s)

Cathode
Cu2+(aq) (1M)|Cu(s) Cu2+(aq) (1M)|Cu(s) Fe3+(aq) (1M), Fe2+(aq) (1M)|C(graphite) Cu(s)|Cu2+(aq) (1M) Cu(s)|Cu2+(aq) (1M) Cu(s)|Cu2+(aq) (1M)

Anode
Cu(s)|Cu2+(aq) (1M) Zn(s)|Zn2+(aq) (1M) Cu(s)|Cu2+(aq) (1M)

C(graphite)| Cl2(g) |Cl-(aq) (1M) C(graphite)| Br2(l),Br(aq) (1M) C(graphite)| I2(s),I-(aq) (1M)

Variable Half- Calculated Cell Notation Volts
Cu|Cu2+ Zn|Zn2+ Fe3+|Fe C|Cl-,Cl2 C|Br-,Br2 C|I-,I2 0.2504 - 0. 4 0. 54 *0.808 *0.609 *0.46

Book Value
0.34 - 0. 63 0. .359 .08 0.6 5

% Error
26 % 3.0 % 2.2 % 40.54 % 43.9 % 25.04 %

* assuming concentration did not change with electrolysis

€ More

(-) E

red

‡ Higher tendency to be oxidized ‡ Higher reducing power ‡ When placed as anode, reaction is spontaneous
€ More

(+) E

red

‡ Higher tendency to be reduced ‡ Higher oxidizing power ‡ When placed as cathode, reaction is spontaneous

€ Take

Electrolysis for 4th set-up:

C|Cl-, Cl2
2Cl- (aq) Cl2+ 2eReduction potential = 1.359 V spontaneous Oxidation potential = -1.359 V non-spontaneous Voltage is applied

Vapplied = Eanode - Ecathode

2Cl- (aq)

Cl2+ 2e-

At equilibrium, Eanode = Ecathode V=0 Oxidation and reduction at same rate

2Cl- (aq) If Eanode = Ecathode If Eanode > Ecathode If Eanode < Ecathode

Cl2+ 2esystem at equilibrium

Vapplied = Eanode - Ecathode
Ecathode, Eanode Ecathode, Eanode

In the experiment, we want to produce more Cl2

oxidation should predominate Eanode should increase

should be Eanode > Ecathode

2Cl- (aq)

Cl2+ 2e-

Eanode = E - 0.0592 log [Cl2] n [Cl-]2 Ecathode = E - 0.0592 log [Cl-]2 n [Cl2]

Cl2 = Ecathode = Ered = spontaneity

€ Concentration

changed as the halogen solutions were electrolyzed € Electrolysis did not produce enough halogen, X2 that will be reduced € Slightly different concentrations (not both exactly 1 M) increase in voltage reading (concentration difference can also cause potential diff)

Current X Time

no. of Coulombs

Mol. of epassed

Mass of substance

€ Example: Calculate

the mass of copper metal produced at the cathode during the passage of 2.50 amperes of current through a solution of copper(II) sulfate for 50.0 minutes.

Useful Conversions: 1 J = 1 CV 1 A = 1 C/s

¨ 60 s ¸¨ 2.50 C ¸¨ 1 mol e  ¸¨ 63.5 g Cu ¸ ¹ ¹© ¹© © g Cu ! 50.0 min ¹© © 1 min ¹© s ¹© 96,485 C ¹© 2 mol e  ¹ ! 2.47 g Cu ºª º ºª ºª ª

€ Cu2+(aq)

+ 2e-

Cu(s)

€

A galvanic cell is to be constructed using a Fe3+/Fe2+ half cell and a Br2/Br- half-cell. The Br2/Br- half-cell was constructed by electrolyzing 50 mL of 0.5 M KBr using a 2.5 A current for 3 minutes. The Fe3+/Fe2+ half cell was constructed by mixing 25 mL of 2 M FeSO4 and 25 mL of 2 M FeCl3. (MW Br2: 159.8 g/mol) Fe3+ (aq) + eBr2(aq) + 2ea) b) c)

Fe2+(aq) 2Br-(aq)

Eored = +0.771 V Eored = +1.087 V

Assuming that the bromide ions are converted to Br2(aq), crcalculate [Br2] and [Br-] upon electrolysis. Write the cell notation (with the correct phases and concentrations of ions) for the galvanic cell Calculate the Ecell for the galvanic cell.

€ Answers:

[Br2] = 0.046638 M, [Br-] = 0.406722 M b) Fe2+(aq) (1M), Fe3+(aq) (1M)||Br2(aq)(0.046638 M), Br-(aq) (0.406722 M) c) 0.2997243 V
a)

Inorganic Analysis,1970 € Christian, G.D. Analytical Chemistry, 1986 € Day, Underwood, et al. Quantitative Analysis, 1967 € Haenisch, Pierce, et al. Quantitative Analysis, 1958 € Skoog, et al., Fundamentals of Analytical Chemistry, Eighth edition, 2004 € http://academic.pgcc.edu/psc/chm103/103_m anual.pdf
€ Belcher, R. Quantitative

Sign up to vote on this title
UsefulNot useful