Analisis

Elektrokimia
Oleh
Moh. Hayat

Elektrokimia
Merupakan cabang Ilmu Kimia yang membahas
mengenai sifat kelistrikan dan pengaruhnya
terhadap zat-zat kimia.
Sebagian besar mempelajari perubahan kimiawi
yang disebabkan oleh adanya arus listrik dan
timbulnya kelistrikan karena adanya reaksi kimia.
Kajian elektrokimia meliputi banyak fenomena
(mis: elektroporesis, korosi); peralatan (display
elektrokromik, sensor elektroanalitik, baterai, fuel
cell); dan teknologi (elektroplating, produksi
aluminium)

Elektroanalitik
Kumpulan metode analitik kuantitatif yang
didasarkan pada sifat-sifat listrik larutan analit
ketika ditempatkan dalam sel elektrokimia.
Teknik elektroanalitik mampu memberikan
pengukuran dengan limit deteksi yang rendah
dan mampu memberikan banyak informasi,
stoikhiometri dan kecepatan transfer muatan,
kecepatan transfer massa, kecepatan dan
konstanta kesetimbangan reaksi kimia.
Pemanfaatan elektrokimia untuk analisis

Pengantar Elektrokimia
Elektrokimia didasarkan pada reaksi redoks.
Sifat khas dari reaksi redoks adalah adanya
transfer elektron dan dapat ditempatkan dalam
suatu sel elektrokimia.
Dalam sel tersebut, oksidator dan reduktor
ditempatkan dalam sel terpisah.
Kedua sel tersebut dihubungkan dengan
jembatan garam yang mengisolasi pereaksi
namun memungkinkan transfer muatan listrik.

Sel Elektrokimia
Suatu sel elektrokimia terdiri dari dua
konduktor yang disebut elektroda, yang masingmasing direndam dalam larutan elektrolit.
Dalam kebanyakan kasus, larutan yang
digunakan untuk masing-masing elektroda
merupakan elektrolit yang berbeda, dan harus
dipisahkan untuk menghindari reaksi.

Common Components
Electrodes:
conduct electricity between cell and
surroundings
Electrolyte:
mixture of ions involved in reaction or
carrying charge
Salt bridge:
completes circuit (provides charge balance)

 Connected this way the reaction starts

Stops immediately because charge builds up.

H+
MnO4-

Fe+2

Salt
Bridge
allows
current
to flow
H+
MnO4-

Fe+2

 Electricity

travels in a complete circuit

H+
MnO4-

e-

Fe+2

Instead

of a salt bridge

H+
MnO4-

Porous
Disk

Fe+2

Electrodes
Anode:
Oxidation occurs at the anode
Cathode:
Reduction occurs at the cathode

e-

ee-

e-

Anode
eReducing
Agent

Cathode
eOxidizing
Agent

Types of cells
Voltaic (galvanic) cells:
Energy released from spontaneous redox reaction
can be transformed into electrical energy.
Electrolytic cells:
Electrical energy is used to drive a
nonspontaneous redox reaction source to drive a
nonspontaneous reaction

Fundamentals of Electrochemistry
1.) Electrical Measurements of Chemical Processes

Redox Reaction involves transfer of electrons from one species to another.

-

Can monitor redox reaction when electrons flow through an electric current
-

Chemicals are separated

Electric current is proportional to rate of reaction

Cell voltage is proportional to free-energy change

Batteries produce a direct current by converting chemical energy to electrical

energy.
-

Common applications run the gamut from cars to ipods to laptops

Fundamentals of Electrochemistry
Basic Concepts
1.) A Redox titration is an analytical technique based on the transfer of
electrons between analyte and titrant

Reduction-oxidation reaction

A substance is reduced when it gains electrons from another substance

-

gain of e- net decrease in charge of species

Oxidizing agent (oxidant)

A substance is oxidized when it loses electrons to another substance

-

loss of e- net increase in charge of species

Reducing agent (reductant)

(Reduction)
(Oxidation)

Oxidizing
Agent

Reducing
Agent

Fundamentals of Electrochemistry
Basic Concepts
2.) The first two reactions are known as 1/2 cell reactions

3.)

Include electrons in their equation

The net reaction is known as the total cell reaction

No free electrons in its equation

cell reactions:
Net Reaction:
4.) In order for a redox reaction to occur, both reduction of one compound
and oxidation of another must take place simultaneously

Total number of electrons is constant

Fundamentals of Electrochemistry
Basic Concepts
5.) Electric Charge (q)

Measured in coulombs (C)

Charge of a single electron is 1.602x10-19C

Faraday constant (F) 9.649x104C is the charge of a mole of

electrons
Relation between
charge and moles:

q nF
Coulombs

moles

Coulombs
mol e

6.) Electric current

Quantity of charge flowing each second

through a circuit
Ampere: unit of current (C/sec)

Fundamentals of Electrochemistry
Basic Concepts
7.) Electric Potential (E)

Measured in volts (V)

Work (energy) needed when moving an electric
charge from one point to another
-

Relation between
free energy, work
and voltage:

Measure of force pushing on electrons

G work E q
Joules

Volts

Higher potential difference requires

more work to lift water (electrons) to
higher trough

Coulombs

Higher potential
difference

Fundamentals of Electrochemistry
Basic Concepts
7.) Electric Potential (E)

Combining definition of electrical charge and potential

G work E q
Relation between free energy
difference and electric potential
difference:

q nF

G nFE

Describes the voltage that can be generated by a chemical reaction

Fundamentals of Electrochemistry
Basic Concepts
8.) Ohms Law

Current (I) is directly proportional to the potential difference (voltage)

across a circuit and inversely proportional to the resistance (R)
-

Ohms (W) - units of resistance

E
I
R
9.) Power (P)

Work done per unit time

-

Units: joules per second J/sec or watts (W)

q
P E EI
t

Galvanic Cells
1.) Galvanic or Voltaic cell

Spontaneous chemical reaction to generate electricity

-

One reagent oxidized the other reduced

two reagents cannot be in contact

Electrons flow from reducing agent to oxidizing agent

-

Flow through external circuit to go from one reagent to the other

Reduction:
Oxidation:
Net Reaction:

AgCl(s) is reduced to Ag(s)

2+
Electrons
Cd(s) is oxidized
travel
from
to Cd
Cd
Ag deposited
on
electrode
and
Cl2+
Cdgoesgoes
solution
electrode
tointo
Ag
electrode
into
solution

Galvanic Cells
1.) Galvanic or Voltaic cell

Example: Calculate the voltage for the following chemical reaction

G = -150kJ/mol of Cd

n number of moles of electrons

Solution:

G nFE E

G
nF

150 10 3 J
E
0.777 J 0.777 V
C
C

( 2 mol ) 9.649 10 4

mol

Galvanic Cells
2.) Cell Potentials vs. G

Reaction is spontaneous if it does not require external energy

Galvanic Cells
2.) Cell Potentials vs. G

Reaction is spontaneous if it does not require external energy

Potential of overall cell = measure of the tendency of this reaction to proceed to

equilibrium

Larger the potential, the further the reaction is from equilibrium

and the greater the driving force that exists

Similar in concept to balls

sitting at different heights
along a hill

Galvanic Cells
3.) Electrodes

Anode: electrode where

oxidation takes place

Cathode: electrode
where reduction takes
place

Galvanic Cells
4.) Salt Bridge

Connects & separates two half-cell reactions

Prevents charge build-up and allows counter-ion migration

Salt Bridge
Contains electrolytes not
involved in redox reaction.

TwoCd
half-cell
reactions
2+) moves
K+ (and
to cathode with
e through salt bridge (counter
balances charge build-up
NO3- moves to anode (counter
balances +charge build-up)
Completes circuit

Galvanic Cells
5.) Short-Hand Notation

Representation of Cells: by convention start with anode on left

Phase boundary
Electrode/solution interface
anode

Zn|ZnSO4(aZN2+ = 0.0100)||CuSO4(aCu2+ = 0.0100)|Cu

Solution in contact with

anode & its concentration

2 liquid junctions
due to salt bridge

cathode

Solution in contact with

cathode & its concentration

Batteries are Galvanic Cells

Car batteries are lead storage batteries.
Pb +PbO2 +H2SO4 PbSO4(s) +H2O

Batteries are Galvanic Cells

Dry Cell
Zn + NH4+ +MnO2
Zn+2 + NH3 + H2O + Mn2O3

Batteries are Galvanic Cells

Alkaline
Zn +MnO2 ZnO+ Mn2O3 (in base)

Batteries are Galvanic Cells

NiCad
NiO2 + Cd + 2H2O Cd(OH)2 +Ni(OH)2

Corrosion
Rusting - spontaneous oxidation.
Most structural metals have reduction potentials
that are less positive than O2 .
Fe Fe+2 +2eE= 0.44 V
O2 + 2H2O + 4e- 4OH- E= 0.40 V
Fe+2 + O2 + H2O Fe2O3 + H+
Reactions happens in two places.

Salt speeds up process by increasing

conductivity
Water
Fe2+

Iron DissolvesFe Fe+2

Rust

eO2 + 2H2O +4e- 4OH-

Fe2+ + O2 + 2H2O Fe2O3 + 8 H+

Preventing Corrosion
Coating to keep out air and water.
Galvanizing - Putting on a zinc coat
Has a lower reduction potential, so it is more
easily oxidized.
Alloying with metals that form oxide coats.
Cathodic Protection - Attaching large pieces of
an active metal like magnesium that get oxidized
instead.

Electrolysis
Use Faradays Laws to evaluate the number of moles of
a substance oxidised or reduced by passage of charge
(current over a given period of time = I.t) through an electrode

Faraday:

Q (charge) = nF

N=number of moles of electrons

F=constant of 96500 Coulomb/mole

Example (try it): What current is needed to deposit 0.500g of

chromium from a solution containing Cr3+ over a one hour
period (MW for Cr=52)? (Ans=0.77A)

Electrolysis
Running a galvanic cell backwards.
Put a voltage bigger than the potential and
reverse the direction of the redox reaction.
Used for electroplating.

1.10
e-

e-

Zn
1.0 M
Zn+2
Anode

1.0 M
Cu+2
Cathode

Cu

e-

e-

A battery
>1.10V

Zn
1.0 M
Zn+2
Cathode

1.0 M
Cu+2
Anode

Cu

Calculating plating

Have to count charge.

Measure current I (in amperes)
1 amp = 1 coulomb of charge per second
q=Ixt
q/nF = moles of metal
Mass of plated metal
How long must 5.00 amp current be applied to
produce 15.5 g of Ag from Ag+

Calculating plating
1. Current x time = charge
2. Charge Faraday = mole of e3. Mol of e- to mole of element or compound
4. Mole to grams of compound
Or the reverse if you want time to plate

 Calculate the mass of copper which can be

deposited by the passage of 12.0 A for 25.0 min
through a solution of copper(II) sulfate.
How long would it take to plate 5.00 g Fe from
an aqueous solution of Fe(NO3)3 at a current of
2.00 A?

Other uses
Electrolysis of water.
Separating mixtures of ions.
More positive reduction potential means the
reaction proceeds forward.
We want the reverse.
Most negative reduction potential is easiest to
plate out of solution.