Chapter 10

Electrochemistry

Electrochemistry
Is the study of the relationship between electricity and chemical reaction Chemical reactions involved in electrochemistry are :

Reduction Oxidation

REDOX REACTION

One type of reaction cannot occur without the other.

REDOX Reaction
REDUCTION
gain of electron Oxidation no. decrease Reaction at cathode

OXIDATION
loss of electron Oxidation no. increase Reaction at anode Example:

Remember RED CAT

= RED REDuction at CAT CAThode Example:

Mg p Mg2+ + 2eOxidation no. o

Cu2+ + 2e- p Cu
Oxidation no. q

Electrochemical reaction consists of reduction and oxidation. These two reactions are called half-cell reactions The combination of 2 half reactions are called cell reaction

Example
Reduction : Cu2+(aq) + 2e- p Cu(s) Oxidation :

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

Half-cell reaction

Overall cell Cu2+(aq) + Zn(s) p Cu(s) + Zn2+(aq) reaction :

Cells
There are 2 type of cells

Electrochemical Cells
where chemical reaction produces electricity

Electrolytic Cells
Uses electricity to produce chemical reaction

Also called; Galvanic cell or Voltaic cell Chemical Energy Electrical Energy Electrical Energy Chemical Energy

Component and Operation of Galvanic cell

Consists of : 1) Zn metal in an aqueous solution of Zn2+ 2) Cu metal in an aqueous solution of Cu2+ - The 2 metals are connected by a wire - The 2 containers are connected by a salt bridge. - A voltmeter is used to detect voltage generated.

Galvanic cell
Voltmeter

Zn electrode Zn2+ ZnSO4(aq) solution Cu2+

Cu electrode

Salt bridge

CuSO4(aq) solution

What happens at the zinc electrode ?

Zinc is more electropositive than copper. Tendency to release electrons: Zn > Cu.

Zn (s) p Zn2+ (aq) + 2eZinc dissolves. Oxidation occurs at the Zn electrode. Zn2+ ions enter ZnSO4 solution. Zn is the ve electrode since it is a source of electrons p anode.

What happens at the copper electrode ?

The electron from the Zn metal moves out through the wire enter the Cu metal Cu2+ ions from the solution accept electrons.

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

Copper is deposited. Reduction occurs at the Cu electrode. Cu is the +ve electrode p cathode

Reactions Involved:

Anode : Cathode : Overall cell reaction :

Zn (s) p Zn2+ (aq) + 2eCu2+ (aq) + 2e- p Cu (s)

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

Salt bridge
An inverted U tube containing a gel permeated with solution of an inert electrolyte such as KCl, Na2SO4, NH4NO3.

Functions
Salt bridge helps to maintain electrical neutrality Completes the circuit by allowing ions carrying charge to move from one half-cell to the other.

What happened if there is no salt bridge? V Zn

Zn2+

Cu
e e e e e e

ZnSO4(aq)

Cu2+

CuSO4(aq)

As the zinc rod dissolves, the concentration of Zn2+ in the left beaker increase. The reaction stops because the nett increase in positive charge is not neutralized. This excess charge build-up can be reduced by adding a salt bridge

Zn (s) p Zn2+ (aq) + 2eANODE (-)

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

E = +1.10 V

Zn
Zn2+ e e

Cu

ZnSO4(aq)

Cu2+ Salt bridge (KCl)

CuSO4(aq)

How does the cell maintains its electrical neutrality?

Left Cell Zn (s) p Zn2+ (aq) + 2eZn2+ ions enter the solution. Causing an overall excess of tve charge. Cl- ions from salt bridge move into Zn half cell Right Cell Cu2+ (aq) + 2e- p Cu (s) Cu 2+ ions leave the solution. Causing an overall excess of -ve charge. K+ ions from salt bridge move into Cu half cell

Electrical neutrality is maintained

Electrochemical Cells

anode oxidation

cathode reduction

spontaneous redox reaction

half

19.2

Cell notation
Zn (s) + Cu2+ (aq)
Also can be represented as: Salt bridge Phase boundary

Cu (s) + Zn2+ (aq)

Zn (s) | Zn2+ (aq) || Cu2+ (aq) | Cu (s) anode cathode Cell notation

Exercise
For the cell below, write the reaction at anode and cathode and also the overall cell reaction. Cell notation

Zn (s) | Zn2+(aq) || Cr3+ (aq) | Cr (s)

Anode : Cathode :

3 Zn(s)

2e 3Zn2+(aq) + 6e-

X3 X2

6e 2 Cr3+(aq) + 3e-

2Cr(s)

Overall cell 3Zn(s) + 2Cr3+(aq) + reaction:

3Zn2+ (aq) +2Cr(s)

The difference in electrical potential between the anode and cathode is called: cell voltage electromotive force (emf) cell potential measured by a voltmeter

Acts as electrical pressure that pushes electron through the wire.

Electrode Potential
A measure of the ability of a half-cell to attract electrons towards it. half-

Cu2+(aq) + 2e Zn2+(aq) + 2e

Cu(s) Zn(s)

Eored = +0.34 V Eored = -0.76 V

Standard reduction potential

The more positive the half-cells electrode potential, the stronger the attraction for electrons.
Tendency for reduction (cathode)

Standard reduction potential of copper half-cell is more positive compared to zinc. Zinc half-cell becomes anode.

Cu2+(aq) + 2e Zn2+(aq) + 2e

Cu(s) Zn(s)

Eored = +0.34 V Eored = -0.76 V

Cell Potential (Eocell)= Eocatode Eoanode = +0.34 (-0.76) = +1.1 V

Zn2+ (aq) + 2e- p Zn (s) Cu2+ (aq) + 2e- p Cu (s) E0cell = E0cathode - E0anode
= +0.34 (-0.76) = +1.10 V

E0 = -0.76V E0 = +0.34V

or

E0cell = E0red + E0ox

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

Change the sign

Half-cell equation at:

Anode : Cathode :

Zn (s) p Zn2+ (aq) + 2eCu2+ (aq) + 2e- p Cu (s)

Standard Electrode Potentials (Eo)

A measure of the ability of half-cell to attract electrons towards it at 25oC, the pressure is 1 atm (for gases), and the concentration of electrolyte is 1M.

The sign of E0 changes when the reaction is reversed Changing the stoichiometric coefficients of a half-cell reaction does not change the value of E0

For example: Cl2(g) + 2e- p 2Cl-(aq) Cl2(g) + e- p Cl-(aq) Cl-(aq) p Cl2(g) + eE0 = +1.36 V E0 = +1.36 V E0 = -1.36 V

Standard Hydrogen Electrode (SHE)

Made up of a platinum electrode, immersed in an aqueous solution of H+ (1 M) and bubbled with hydrogen gas at 1 atm pressure, and temperature at 25oC

H2 gas at 1 atm Pt electrode

H+ (aq) 1 M

The standard reduction of SHE is 0 V

Standard reduction potential of Zinc half cell is measured by setting up the electrochemical cell as below. E0 = +0.76
Zn
e e e 2+e Zn

+ +

E0 = 0
H2 (g), 25oC,1 atm.

H+(aq),1 M Pt

ZnSO4(aq) 1M

Standard Electrode Potentials

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s) Anode (oxidation): Cathode (reduction): Zn (s) 2e- + 2H+ (aq,1 M) Zn2+ (1 M) + 2eH2 (g,1 atm) Zn2+(aq) + H2 (g,1 atm)

Cell reaction Zn (s) + 2H+ (aq,1 M)

0 0 0 Ecell = EH +/H2 - EZn2+/Zn 0 0.76 V = 0 - EZn2+/Zn 0 EZn 2+/Zn = -0.76 V

Zn2+ + 2e- Zn

E0 = -0.76 V

Standard reduction potential of Copper half cell is measured by setting up the electrochemical cell as below. E0 = 0
H2 (g) 25oC 1 atm.

+V + Cu

Cu2 CuSO4(aq) 1M

H+(aq) 1M

Pt

Pt (s) | H2 (1 atm) | H+ (1 M) || Cu2+ (1 M) | Cu (s) Anode (oxidation): H2 (1 atm) H2 + Cu2+ 2H+ + 2eCu (s) Cu (s) + 2H+ Cathode (reduction): 2e- + Cu2+ (1 M)

0 0 0 Ecell = Ecathode - Eanode 0 0 0 Ecell = ECu 2+/Cu EH +/H 2 0 0.34 = ECu2+ /Cu - 0 0 ECu2+ /Cu = 0.34 V

The direction of half-reaction of SHE depends on the other half-cell connected on it. The cell notation for SHE is either:

 H+(aq) | H2(g) | Pt(s) when it is cathode  Pt(s) | H2(g) | H+ (aq) when it is anode

In either case, E0 of SHE remains 0

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

E0 = -0.76V E0 = +0.34V

E0cell = E0cathode - E0anode

= +0.34 (-0.76) = +1.10 V

or

E0cell = E0red + E0ox

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

Change the sign

Half-cell equation at:

Anode : Cathode :

Zn (s) p Zn2+ (aq) + 2eCu2+ (aq) + 2e- p Cu (s)

At standard-state condition

E0cell = E0cathode - E0anode or E0cell = E0red + E0ox

Exercise
Calculate the standard cell potential of the following electrochemical cell. Co(s) | Co2+(aq) || Ag+(aq) | Ag(s) Ag+(aq) + e- p Ag(aq) E0 = +0.80V E0 = -0.28V E0 = +0.80V E0ox = +0.28V

Answer

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

Ag+(aq) + e- p Ag(aq) Cathode (Red) : Anode (Ox) : Co(s) p Co2+(aq) + 2e-

E0cell = E0cathode - E0anode

= +0.80 (-0.28) = +1.08 V

Refer to the list of Standard Reduction Potential: Oxidation agent Reduction agent Example : Ni2+ (aq) + 2eCu2+ (aq) + 2eAg+ (aq) + eOxidation agent left of the half cell equation right of the half cell equation Ni (s) E0 = -0.25 V Cu (s) E0 = +0.34 V Ag (s) E0 = +0.80 V Reducing agent Increase strength as reducing agent

The more -ve the value of E0 The more +ve the value of E0

the stronger the reducing agent the stronger the oxidizing agent

Exercise
Arrange the 3 elements in order of increasing strength of reducing agents X3+ + 3e- p X Y2+ + 2e- p Y L2+ + 2e- p L E0 = -1.66 V E0 = -2.87 V E0 = +0.85 V

Answer : L < X < Y

Example
Calculate the E0 cell for the reaction :: Mg(p) | Mg2+(ak) || Sn4+(ak),Sn2+(ak) | Pt(p) Given : Mg2+(ak) + 2e Sn4+(ak) + 2e Mg(p) E = -2.38 V

E0cell = Ecathode - Eanode =+0.15- (-2.38) =+2.53V

Eoox = +2.38 V Eo = +0.15 V Ecell = +2.53 V

Sn2+(ak) E = +0.15 V Mg2+(ak) + 2e + 2e Sn2+(ak)

Oxidation Reduction

: Mg(p) : Sn4+(ak)

Mg(p) + Sn4+(ak)

Mg2+(ak) + Sn2+(ak)

E cell = E o red

E o ox

= +2.38 + 0.15 = +2.53 V

Exercise
A cell is set up between a chlorine electrode and a hydrogen electrode
Pt | H2(g, 1 atm) | H+(aq, 1M) || Cl2(g, 1atm) | Cl-(aq, 1M) | Pt

E0cell = +1.36 V (a) Draw a diagram to show the apparatus and chemicals used. (b) Discuss the chemical reactions occurring in the electrochemical cell.

Answer
E0cell =1.36V
H2 (g), 1 atm.
-

+ +

Cl2 (g), 1 atm.

Pt H+(aq), 1M Cl-(aq), 1M

Pt

1. Show the process occur at anode and cathode - Half-cell reaction 2. Overall reaction

Answer
 Reduction (cathode) Cl2 (g) + 2e- p 2Cl- (aq)  Oxidation(anode) H2 (g) p 2H+ (aq) + 2e Eocell =+1.36 V Eocell = Eocathode - E0anode +1.36 = Eocathode 0 E0cathode = +1.36 V So the standard reduction potential for Cl2 is: Eo = +1.36 V E0 = 0

Spontaneous & Non-Spontaneous reactions Non- Redox reaction is spontaneous when Ecell is +ve. - Non spontaneous is when Ecell is ve.

cell

=0

The reaction is at equilibrium

Predict whether the following reactions occur spontaneously or non-spontaneously under standard noncondition. Eo 4+/Sn2+ =+0.15V Sn Zn + Sn4+ Sn2+ + Zn2+ EoZn/Zn2 = - 0.76V. The two half-cells involved are:halfare:+ Anod : Zn Zn2+ + 2e Eoox = +0.76 V Cathode: Sn4+ + 2e Sn2+ Eo = +0.15 V

Zn + Sn4+ Eocell = Eo Sn4+/Sn2+

= +0.15 (-0.76 ) = +0.91 V spontaneous

Zn2+ + Sn2+ Eo Zn/Zn2

+

Eocell= Eored + Eoox = (+0.15) + (0.76) = +0.91 V

Or

Predict : Spontaneous or nonnonspontaneous?

Pb2+(aq) + 2Cl-(aq)

Pb(s) + Cl2(g)

Pb2+(aq) + 2Cl-(aq) Pb2+(aq)

Reduction + 2Cl-(aq)

Pb(s)Cl (g) 2(g) + Cl Pb(s) +

2

Oxidation cathode: Pb2+(aq) + 2e Pb(s) anode: 2Cl-(aq) Cl2(g) + 2e Pb2+(aq) + 2Cl-(aq) Eocell= Eored + Eoox = (-1.36) + (-0.13) = -1.48 V Non-spontaneous No Reaction Eo = -0.13 V Eoox = -1.36

Pb(s) + Cl2(g)

Example : Predict whether the following reactions occur spontaneously : 2Ag(s) + Br2(aq)
0 EAg + /Ag

2Ag+(aq) = +0.8 V

+ 2Br-(aq)
standard reduction potential

Answer : 2Ag(s) Br2(aq)

0 EBr 2 /Br - = +1.07 V

2Ag+(aq) + 2e

2e

ox =

- 0.80 V

2Br -(aq) 2Ag+(aq) + 2Br-(aq)

E = +1.07 V Esel = + 0.27 V

2Ag(s) + Br2(aq)

The reaction is spontaneous

Exercise
A cell consists of silver and tin in a solution of 1 M silver ions and tin (II) ions. Determine the spontaneity of the reaction and calculate the cell voltage of this reaction.

Ag+ (aq) + eSn2+ (aq) + 2e-

Ag (s)

E0 = +0.80 V Sn (s) E0 = -0.14 V

(cathode) (anode)

E0cell = E0cathode - E0anode

= +0.80 (-0.14) = +0.94 V = +ve ( reaction is spontaneous)

E0cell

Nernst equation
Nernst equation can be used to calculate the E for any chosen concentration : Ecell = Eocell RT nF ln [ product ]x [ reactant]y
cell

At 298 K and R = 8.314 J K-1 mol-1 , 1 F = 96500 C Ecell = Eocell 0.0257 n [ product ]x [ reactant]y

2.303 log

Ecell = Eocell 0.0592 n

log

[ product ]x [ reactant]y

[ product ]x [ reactant]y

Ecell = Eocell

0.0592 n

log Q

n = no of e- that are involved Q = reaction quotient

Example 1
Calculate the Ecell for the following cell Zn(s) / Zn2+ (aq, 0.02M) // Cu2+(aq, 0.40 M) / Cu(s)

Answer n(s) + Cu2+(aq) @ Zn2+(aq) + Cu(s)

Eocell = Eored + Eoox = +1.10 V

Eocell = Eocathode Eoanode = +0.34 V - (- 0.76 V) = +1.10 V

= +0.34 V + 0.76 V

E = Eo 0.0592 n

log [ Zn2+] [ Cu2+]

E = +1.10 V 0.0592 log (0.02 ) 2 ( 0.40)

= +1.10 V (-0.0385) = +1.139 V

At equilibrium: ~ No net reaction occur (Q=K) ~ Ecell = 0 Ecell = Eocell 0.0592 n 0 = Eocell 0.0592 n E cell = 0.0592 n

log K

log K

log K

Example 2
Calculate the equilibrium constant (K) for the following reaction. Cu(s) + Answer At equilibrium, E cell = 0 Eocell = Eo cathode Eo anode 2Ag+(ak) Cu2+(ak) + 2Ag(s)

= +0.80 ( +0.34) = +0.46 V

Ecell = Eocell 0.0592 2 0 = 0.46 0.0592 2 0.0592 log K = 0.46 2 log K = 15.54 K = 3.467

log K

log K

x 1015

Electrolysis
Electrolysis is a chemical process that uses electricity for a non-spontaneous redox reaction to occur. Such reactions take place in electrolytic cells.

Electrolytic Cell
 It is made up of 2 electrodes immersed in an electrolyte.  A direct current is passed through the electrolyte from an external source.  Molten salt and aqueous ionic solution are commonly used as electrolytes.

Electrolytic Cell
+ -

Oxidation

Reduction
Electrolyte (M+X-)
X-,OHM+,H+

Anion

Cation

A n o d e

Positive electrode The electrode which is connected to the positive terminal of the battery Oxidation takes place Electrons flow from anode to cathode

C a t h o d e

Negative electrode The electrode which is connected to the negative terminal of the battery Reduction takes place

Electrode as circuit connectors as sites for the precipitation of insoluble products example: Platinum , Graphite (inert electrode) Electrolyte a liquid that conducts electricity due to the presence of +ve and ve ions must be in molten state or in aqueous solution so that the ions can move freely example: KCl(l), HCl(aq), CH3COOH(aq)

Comparison between an electrochemical cell and an electrolytic cell

Electrolytic Cell
+ e+ ee+ e-

Electrochemical Cell

Anode

Cathode

Anode

Cathode

Electrolytic Cell
Cathode = negative Anode = positive

Electrochemical Cell
Cathode = positive Anode = negative

Non-spontaneous redox Spontaneous redox reaction requires energy reaction releases energy to drive it Similarities: Oxidation occurs at anode, reduction occurs at cathode Anions move towards anode, cations move towards cathode. Electrons flow from anode to cathode in an external circuit.

Electrolysis of molten salt

Electrolysis of molten salt requires high temp. Electrolysis of molten NaCl Cation : Na+ Anode : Cl- (l) Anion : ClCl2(g) + 2eNa (s) 2Na (s) Cl2(g) + 2Na(s)

Cathode : Na+ (l) + e2Na+ (l) + 2eOverall :

2Na+ (l) + 2Cl-(l)

Electrolysis of molten NaCl gives sodium metal deposited at cathode and chlorine gas evolved at anode. Electrolysis of molten NaCl is industrially important. The industrial cell is called Downs Cell

Electrolysis of Aqueous Salt

Electrolysis of aqueous salt is more complex because the presence of water. Aqueous salt solutions contains anion, cation and water. Water is an electro-active substance that may be oxidised or reduced in the process depending on the condition of electrolysis. Reduction : 2H2O (l) + 2eOxidation : 2H2O (l) 4H+ (aq) + O2 (g) + 4eE0 = -1.23 V H2 (g) + 2OH- (aq) E0 = -0.83 V

Predicting the products of electrolysis

Factors influencing the products :

1. Reduction/oxidation potential of the species in electrolyte 2. Concentrations of ions 3. Types of electrodes used active or inert

Electrolysis of Aqueous NaCl

NaCl aqueous solution contains Na+ cation, Cl- anion and water molecules On electrolysis,  the cathode attracts Na+ ion and H2O molecules  the anode attracts Cl- ion and H2O molecules The electrolysis of aqueous NaCl depends on the concentration of electrolyte.

Electrolysis of diluted NaCl solution

Cathode
Na+ (aq) + e2H2O (l) + 2eNa (s) H2 (g) + 2OH- (aq) E0 = -2.71 V E0 = -0.83 V

E0 for water molecules is more positive. H2O easier to reduce.

Anode
Cl2 (g) + 2eO2 (g) + 4H+ (aq) + 4e2Cl- (aq) 2H2O (l) E0 = +1.36 V E0 = +1.23 V

In dilute solution, water will be selected for oxidation because of its lower Eo.

Reactions involved
2H2O (l) + 2eCathode: 4H2O (l) + 4eAnode:

H2 (g) + 2OH- (aq) E0 = -0.83 V 2H2 (g) + 4OH- (aq) O2 (g) + 4H+ (aq) + 4eE0 = -1.23 V

2H2O (l)

Cell 6H2O(l) reaction:

O2(g) + 2H2(g) + 4OH-(aq) + 4H+(aq) 4 H2O O2(g) + 2H2(g) E0cell = -2.06 V

2H2O(l)

Electrolysis of Concentrated NaCl solution

Cathode
Na+ (aq) + e2H2O (l) + 2eNa (s) H2 (g) + 2OH- (aq) E0 = -2.71 V E0 = -0.83 V

 E0 for water molecules is more positive  H2O easier to be reduce

Anode
Cl2 (g) + 2eO2 (g) + 4H+ (aq) + 4e2Cl- (aq) 2H2O (l) E0 = +1.36 V E0 = +1.23 V

In concentrated solution, chloride ions will be oxidised because of its high concentration.

Reactions involved
Cathode: 2H2O (l) + 2eAnode:

H2 (g) + 2OH- (aq) E0 = -0.83 V Cl2 (g) + 2eE0 = -1.36 V

2Cl- (aq)

Cell 2H2O(l) + 2Clreaction:

Cl2(g) + H2(g) + 2OH-(aq) E0cell = -2.19 V

Exercise
Predict the electrolysis reaction when Na2SO4 solution is electrolysed using platinum electrodes.

Solution
Na2SO4 aqueous solution contains Na+ ion, SO42- ion and water molecules On electrolysis,  the cathode attracts Na+ ion and H2O molecules  the anode attracts SO42- ion and H2O molecules

Cathode
Na+ (aq) + e2H2O (l) + 2eNa (s) H2 (g) + 2OH- (aq) E0 = -2.71 V E0 = -0.83 V

 E0 for water molecules is more positive H2O easier to reduce

Anode
S2O82- (aq) + 2eO2 (g) + 4H+ (aq) + 4e2SO42- (aq) 2H2O (l) E0 = +2.01 V E0 = +1.23 V

 E0 for water molecules is less positive H2O easier to oxidise

Equation
Cathode: 2H2O (l) + 2eAnode:

H2 (g) + 2OH- (aq) E0 = -0.83 V O2 (g) + 4H+ (aq) + 4eO2(g) + 2H2(g) E0 = -1.23 V

2H2O (l)

Cell 2H2O(l) Reaction:

E0cell = -2.06 V

Cathode = H2 gas is produced and solution become basic at cathode because OH- ions are formed Anode = O2 gas is produced and solution become acidic at anode because H+ ions are formed

Faradays Law of Electrolysis

Describes the relationship between the amount of electricity passed through an electrolytic cell and the amount of substances produced at electrode.

Faradays First Law

States that the quantity of substance formed at an electrode is directly proportional to the quantity of electric charge supplied.

Faradays 1st Law

Q = electric charge in coulombs (C) m = mass of substance discharged

The End

Q = It
Q = electric charge in coulombs (C) I = current in amperes (A) t = time in second (s)

Faraday constant (F)

is the charge on 1 mole of electron

1 F = 96 500 C

Example
An aqueous solution of CuSO4 is electrolysed using a current of 0.150 A for 5 hours. Calculate the mass of copper deposited at the cathode.

Answer
Electric charge, Q = Current (I) x time (t) Q = (0.150 A) x ( 5 x 60 x 60 )s Q = 2700 C 1 mole of electron No. of e1F 96 500 C 2700 96 500 = 0.028 mol

passed through =

Cu2+ (aq) + 2e- p Cu (s) From equation: 2 mol electrons p 1 mol Cu 0.028 mol electrons p 0.014 mol Cu Mr for Cu = 63.5 Mass of Copper deposited = 0.014 x 63.5 = 0.889 g