(b) Electrode processes Candidates should be able to: show awareness that electrode processes represent oxidations and

reductions;

Electrode processes involve oxidations and reductions e.g. during electrolysis, oxidation takes place at the anode and reduction takes place at the cathode. Many industrial processes involve electrolysis e.g. reactive metals such as sodium and aluminium are extracted electrolytically, the metal ions gaining electrons at the cathodes of the electrolytic cells. (d), (e), (f) Recall, use and describe redox systems Candidates should be able to: (c) recall and use the redox systems specified below, including the appropriate colour change and ion/electron half-equations. Cu (aq) " Cu(s); #n (aq) " #n(s); $ (aq) " $ (g) %t; &e (aq), &e (aq) " + ! %t; (n)* (aq), (n (aq) " %t; , (g) " , (aq) (, - Cl , .r , / ); (d)use redox systems in addition to those in (d), for which all rele0ant information is supplied; (f) describe simple electrochemical cells in0ol0ing; (i) metal/metal ion electrodes, and (ii) electrodes based on different oxidation states of the same element. Consider the changes that occur when small pieces of inc metal are dropped into a!ueous copper("") sulfate. "f the mixture is stirred, gradually the blue colour of the solution begins to fade and a reddish deposit is seen on the pieces of inc and at the bottom of the beaker. # redox reaction has taken place. $n(s)
%& ! ! ! '! !

$n (a!) & %e Cu(s) $n (a!) & Cu(s)

%&

%&

Cu (a!) & %e 'verall reaction $n(s) & Cu (a!)

%&

(he a!ueous inc ion is colourless and the blue colour of the a!ueous copper("") ion disappears as the ions are reduced to the metal. "f the two halves of the reaction are kept separate, chemical energy is changed into electrical energy producing a voltage.

)%
flow of electrons high resistance voltmeter

salt bridge

copper foil

inc foil

a!ueous copper("") sulfate

a!ueous inc sulfate

(he salt bridge is needed to allow ions to flow from one solution to the other while the two solutions themselves are kept separate. Electrons are released at the inc electrode and will flow through the external wire to the copper electrode where copper ions accept electrons. (he emf of this cell is of the order of ).) volts. *y convention the cell is represented by a cell diagram but note that a cell diagram is not the same as a diagram of a cell which is the diagram above. (his cell diagram representing the above system is substance being oxidised $n(s) $n (a!)
+ve electrode
%&

substance being reduced Cu

%&

(a!) Cu(s)

&ve electrode

(his cell diagram represents $n(s) & Cu (a!)

%&

Cu(s) & $n (a!)

%&

), (g) The standard hydrogen electrode Candidates should be able to: explain and use the term standard electrode potential especially (i) (ii) (iii) the use of the standard hydrogen electrode in determining standard electrode potential; to calculate standard potentials of cells formed by combining different electrodes and; to predict the feasibility of specified reactions.

#s can be seen above a combination of two electrodes produces an emf. *y convention all such emfs are measured with respect to the standard hydrogen electrode.

hydrogen gas at ) atmosphere

platinum electrode- platinum foil covered with platinum black hydrochloric acid ( ).. mol dm ) (emperature %/01
,

*y convention the electrode process at the platinum electrode %2 (a!) & e standard and other potentials are measured with respect to it. Electrode potential
%&

&

2%(g) is taken as the

*y definition, the electrode potential of a half cell, say $n $n (a!), is the emf of a cell represented by the cell diagram 3t 2%(g) %2 (a!)
&

$n (a!) $n
,

%&

4hen conditions are standard i.e. %/01 and unit concentrations ().. mol dm ) the emf is called the Standard Electrode Potential (E ) (he sign of the electrode potential is the sign of the right hand electrode in the cell diagram. (he emf of a cell is measured using a high resistance voltmeter which takes no current itself. (he emf is the potential difference across the cell when it takes no current. (he emf is a measure of the maximum amount of energy which can be given by the cell.

)5 Some Standard Electrode Potentials 6eaction 9i (a!) & e

& & %&

1 78 ,..5 %./% %.:; %.:) %.,0 ).;;

+

9i(s) 1 (a!) & e 1(s)

&

Ca (a!) & %e Ca(s) <a (a!) & e <a(s) Mg (a!) & %e Mg(s) #l (a!) & ,e #l(s) %2%'(l) & %e 2%(g) & %'2 (a!) $n (a!) & %e $n(s) Cr (a!) & ,e Cr(s) =e (a!) & %e =e(s) <i (a!) & %e <i(s) >n (a!) & %e >n(s) 3b (a!) & %e 3b(s) =e (a!) & ,e =e(s) %2 (a!) & %e 2%(g) >n (a!) & %e >n (a!) Cu (a!) & e Cu (a!) Cu (a!) & %e Cu(s) Cu (a!) & e Cu(s) (a!) =e (a!) & e =e (a!)
,& %& %& 2g% (a!) & %& & %& + %& & 5& %& & ,& %& %& %& %& ,& %& ,& %&

..0, ..:; ..:5 ..5) ..%, ..)5 ..), ...5 .... &..)? &..); &..,5 &..?% &..?5 &..:: &..0. &..0. &..0? &../. &../; &)..: &).%, &).,, &).,; &).55 &).?) &).:0 &).0% &%.0:

"%(s) & %e %"

& %e %2g(l)

#g (a!) & e #g(s)

%& %&

2g (a!) & %e 2g(l) %2g (a!) & %e 2g% (a!) <', (a!) & 52 (a!) & ,e <'(g) & %2%'(l) *r%(l) & %e %*r (a!) '%(g) & 52 (a!) & 5e %2%'(l) Cr%': (a!) & )52 (a!) & ;e %Cr (a!) & :2%'(l) Cl%(g) & %e %Cl (a!) Ce (a!) & e Ce (a!) Mn'5 (a!) & 02 (a!) & ?e Mn (a!) & 52%'(l) 2%'%(a!) & %2 (a!) & %e %2%'(l) Co (a!) & e Co (a!) =%(g) & %e %= (a!)
,& %& & & %& 5& ,& % & ,& & + + &

)? <ote that some standard electrode potentials above are given for cells containing ions in different oxidation states e.g. =e (a!) & e
,& %&

=e (a!).

3hysically these cells use an inert platinum electrode to allow the passage of electrons. (he cell diagram for determining the standard electrode potential is written 3t 2%(g) %2 (a!) and standard conditions apply. The uses of standard electrode potentials (o calculate the emf of a cell made by combining different electrodes. Consider the following practical setup.
&

=e (a!),=e (a!) 3t

,&

%&

Cu #g Cu>'5(a!) #g<',(a!)

=rom the table above Cu (a!) & %e Cu(s) #g (a!) & e #g(s)
& %&

1 1

@ & ..,5 8 @ & ..0. 8

Careful observation shows that silver is deposited on the silver electrode and the copper electrode starts to dissolve. (he reaction with the more positive 1 direction because reduction is more favourable. (he overall reactions are Cu(s) Cu (a!) & %e %#g (a!) & %e %#g(s)
& %&

will proceed in the forward

1 1

@ ..,5 8 (change in sign as e!uation has been reversed) @ & ..0. 8 (value of 1 does not change although the number of moles is doubled)

'verall we can add the two e!uations to obtain the overall redox e!uation and also add the 1 values Cu(s) & %#g (a!)
&

Cu (a!) & %#g(s) 1

%&

@ & ..5; 8

(his value agrees with the experimentally determined value under standard conditions and a positive value for 1 means that the reaction is feasible.

); !ther examples of redox cell chemistry (i)

=e 3t
=e>'5(a!)

%/0 1
Mn'5 (a!) ).. mol dm , 2&(a!) ).. mol dm , Mn%&(a!) ).. mol dm ,

).. mol dm ,

=rom the table above 1 78 =e (a!) & e =e (a!) Mn'5 (a!) & 02 (a!) & ?e Mn (a!) & 52%'(l)
A & %& ,& %&

& ..:: & ).?)

Mn'5 has the more positive 1 value so this reaction proceeds in the forward direction and acidified potassium manganate(8"") oxidises iron(""). 6earranging ?=e (a!) ?=e (a!) & ?e
%& ,&

1 @ ..:: 8 (note change in sign)

%&

Mn'5 (a!) & 02 (a!) & ?e Mn (a!) & 52%'(l) 'verall Mn'5 (a!) & 02 (a!) & ?=e (a!)
& %& %&

&

1 @ & ).?)8
,&

Mn (a!) & 52%'(l) & ? =e (a!) 1 @ & ..:5 8

(he =e electrode is negatively charged and the 3t electrode is positively charged meaning that electrons would flow from the iron to the platinum if the cell were short circuited.

): (ii) >tate what the spontaneous reaction would be in the following set up.

3t 3t =e%&7=e,&(a!) each
).. mol dm+, *r%(l)

1*r(a!)
).. mol dm
+,

=rom the table of standard redox potentials %=e (a!) & %e %=e (a!) *r%(l) & %e
%& ,& %&

& ..:: 8 & )..: 8 1 @ ..:: 8 (note change in sign) 1 @ &)..: 8

%*r (a!)
,&

%=e (a!) %=e (a!) & %e *r%(l) & %e %*r (a!)

(he spontaneous reaction is *r%(l) & %=e (a!)

%&

%*r (a!)&

%=e (a!)

,&

1 @ &..,.8