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45 STANDARD ELECTRODE POTENTIALS & THE FEASIBILITY OF REACTIONS

45 STANDARD ELECTRODE POTENTIALS & THE FEASIBILITY OF REACTIONS

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Standard Electrode Potentials &The Feasibility of Reactions
C
 hem
 F
 actsheet
January 2003Number 45
1
To succeed with this topic you need to:
ensure you are
fully
able to write equations for cells and work of E
 ê
cell values (covered in Factsheets No.37 & 41).After working through this Factsheet you will:
understand the concepts of ‘feasibility’ of a chemical reaction and‘spontaneous change’;
be able to use E
 ê
data to decide if a chemical reaction is ‘feasible’ or not;
have met the concept of the ‘anti-clockwise rule’ as one way of assessing if a reaction is ‘feasible’;
be able to write balanced chemical equations from half equations usingthe ‘electron balance method;
have met the concept of ‘disproportionation’;
understand how ‘non-standard’ conditions affect the ‘feasibility’ of areaction.
Introduction
We need to pick out some
key points
from earlier work before we start:1.
REDOX
means reduction and oxidation2.
OXIDATION NUMBERS
define whether reduction or oxidationis taking place3.
HALF EQUATIONS
are equilibria and relate oxidised and reducedforms4.
SEP (E
 ê ê ê ê ê
) VALUES (+/-)
show the tendency for oxidation orreduction for a particular half equation5.
THE TABLE OF E
 ê ê ê ê ê
VALUES
below shows the
trend
in oxidising/ reducing power for particular half equations6.
COMBINING HALF EQUATIONS
based on reduction andoxidation using E
 ê
values (+/-) gives the BALANCED CHEMICALEQUATION 
‘Feasibility’
- will these two substances react or not?
E
 ê ê ê ê ê
Values and Feasibility
The best example you can use to help you look at these key questions isthe cell made by combining zinc and copper.
The Data
(a)Zn
2+
+ 2e
¾ 
ZnE
 ê
=
0.76 VCu
2+
+ 2e
¾ 
CuE
 ê
= +0.34 V
Using the data
(b)Zn/Zn
2+
is
above
Cu/Cu
2+
in the table i.e. zinc will be the
cathode
i.e.the electron provider so needs to be written the other way roundZn
Zn
2+
+ 2ei.e.
oxidation
O.N. 0 +2(Zn is the
reducing agent
because it is
oxidised
)Copper is the
anode
i.e. the electron acceptor so stays in the sameorder as in the tableCu
2+
+ 2e
Cui.e.
reduction
+2 0(Cu is the
oxidising agent
because it is
reduced
)
Writing the overall equation (the cell reaction)
(c)Zn
Zn
2+
+ 2eCu
2+
+ 2e
CuZn + Cu
2+
 
Zn
2+
+ CuNB. there are 2e
on each side - so on addition they are ‘cancelled out’ anddo not appear in the final equation.Let us look at this cell and E
 ê
values again if you were asked the question:
Q. Will zinc react when put into copper sulphate solution?
i.e. What is the
feasibility
of a reaction between Zn(s) and Cu
2+
(aq)?Before you go any further– can
you
answer the question: will Zn(s) reactwith Cu
2+
(aq)?Not sure? Go back again – there is no other way. Sorry!You must keep these ideas at the forefront of your thinking as you work through this Factsheet because all we are doing is putting them together ina slightly different way to answer these key questions:
1.
Will
this
substance react with
that
substance?
2.I
they
do
react what is the final balanced chemical equation?
3.
If they
do not
react – why not?
4.
What could be done to
make
them react?
Table of E
 
valuesHalf EquationE
 
 /V
Mg
2+
+ 2e
 
Mg-2.37Al
3+
+ 3e
 
Al-1.66Zn
2+
+ 2e
 
Zn-0.76Fe
2+
+ 2e
 
Fe-0.44V
2+
+ 2e
 
V-0.26Ni
2+
+ 2e
 
Ni-0.252H
+
+ 2e
 
H
2
0.00Cu
2+
+ 2e
 
Cu+0.34I
2
+ 2e
 
2I
+0.54Fe
2+
+ e
 
Fe
2+
+0.77Ag
+
+ e
 
Ag+0.80Cl
2
+ 2e
 
2Cl
+1.36
 
Chem Factsheet
2
Standard Electrode Potentials & The Feasibility of Reactions
The Anti-Clockwise Rule
Study the following way of showing what has been talked about with theZn/Zn
2+
and Cu/Cu
2+
example.0-0.76+0.34E
 ê
v
+3+2+10-1Cu
2+
+ 2e
¾ 
CuZn
2+
+ 2e
¾ 
Zn
reductionoxidation
i.e. bottom line left (Cu
2+
) reacts with top line right (Zn)These are the key points that you need to note:1.the anti-clockwise rule is just another way of presenting the answerto the questions ‘Will Zn(s) react with Cu
2+
(aq)?’2.the axes can be easily remembered:E
 ê
00++
Write it on your examination paper once given the instruction to ‘start’to help you remember it.3.It's called the Anti-clockwise rule because
if 
the ‘graph’ is presentedlike this (E
 ê
 /-/+ and ONs +/-) then:
bottom left
reacts with
top right
If the graph is written on your paper according to these guidelinesyou can use the data in a question on the paper(i.e. E
 ê
data are given –
over
+,
and
ions on left, metal on right (likeZn
2+
+ 2e
 
¾ 
 
Zn)You can then say
‘bottom left
with
top right
’ will work.
Exam Hint 
:- To test your understanding of this difficult concept the examination question will often give you the data in the following way: (1)
 ê
data with the (+) values 
over 
the ( 
− 
 ) values (2)ions on 
right,
 
not 
the left.The Zn/Zn 
2+ 
and Cu/Cu 
2+ 
example would look like this: Cu 
¾ 
Cu 
2+ 
+ 2e 
− 
ê 
 = +0.34 V Zn 
¾ 
Zn 
2+ 
+ 2e 
− 
ê 
= -0.76 V Find a blank part of the paper and put it in a format you can use to answer the question and re-write.(a)ions (oxidised from on the 
left 
 ) (b)put
ê 
(-) 
over 
ê 
(+) 
Using Electrons to Balance Equations
We combine the half equations to give the chemical equation – we use theelectrons to
balance
the equation.These two examples show the principle involved:
Example 1
Will manganese react with tin (II) solutions?Mn
2+
(aq) + 2e
 
¾ 
Mn(s)E
 ê
= -1.19 VSn
2+
(aq) + 2e
 
¾ 
Sn(s)E
 ê
= -0.14 V(Method arranged like this i.e. electrons on the left and more negativeE
 ê
over the less negative half cell we can say ‘yes’ – top right, Mn(s),with bottom left, Sn
2+
(aq))Mn(s)
Mn
2+
(aq) + 2e
(reversed)Sn
2+
(aq) + 2e
 
Sn(s)Mn(s) + Sn
2+
(aq)
Mn
2+
(aq) + Sn(s) (add electrons cancel out)
Example 2
Will Cu(s) react with Ag
+
(aq)?Cu
2+
(aq) + 2e
 
¾ 
Cu(s)E
 ê
= +0.34 VAg
+
(aq) + e
¾ 
Ag(s)E
 ê
= +0.80 VThe answer is
yes
. (Can you explain why? Remind yourself of themethod shown in Example 1.)Cu(s)
Cu
2+
(aq) + 2e
(reversed)Ag
+
(aq) + 2e
 
2Ag(s) (doubled to get 2e
as for copper equation)Cu(s) + 2Ag
+
(aq)
Cu
2+
(aq) + 2Ag(s) (add electrons cancelled)
Disproportionation
The use of E
 ê
values explains this term.
Disproportionation
is when the same species is simultaneouslyoxidised and reducedThe best example to remember is
copper
:Cu
2+
(aq) + e
 
¾ 
Cu
+
(aq)E
 ê
= +0.15 VCu
+
(aq) + e
 
¾ 
Cu(s)E
 ê
= +0.53 VUsing the method,Cu
+
 
Cu
2+
+ e
(reversed)Cu
+
+ e
 
Cu2Cu
+
 
Cu
2+
+ Cu(add – cancel electrons)The Cu
+
has been oxidised to Cu
2+
and reduced to Cu:2Cu
+
 
Cu
2+
+ CuO.N. +1 +2 0oxidationreduction

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